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Sample records for pseudo-first-order rate constant

  1. 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.

  2. 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):

  3. 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.

  4. 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.

  5. Type-I pseudo-first-order phase transition induced electrocaloric effect in lead-free Bi0.5Na0.5TiO3-0.06BaTiO3 ceramics

    Science.gov (United States)

    Li, Feng; Chen, Guorui; Liu, Xing; Zhai, Jiwei; Shen, Bo; Li, Shandong; Li, Peng; Yang, Ke; Zeng, Huarong; Yan, Haixue

    2017-05-01

    In this study, the electrocaloric effect (ECE) of Bi0.5Na0.5TiO3-0.06BaTiO3 (BNT-0.06BT) ceramic has been directly measured using a home-made adiabatic calorimeter. The maximum adiabatic temperature change (ΔT) approaches 0.86 K under an electric field of 5 kV/mm at 110 °C, which provides experimental evidence for optimizing the ECE near the type-I pseudo-first-order phase transition (PFOPT). Most importantly, a considerable ΔT value can be maintained over a wide temperature range well above the temperature of the PFOPT under a high electric field. In addition, ΔT is closely related to the structural transition and electric field strength. This work provides a guideline to investigate the high ECE in BNT-based ferroelectric ceramics for applications in cooling technologies.

  6. 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.

  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. Direct measurements of the rate constants of the reactions NCN + NO and NCN + NO2 behind shock waves.

    Science.gov (United States)

    Dammeier, J; Friedrichs, G

    2011-12-22

    The high-temperature rate constants of the reactions NCN + NO and NCN + NO(2) have been directly measured behind shock waves under pseudo-first-order conditions. NCN has been generated by the pyrolysis of cyanogen azide (NCN(3)) and quantitatively detected by sensitive difference amplification laser absorption spectroscopy at a wavelength of 329.1302 nm. The NCN(3) decomposition initially yields electronically excited (1)NCN radicals, which are subsequently transformed to the triplet ground state by collision-induced intersystem crossing (CIISC). CIISC efficiencies were found to increase in the order of Ar < NO(2) < NO as the collision gases. The rate constants of the NCN + NO/NO(2) reactions can be expressed as k(NCN+NO)/(cm(3) mol(-1)s(-1)) = 1.9 × 10(12) exp[-26.3 (kJ/mol)/RT] (±7%,ΔE(a) = ± 1.6 kJ/mol, 764 K < T < 1944 K) and k(NCN+NO(2))/(cm(3) mol(-1)s(-1)) = 4.7 × 10(12) exp[-38.0(kJ/mol)/RT] (±19%,ΔE(a) = ± 3.8 kJ/mol, 704 K < T < 1659 K). In striking contrast to reported low-temperature measurements, which are dominated by recombination processes, both reaction rates show a positive temperature dependence and are independent of the total density (1.7 × 10(-6) mol/cm(3) < ρ < 7.6 × 10(-6) mol/cm(3)). For both reactions, the minima of the total rate constants occur at temperatures below 700 K, showing that, at combustion-relevant temperatures, the overall reactions are dominated by direct or indirect abstraction pathways according to NCN + NO → CN + N(2)O and NCN + NO(2) → NCNO + NO.

  9. Rate constants, timescales, and free energy barriers

    Science.gov (United States)

    Salamon, Peter; Wales, David; Segall, Anca; Lai, Yi-An; Schön, J. Christian; Hoffmann, Karl Heinz; Andresen, Bjarne

    2016-01-01

    The traditional connection between rate constants and free energy landscapes is extended to define effective free energy landscapes relevant on any chosen timescale. Although the Eyring-Polanyi transition state theory specifies a fixed timescale of τ=h/kBT}, we introduce instead the timescale of interest for the system in question, e.g. the observation time. The utility of drawing such landscapes using a variety of timescales is illustrated by the example of Holliday junction resolution. The resulting free energy landscapes are easier to interpret, clearly reveal observation time dependent effects like coalescence of short-lived states, and reveal features of interest for the specific system more clearly.

  10. Determination of Rate Constants for Ouabain Inhibition of Adenosine Triphosphatase: An Undergraduate Biological Chemistry Laboratory Experiment

    Science.gov (United States)

    Sall, Eri; And Others

    1978-01-01

    Describes an undergraduate biological chemistry laboratory experiment which provides students with an example of pseudo-first-order kinetics with the cardiac glycoside inhibition of mammalism sodium and potassium transport. (SL)

  11. The rate constant of the reaction NCN + H2 and its role in NCN and NO modeling in low pressure CH4/O2/N2-flames.

    Science.gov (United States)

    Faßheber, Nancy; Lamoureux, Nathalie; Friedrichs, Gernot

    2015-06-28

    Bimolecular reactions of the NCN radical play a key role in modeling prompt-NO formation in hydrocarbon flames. The rate constant of the so-far neglected reaction NCN + H2 has been experimentally determined behind shock waves under pseudo-first order conditions with H2 as the excess component. NCN3 thermal decomposition has been used as a quantitative high temperature source of NCN radicals, which have been sensitively detected by difference UV laser absorption spectroscopy at [small nu, Greek, tilde] = 30383.11 cm(-1). The experiments were performed at two different total densities of ρ≈ 4.1 × 10(-6) mol cm(-3) and ρ≈ 7.4 × 10(-6) mol cm(-3) (corresponding to pressures between p = 324 mbar and p = 1665 mbar) and revealed a pressure independent reaction. In the temperature range 1057 K rate constant can be represented by the Arrhenius expression k/(cm(3) mol(-1) s(-1)) = 4.1 × 10(13) exp(-101 kJ mol(-1)/RT) (Δlog k = ±0.11). The pressure independent reaction as well as the measured activation energy is consistent with a dominating H abstracting reaction channel yielding the products HNCN + H. The reaction NCN + H2 has been implemented together with a set of reactions for subsequent HNCN and HNC chemistry into the detailed GDFkin3.0_NCN mechanism for NOx flame modeling. Two fuel-rich low-pressure CH4/O2/N2-flames served as examples to quantify the impact of the additional chemical pathways. Although the overall NCN consumption by H2 remains small, significant differences have been observed for NO yields with the updated mechanism. A detailed flux analysis revealed that HNC, mainly arising from HCN/HNC isomerization, plays a decisive role and enhances NO formation through a new HNC → HNCO → NH2→ NH → NO pathway.

  12. An Introduction to Collision Theory Rate Constants via Distribution Functions.

    Science.gov (United States)

    McAlduff, E. J.

    1980-01-01

    Described is an introduction to the collision theory by arriving at the many degrees of freedom rote constant and showing that the (-Ea/RT) is a special case and corresponds to activation in 2 squared terms on the line of center rate constant, which is found through the use of distributed functions. (Author/DS)

  13. 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.

  14. Quantum corrections to the equilibrium rate constants of inelastic processes

    Energy Technology Data Exchange (ETDEWEB)

    Eletskii, Aleksandr V [Russian Research Centre ' Kurchatov Institute' , Moscow (Russian Federation); Starostin, Andrei N; Taran, Mikhail D [State Research Center of Russian Federation ' Troitsk Institute for Innovation and Fusion Research' , Troitsk, Moscow Region (Russian Federation)

    2005-03-31

    The quantum corrections which the equilibrium rate constants of inelastic processes acquire due to particle momenta deviating from the Maxwell distribution at high gas pressures and relatively low temperatures are considered. This deviation can be interpreted as a manifestation of the time-energy uncertainty relation for particles colliding elastically at a high rate, with the characteristic energy {approx}h{nu} (where {nu} is the collision frequency) put into correspondence with the temperature. Taking account of this deviation changes the temperature dependences of the rate constants of adiabatic and exothermal processes, as illustrated by the examples of vibrationally relaxing diatomic molecules and nuclear fusion and chemical processes. The experimental anomalies in the temperature dependences of the corresponding rate constants are accounted for adequately by introducing the non-Maxwellian corrections. (methodological notes)

  15. 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.

  16. Charring rate of wood exposed to a constant heat flux

    Science.gov (United States)

    R. H. White; H. C. Tran

    1996-01-01

    A critical factor in the fire endurance of a wood member is its rate of charring. Most available charring rate data have been obtained using the time-temperature curves of the standard fire resistance tests (ASTM E 119 and ISO 834) to define the fire exposure. The increased use of heat release calorimeters using exposures of constant heat flux levels has broadened the...

  17. A Comparative Study of the Drying Rate Constant, Drying Efficiency ...

    African Journals Online (AJOL)

    The adoption of the drying techniques would ensure steady availability of these vegetables all the year round as well as reduce carbon emissions from the conventional drying methods and hence mitigate global warming. KEYWORDS: Solar drying, open- air sun drying, drying rate constant, falling rate, climate change, food ...

  18. Reaction rate constant for radiative association of CF+

    Science.gov (United States)

    Ã-ström, Jonatan; Bezrukov, Dmitry S.; Nyman, Gunnar; Gustafsson, Magnus

    2016-01-01

    Reaction rate constants and cross sections are computed for the radiative association of carbon cations (C+) and fluorine atoms (F) in their ground states. We consider reactions through the electronic transition 11Π → X1Σ+ and rovibrational transitions on the X1Σ+ and a3Π 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 10-21 cm3 s-1, rising toward 10-16 cm3 s-1 for a temperature of 30 000 K.

  19. Distribution of adhesion rate constant in the coal sample

    Directory of Open Access Journals (Sweden)

    Marian Brožek

    2005-11-01

    Full Text Available Flotation is the process of enrichment which consists in differentiating the useful component (volume property in the separation products. Flotation leads to the differentiation of the volume property by means of applying the differentiation of surface properties. Since there is a correlation between these properties, the authors determined the distribution of adhesion rate constant in relation with the content of the useful component and applying the dispersive model of a particle. The content of the useful component is directly connected with the volume physical property, represented by particle density. The paper present distribution functions of density and adhesion rate constant in the sample. Also the relation between adhesion rate constant and ash content for narrow density fractions has been revealed.

  20. 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.

  1. Oxygen Uptake in Maximal Effort Constant Rate and Interval Running

    Directory of Open Access Journals (Sweden)

    Daniel Pratt

    2013-01-01

    Full Text Available This study investigated differences in average of maximal effort interval running to maximal effort constant rate running at lactate threshold matched for time. The average and distance covered of 10 recreational male runners (: 4158 ± 390 mL·min−1 were compared between a maximal effort constant-rate run at lactate threshold (CRLT, a maximal effort interval run (INT consisting of 2 min at speed with 2 minutes at 50% of repeated 5 times, and a run at the average speed sustained during the interval run (CR submax. Data are presented as mean and 95% confidence intervals. The average for INT, 3451 (3269–3633 mL·min−1, 83% , was not significantly different to CRLT, 3464 (3285–3643 mL·min−1, 84% , but both were significantly higher than CR sub-max, 3464 (3285–3643 mL·min−1, 76% . The distance covered was significantly greater in CLRT, 4431 (4202–3731 metres, compared to INT and CR sub-max, 4070 (3831–4309 metres. The novel finding was that a 20-minute maximal effort constant rate run uses similar amounts of oxygen as a 20-minute maximal effort interval run despite the greater distance covered in the maximal effort constant-rate run.

  2. The specific gamma-ray constant and exposure rate constant of 182Ta.

    Science.gov (United States)

    Glasgow, G P; Dillman, L T

    1982-01-01

    Reported values of the specific gamma-ray constant gamma for 182Ta range from the original value of 6.1 to 7.692 R cm2h-1mCi-1, recommended in NCRP Report No. 41. The original calculation of gamma was based on inadequate nuclear spectroscopy and decay scheme data. The higher value of gamma occurs because of a computational error in the relative intensity of the 1.2575-MeV gamma ray. Using nuclear spectroscopy data from the most recent Evaluated Nuclear Data File (ENSDF), gamma is calculated to be 6.71 +/- 0.06 R cm2h-1mCi-1 and the exposure rate constant gamma gamma is 6.87 +/- 0.06 R cm2h-1mCi-1. These new calculations are presented and previously reported values of gamma and gamma gamma are reviewed.

  3. 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.

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

    African Journals Online (AJOL)

    In this study, the analgesic potency of constant rate infusion of tramadol hydrochloride and as adjunct to ketoprofen on laparotomy-induced pain was evaluated. Dogs were randomly assigned to 4 groups (n=5). Groups 1, 2 and 3 received 0.5mg/kg/hr, 1.0mg/kg/hr and 2.0mg/kg/hr IV; CRI of tramadol hydrochloride ...

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

    CERN Document Server

    Öström, Jonatan; Nyman, Gunnar; Gustafsson, Magnus

    2015-01-01

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

  6. 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.

  7. Comparison of TID Effects in Space-Like Variable Dose Rates and Constant Dose Rates

    Science.gov (United States)

    Harris, Richard D.; McClure, Steven S.; Rax, Bernard G.; Evans, Robin W.; Jun, Insoo

    2008-01-01

    The degradation of the LM193 dual voltage comparator has been studied at different TID dose rate profiles, including several different constant dose rates and a variable dose rate that simulates the behavior of a solar flare. A comparison of results following constant dose rate vs. variable dose rates is made to explore how well the constant dose rates used for typical part testing predict the performance during a simulated space-like mission. Testing at a constant dose rate equal to the lowest dose rate seen during the simulated flare provides an extremely conservative estimate of the overall amount of degradation. A constant dose rate equal to the average dose rate is also more conservative than the variable rate. It appears that, for this part, weighting the dose rates by the amount of total dose received at each rate (rather than the amount of time at each dose rate) results in an average rate that produces an amount of degradation that is a reasonable approximation to that received by the variable rate.

  8. Specific gamma-ray constant and exposure rate constant of 192Ir.

    Science.gov (United States)

    Glasgow, G P; Dillman, L T

    1979-01-01

    Calculated values of the 192Ir specific gamma-ray constant, Gamma range from the low value of 3.948 R cm2h-1mCi-1 recommended in NCRP No. 41 to a high of 4.89 R cm2h-1mCi-1. Measured values of Gamma range only from 4.85 to 5.0 Rcm2h-1mCi-1. Discrepancies in reported calculated values exist because the isotope decay scheme and other nuclear spectroscopy data pertinent to these calculations were not well known. Using the 28 gamma rays and relative intensities from the most recent Evaluated Nuclear Structure Data File (ENSDF), Gamma is calculated to be 4.62 +/- 0.05 Rcm2h-1mCi-1 and the exposure rate constant Gamma delta is 4.69 +/- 0.05 Rcm2h-1mCi-1. These new calculations are presented and previously reported values of Gamma and Gamma delta are reviewed.

  9. 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.

  10. Measurement of both the equilibrium constant and rate constant for electronic energy transfer by control of the limiting kinetic regimes.

    Science.gov (United States)

    Vagnini, Michael T; Rutledge, W Caleb; Wagenknecht, Paul S

    2010-02-01

    Electronic energy transfer can fall into two limiting cases. When the rate of the energy transfer back reaction is much faster than relaxation of the acceptor excited state, equilibrium between the donor and acceptor excited states is achieved and only the equilibrium constant for the energy transfer can be measured. When the rate of the back reaction is much slower than relaxation of the acceptor, the energy transfer is irreversible and only the forward rate constant can be measured. Herein, we demonstrate that with trans-[Cr(d(4)-cyclam)(CN)(2)](+) as the donor and either trans-[Cr([15]ane-ane-N(4))(CN)(2)](+) or trans-[Cr(cyclam)(CN)(2)](+) as the acceptor, both limits can be obtained by control of the donor concentration. The equilibrium constant and rate constant for the case in which trans-[Cr([15]ane-ane-N(4))(CN)(2)](+) is the acceptor are 0.66 and 1.7 x 10(7) M(-1) s(-1), respectively. The equilibrium constant is in good agreement with the value of 0.60 determined using the excited state energy gap between the donor and acceptor species. For the thermoneutral case in which trans-[Cr(cyclam)(CN)(2)](+) is the acceptor, an experimental equilibrium constant of 0.99 was reported previously, and the rate constant has now been measured as 4.0 x 10(7) M(-1) s(-1).

  11. High-Temperature Slow Crack Growth of Silicon Carbide Determined by Constant-Stress-Rate and Constant-Stress Testing

    Science.gov (United States)

    Choi, Sung H.; Salem, J. A.; Nemeth, N. N.

    1998-01-01

    High-temperature slow-crack-growth behaviour of hot-pressed silicon carbide was determined using both constant-stress-rate ("dynamic fatigue") and constant-stress ("static fatigue") testing in flexure at 1300 C in air. Slow crack growth was found to be a governing mechanism associated with failure of the material. Four estimation methods such as the individual data, the Weibull median, the arithmetic mean and the median deviation methods were used to determine the slow crack growth parameters. The four estimation methods were in good agreement for the constant-stress-rate testing with a small variation in the slow-crack-growth parameter, n, ranging from 28 to 36. By contrast, the variation in n between the four estimation methods was significant in the constant-stress testing with a somewhat wide range of n= 16 to 32.

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

    DEFF Research Database (Denmark)

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

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

  13. Estimating hydraulic properties of volcanic aquifers using constant-rate and variable-rate aquifer tests

    Science.gov (United States)

    Rotzoll, K.; El-Kadi, A. I.; Gingerich, S.B.

    2007-01-01

    In recent years the ground-water demand of the population of the island of Maui, Hawaii, has significantly increased. To ensure prudent management of the ground-water resources, an improved understanding of ground-water flow systems is needed. At present, large-scale estimations of aquifer properties are lacking for Maui. Seven analytical methods using constant-rate and variable-rate withdrawals for single wells provide an estimate of hydraulic conductivity and transmissivity for 103 wells in central Maui. Methods based on constant-rate tests, although not widely used on Maui, offer reasonable estimates. Step-drawdown tests, which are more abundantly used than other tests, provide similar estimates as constant-rate tests. A numerical model validates the suitability of analytical solutions for step-drawdown tests and additionally provides an estimate of storage parameters. The results show that hydraulic conductivity is log-normally distributed and that for dike-free volcanic rocks it ranges over several orders of magnitude from 1 to 2,500 m/d. The arithmetic mean, geometric mean, and median values of hydraulic conductivity are respectively 520, 280, and 370 m/d for basalt and 80, 50, and 30 m/d for sediment. A geostatistical approach using ordinary kriging yields a prediction of hydraulic conductivity on a larger scale. Overall, the results are in agreement with values published for other Hawaiian islands. ?? 2007 American Water Resources Association.

  14. A Novel Rate Control Scheme for Constant Bit Rate Video Streaming

    Directory of Open Access Journals (Sweden)

    Venkata Phani Kumar M

    2015-08-01

    Full Text Available In this paper, a novel rate control mechanism is proposed for constant bit rate video streaming. The initial quantization parameter used for encoding a video sequence is determined using the average spatio-temporal complexity of the sequence, its resolution and the target bit rate. Simple linear estimation models are then used to predict the number of bits that would be necessary to encode a frame for a given complexity and quantization parameter. The experimental results demonstrate that our proposed rate control mechanism significantly outperforms the existing rate control scheme in the Joint Model (JM reference software in terms of Peak Signal to Noise Ratio (PSNR and consistent perceptual visual quality while achieving the target bit rate. Furthermore, the proposed scheme is validated through implementation on a miniature test-bed.

  15. Determination of rate constants and equilibrium constants for solution-phase drug-protein interactions by ultrafast affinity extraction.

    Science.gov (United States)

    Zheng, Xiwei; Li, Zhao; Podariu, Maria I; Hage, David S

    2014-07-01

    A method was created on the basis of ultrafast affinity extraction to determine both the dissociation rate constants and equilibrium constants for drug-protein interactions in solution. Human serum albumin (HSA), an important binding agent for many drugs in blood, was used as both a model soluble protein and as an immobilized binding agent in affinity microcolumns for the analysis of free drug fractions. Several drugs were examined that are known to bind to HSA. Various conditions to optimize in the use of ultrafast affinity extraction for equilibrium and kinetic studies were considered, and several approaches for these measurements were examined. The dissociation rate constants obtained for soluble HSA with each drug gave good agreement with previous rate constants reported for the same drugs or other solutes with comparable affinities for HSA. The equilibrium constants that were determined also showed good agreement with the literature. The results demonstrated that ultrafast affinity extraction could be used as a rapid approach to provide information on both the kinetics and thermodynamics of a drug-protein interaction in solution. This approach could be extended to other systems and should be valuable for high-throughput drug screening or biointeraction studies.

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

    NARCIS (Netherlands)

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

    2009-01-01

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

  17. 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.

  18. Universality of thermodynamic constants governing biological growth rates.

    Science.gov (United States)

    Corkrey, Ross; Olley, June; Ratkowsky, David; McMeekin, Tom; Ross, Tom

    2012-01-01

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

  19. Universality of thermodynamic constants governing biological growth rates.

    Directory of Open Access Journals (Sweden)

    Ross Corkrey

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

  20. Iterative rate-distortion optimization of H.264 with constant bit rate constraint.

    Science.gov (United States)

    An, Cheolhong; Nguyen, Truong Q

    2008-09-01

    In this paper, we apply the primal-dual decomposition and subgradient projection methods to solve the rate-distortion optimization problem with the constant bit rate constraint. The primal decomposition method enables spatial or temporal prediction dependency within a group of picture (GOP) to be processed in the master primal problem. As a result, we can apply the dual decomposition to minimize independently the Lagrangian cost of all the MBs using the reference software model of H.264. Furthermore, the optimal Lagrange multiplier lambda* is iteratively derived from the solution of the dual problem. As an example, we derive the optimal bit allocation condition with the consideration of temporal prediction dependency among the pictures. Experimental results show that the proposed method achieves better performance than the reference software model of H.264 with rate control.

  1. The effect of temperature fluctuations of reaction rate constants in turbulent reacting flows

    Science.gov (United States)

    Chinitz, W.; Antaki, P. J.; Kassar, G. M.

    1981-01-01

    Current models of turbulent reacting flows frequently use Arrhenius reaction rate constants obtained from static or laminar flow theory and/or experiments, or from best fits of static, laminar, and turbulent data. By treating the reaction rate constant as a continuous random variable which is temperature-dependent, the present study assesses the effect of turbulent temperature fluctuations on the reaction rate constant. This model requires that a probability density function (PDF) describing the nature of the fluctuations be specified. Three PDFs are examined: the clipped Gaussian, the beta PDF, and the ramp model. All the models indicate that the reaction rate constant is greater in a turbulent flow field than in an equivalent laminar flow. In addition, an amplification ratio, which is the ratio of the turbulent rate constant to the laminar rate constant, is defined and its behavior as a function of the mean temperature fluctuations is described

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

    Indian Academy of Sciences (India)

    J Dey

    which is a good approximation in the log-layer [1, 3], urms is the characteristic velocity scale [4]. The inclusion of urms in this model is for this reason. Since рuurmsЮ1=2 $ OрusЮ in the log-layer, the proposed model for the dissipation rate in. Eq. (5) preserves the essence of Eqs. (1) or (4). At the boundary layer edge, y ! d ...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2007-12-15

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

  4. Measuring kinetic rate constants of multiple-component reactions with optical biosensors.

    Science.gov (United States)

    Edwards, David A; Evans, Ryan M; Li, Wenbin

    2017-09-15

    One may measure the kinetic rate constants associated with biochemical reactions using an optical biosensor: an instrument in which ligand molecules are convected through a flow cell over a surface to which receptors are immobilized. If there are multiple reactants, one is faced with the problem of fitting multiple kinetic rate constants to one signal, since data from all of the reacting species is lumped together. Even in the presence of ambiguous data, one may use a series of experiments to accurately determine the rate constants. Moreover, the true set of rate constants may be identified by either postprocessing the signals or adjusting the ligand inflow concentrations. Published by Elsevier Inc.

  5. 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

  6. 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

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

    DEFF Research Database (Denmark)

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

    1994-01-01

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

  8. Low-energy electron impact cross-sections and rate constants of

    Indian Academy of Sciences (India)

    Anand Bharadvaja

    2017-07-24

    Jul 24, 2017 ... biological processes [2], modelling of combustion phe- nomenon [3,4] etc. The e. −−NH2 collision ..... pole extracted adiabatic nuclei (MEAN) method [53] is used to obtain the DCS. The methodology is .... effects. 2.3 Rate constants. The rate constants for any given process is given by [55] k(Te) = (. 2 me. ) ...

  9. 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...

  10. On the ergodicity bounds for a constant retrial rate queueing model

    OpenAIRE

    Zeifman, Alexander; Satin, Yacov; Morozov, Evsey; Nekrasova, Ruslana; Gorshenin, Andrey

    2015-01-01

    We consider a Markovian single-server retrial queueing system with a constant retrial rate. Conditions of null ergodicity and exponential ergodicity for the correspondent process, as well as bounds on the rate of convergence are obtained.

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

    Science.gov (United States)

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

    2009-08-15

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

  12. Potential energy construction in the diabatic picture for quantum mechanical rate constants of intermolecular proton transfer.

    Science.gov (United States)

    Hori, Yuta; Ida, Tomonori; Mizuno, Motohiro

    2017-06-28

    We propose a simple method for potential construction in the diabatic picture and the estimation of thermal rate constants for intermolecular proton transfer reactions using quantum dynamics simulations carried out on the constructed potentials. For symmetrical and asymmetrical proton transfer pairs, the obtained potentials and rate constants were in good agreement with the reference values. Furthermore, our method is used for the analysis of proton transfer in crystalline imidazolium succinate and discusses the proton conductivity in terms of intermolecular proton transfer. This approach can be used to estimate proton transfer rate constants for large molecular systems, even when the calculation of the transition state is impossible.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-01-21

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

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

    Science.gov (United States)

    Newsome, Ben; Evans, Mat

    2017-12-01

    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 regions such as the tropics, poles and upper

  15. A method to determine pharmacokinetic parameters based on andante constant-rate intravenous infusion

    OpenAIRE

    Yu, Rui-hong; Cao, Yong-Xiao

    2017-01-01

    On account of the disturbance from the distribution phase, the concentration-time curve of drugs cannot fully reflect the characteristics of elimination, and thus, it is difficult for present methods to obtain ideal pharmacokinetic parameters. This paper presents a method to determine pharmacokinetic parameters based on an andante constant-rate intravenous infusion. A mathematical model of the constant-rate intravenous infusion combined with the elimination of first-order kinetics was establi...

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

    Science.gov (United States)

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

    2014-05-15

    Free chlorine is extensively used for water and wastewater disinfection nowadays. However, it still remains a big challenge to determine the rate constants of rapid chlorination reactions although competition kinetics and stopped-flow spectrophotometric (SFS) methods have been employed individually to investigate fast reaction kinetics. In this work, we proposed an SFS competition kinetics method to determine the rapid chlorination rate constants by using a common colorimetric reagent, N,N-diethyl-p-phenylenediamine (DPD), as a reference probe. A kinetic equation was first derived to estimate the reaction rate constant of DPD towards chlorine under a given pH and temperature condition. Then, on that basis, an SFS competition kinetics method was proposed to determine directly the chlorination rate constants of several representative compounds including tetracycline, ammonia, and four α-amino acids. Although Cl2O is more reactive than HOCl, its contribution to the overall chlorination kinetics of the test compounds could be neglected in this study. Finally, the developed method was validated through comparing the experimentally measured chlorination rate constants of the selected compounds with those obtained or calculated from literature and analyzing with Taft's correlation as well. This study demonstrates that the SFS competition kinetics method can measure the chlorination rate constants of a test compound rapidly and accurately. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. 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

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

    Directory of Open Access Journals (Sweden)

    Guohu Feng

    2013-02-01

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

  19. 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.

  20. Numerical methods for realizing nonstationary Poisson processes with piecewise-constant instantaneous-rate functions

    DEFF Research Database (Denmark)

    Harrod, Steven; Kelton, W. David

    2006-01-01

    with piecewise-constant instantaneous rate functions, a capability that has been implemented in commercial simulation software. They test these algorithms in C programs and make comparisons of accuracy, speed, and variability across disparate rate functions and microprocessor architectures. Choice of optimal...

  1. Constant specific growth rate in fed-batch cultivation of Bordetella pertussis using adaptive control

    NARCIS (Netherlands)

    Soons, Z.I.T.A.; Voogt, J.A.; Straten, van G.; Boxtel, van A.J.B.

    2006-01-01

    Monitoring and control of production processes for biopharmaceuticals have become standard requirements to support consistency and quality. In this paper, a constant specific growth rate in fed-batch cultivation of Bordetella pertussis is achieved by a newly designed specific growth rate controller.

  2. On the Values at Equilibrium and Rate Constants in Inter - Conversion Processes.

    Science.gov (United States)

    Olteanu, Octav

    2016-01-01

    Inter - conversion processes of labile molecules obey similar rules to those of reversible chemical reactions. Solving the corresponding linear differential systems is used along this work, as well as in the preceding version. The main purpose of the present mini revue paper is to recall, improve and correct some mathematical methods in determining the optimal values at equilibrium, and remarkable particular rate constants. This part was not proved correctly in my previous work. In my previous work, the proof of the equality of the concentrations of the main species at equilibrium was not correct. In the current manuscript, we use increasing velocity in order to obtain this first important result. To this aim, one applies Schwarz inequality and the case when equality occurs. In order to determine significant rate constants, we characterize these special values in terms of the norm of the linear operator defined by the matrix of the differential system. In my previous work, the normal probability density function was used. The latter method was not realistic. Increasing the velocity, one obtains equal optimal values of the concentrations at equilibrium. This method represents a patent in the field. Secondly, characterization of remarkable rate constants (which are also equal) is deduced. The optimal solutions are written explicitly. Under suitable conditions, the values at equilibrium and the rate constants are equal. The common value at equilibrium equals the common value of the rate constants.

  3. ARTICLE Predicting Rate Constants for Nucleophilic Reactions of Amines with Diarylcarbenium Ions Using an ONIOM Method

    Science.gov (United States)

    Zhang, Zhi-ping; Wang, Chen; Fu, Yao; Guo, Qing-xiang

    2010-12-01

    The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods (B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method) were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM(CCSD(T)/6-311++G(2df,2p):B3LYP/6-311++G(2df,2p))// B3LYP/6-31G(d)/PCM/UFF) method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.

  4. 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.

  5. A new approach using coagulation rate constant for evaluation of turbidity removal

    Science.gov (United States)

    Al-Sameraiy, Mukheled

    2017-06-01

    Coagulation-flocculation-sedimentation processes for treating three levels of bentonite synthetic turbid water using date seeds (DS) and alum (A) coagulants were investigated in the previous research work. In the current research, the same experimental results were used to adopt a new approach on a basis of using coagulation rate constant as an investigating parameter to identify optimum doses of these coagulants. Moreover, the performance of these coagulants to meet (WHO) turbidity standard was assessed by introducing a new evaluating criterion in terms of critical coagulation rate constant (kc). Coagulation rate constants (k2) were mathematically calculated in second order form of coagulation process for each coagulant. The maximum (k2) values corresponded to doses, which were obviously to be considered as optimum doses. The proposed criterion to assess the performance of coagulation process of these coagulants was based on the mathematical representation of (WHO) turbidity guidelines in second order form of coagulation process stated that (k2) for each coagulant should be ≥ (kc) for each level of synthetic turbid water. For all tested turbid water, DS coagulant could not satisfy it. While, A coagulant could satisfy it. The results obtained in the present research are exactly in agreement with the previous published results in terms of finding optimum doses for each coagulant and assessing their performances. On the whole, it is recommended considering coagulation rate constant to be a new approach as an indicator for investigating optimum doses and critical coagulation rate constant to be a new evaluating criterion to assess coagulants' performance.

  6. 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

  7. Apparent rate constant mapping using hyperpolarized [1-(13) C]pyruvate

    DEFF Research Database (Denmark)

    Khegai, O.; Schulte, R. F.; Janich, M. A.

    2014-01-01

    ) and suppression of high perfusion regions with low conversion (e.g. blood vessels). Apparent build-up rate constant mapping provides a novel quantitative image contrast for the characterization of metabolic activity. Its possible implementation as a quantitative standard will be subject to further studies......-13C]pyruvate. Using temporally resolved IDEAL spiral CSI, spatially resolved apparent rate constant maps are also extracted. In comparison to single metabolite images, apparent build-up rate constant maps provide improved contrast by emphasizing metabolically active tissues (e.g. tumors......Hyperpolarization of [1-13C]pyruvate in solution allows real-time measurement of uptake and metabolism using MR spectroscopic methods. After injection and perfusion, pyruvate is taken up by the cells and enzymatically metabolized into downstream metabolites such as lactate, alanine, and bicarbonate...

  8. 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.

  9. mineralization rate constants, half-lives and effects of two organic ...

    African Journals Online (AJOL)

    Total N (g/kg). 1.04. C:N ratio. 1.2. Table 2: Organic C and N contents of cattle dung and swine waste. Parameters. Cattle dung. Swine waste. Organic C (g/kg). Total N (g/kg). C: N ratio. 78.6. 14.6. 5:1. 68.4. 19.2. 3:1. Table 3: Mineralization rate constant and half life. Treatment. Minera. rate constant. Half-life (days). CD0SW0.

  10. 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.

  11. 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

  12. Pseudo first ordered adsorption of noxious textile dyes by low-temperature synthesized amorphous carbon nanotubes

    Science.gov (United States)

    Banerjee, D.; Bhowmick, P.; Pahari, D.; Santra, S.; Sarkar, S.; Das, B.; Chattopadhyay, K. K.

    2017-03-01

    Amorphous carbon nanotubes (a-CNTs) were synthesized by solid state reaction. The as prepared a-CNTs were characterized by X-ray diffraction, field emission scanning and high resolution transmission electron microscope and Raman spectroscopy. As-synthesized a-CNTs were used for, the first time, for removing different organic dyes from water. The dyes mainly include Rhodamine B and Methyl Orange and systematic batch mode studies of a-CNTs assisted adsorption have been executed in detail. The removing efficiency of a-CNTs has also been investigated for various sorption parameters like contact time, dosage, pH, initial dye concentration, contact time etc. It is seen that a-CNTs can be material of potential for removal of dyes. In case of Rhodamine B, the maximum time for removal was 45 min whereas for Methyl orange rapid removal was plausible in about 30 min even in ambient condition. The experimental data have been well correlated with classical Langmuir-Freundlich and Temkin adsorption models.

  13. 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 ...

  14. Low-energy electron impact cross-sections and rate constants of NH2

    Indian Academy of Sciences (India)

    This systematic study reports various electron impact cross-sections, rate constants and transport properties of N H 2 radical in the low-energy limit. The collision study is based on R -matrix formalism and involves the use of various scattering models employing different active spaces. Both electron excited ...

  15. 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.

  16. Numerical bifurcation of predator-prey fractional differential equations with a constant rate harvesting

    Energy Technology Data Exchange (ETDEWEB)

    Erjaee, G H [Mathematics and Physics Department, Qatar University, Doha (Qatar)], E-mail: erjaee@qu.edu.qa

    2008-02-15

    In this article saddle and Hopf bifurcation points of predator-prey fractional differential equations system with a constant rate harvesting are investigated. The numerical results based on Grunwald-Letnikov discretization for fractional differential equations together with the Mickens' non-standard discretization method agree with those found by the corresponding ordinary differential equation system.

  17. Numerical bifurcation of predator-prey fractional differential equations with a constant rate harvesting

    Science.gov (United States)

    Erjaee, G. H.

    2008-02-01

    In this article saddle and Hopf bifurcation points of predator-prey fractional differential equations system with a constant rate harvesting are investigated. The numerical results based on Grunwald-Letnikov discretization for fractional differential equations together with the Mickens' non-standard discretization method agree with those found by the corresponding ordinary differential equation system.

  18. DISSOCIATION OF ARSENITE-PEPTIDE COMPLEXES: TRIPHASIC NATURE, RATE CONSTANTS, HALF LIVES AND BIOLOGICAL IMPORTANCE

    Science.gov (United States)

    We determined the number and the dissociation rate constants of different complexes formed from arsenite and two peptides containing either one (RV AVGNDYASGYHYGV for peptide 20) or three cysteines (LE AWQGK VEGTEHLYSMK K for peptide 10) via radioactive 73As labeled arsenite and ...

  19. Constant Savings Rates and Quasi-arithmetic Population Growth under Exhaustible Resource Constraints

    NARCIS (Netherlands)

    Asheim, G.; Buchholz, W.; Hartwick, J.; 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. 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...

  1. 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.

  2. A new semi-empirical kinetic method for the determination of ion exchange constants for the counterions of cationic micelles.

    Science.gov (United States)

    Khan, M Niyaz

    2010-09-15

    A new method, based upon semi-empirical kinetic approach, for the determination of ion exchange constant for ion exchange processes occurring between counterions at the cationic micellar surface is described in this review article. Basically, the method involves a reaction kinetic probe which gives observed pseudo-first-order rate constants (k(obs)) for a nucleophilic substitution reaction between the nonionic and anionic reactants (R and S) in the presence of a constant concentration of both reactants as well as cationic micelles and varying concentrations of an inert inorganic or organic salt (MX). The observed data (k(obs), versus [MX]) fit satisfactorily (in terms of residual errors) to an empirical equation which could be derived from an equation explaining the mechanism of the reaction of the kinetic probe in terms of pseudophase micellar (PM) model coupled with another empirical equation. This (another) empirical equation explains the effect of [MX] on cationic micellar binding constant (K(S)) of the anionic reactant (say S) and gives an empirical constant, K(X/S). The magnitude of K(X/S) is the measure of the ability of X(-) to expel S(-) from a cationic micellar pseudophase to the bulk aqueous phase through ion exchange X(-)/S(-). The values of K(X/S) and K(Y/S) (where Y(-) is another inert counterion) give the ion exchange constant, K(X)(Y) (=K(X)/K(Y) where K(X) and K(Y) represent cationic micellar binding constants of X(-) and Y(-), respectively). The suitability of this method is demonstrated by the use of three different reaction kinetic probes and various MX. Copyright 2010 Elsevier B.V. All rights reserved.

  3. 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.

  4. 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......, and Longwell. Based on an accurate modeling of the flame structure, in particular the concentration profile of propargyl, we estimate the rate constant by fitting the kinetic modeling predictions to the measured benzene and phenyl profiles. The best agreement is obtained with k = 1.3 x 10(12) cm(3)/mol...

  5. 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.

  6. Low-Temperature Experimental and Theoretical Rate Constants for the O(1D) + H2Reaction.

    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.

  7. 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.

  8. 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....

  9. Mechanism and rate constants of the Cdc42 GTPase binding with intrinsically disordered effectors.

    Science.gov (United States)

    Pang, Xiaodong; Zhou, Huan-Xiang

    2016-05-01

    Intrinsically disordered proteins (IDPs) are often involved in signaling and regulatory functions, through binding to cellular targets. Many IDPs undergo disorder-to-order transitions upon binding. Both the binding mechanisms and the magnitudes of the binding rate constants can have functional importance. Previously we have found that the coupled binding and folding of any IDP generally follows a sequential mechanism that we term dock-and-coalesce, whereby one segment of the IDP first docks to its subsite on the target surface and the remaining segments subsequently coalesce around their respective subsites. Here we applied our TransComp method within the framework of the dock-and-coalesce mechanism to dissect the binding kinetics of two Rho-family GTPases, Cdc42 and TC10, with two intrinsically disordered effectors, WASP and Pak1. TransComp calculations identified the basic regions preceding the GTPase binding domains (GBDs) of the effectors as the docking segment. For Cdc42 binding with both WASP and Pak1, the calculated docking rate constants are close to the observed overall binding rate constants, suggesting that basic-region docking is the rate-limiting step and subsequent conformational coalescence of the GBDs on the Cdc42 surface is fast. The possibility that conformational coalescence of the WASP GBD on the TC10 surface is slow warrants further experimental investigation. The account for the differences in binding rate constants among the three GTPase-effector systems and mutational effects therein yields deep physical and mechanistic insight into the binding processes. Our approach may guide the selection of mutations that lead to redesigned binding pathways. © 2016 Wiley Periodicals, Inc.

  10. Factors underlying the perception of effort during constant heart rate running above and below the critical heart rate.

    Science.gov (United States)

    Bergstrom, Haley C; Housh, Terry J; Cochrane, Kristen C; Jenkins, Nathaniel D M; Zuniga, Jorge M; Buckner, Samuel L; Goldsmith, Jacob A; Schmidt, Richard J; Johnson, Glen O; Cramer, Joel T

    2015-10-01

    This study examined: (1) the sustainability of the critical heart rate (CHR) minus 5 b min(-1) (CHR - 5) and CHR plus 5 b min(-1) (CHR + 5); (2) the ratings of perceived exertion (RPE), velocity, [Formula: see text], minute ventilation ([Formula: see text]), breathing frequency (f b ), and electromyographic amplitude (EMG AMP) and EMG mean power frequency (MPF) responses during treadmill running at CHR - 5 and CHR + 5 to determine what factors underlie the perception of effort when heart rate (HR) is held constant; and (3) the relationships among RPE, [Formula: see text], and HR, to determine which variable(s) reflect exhaustion during exercise performed at a constant HR. The CHR was determined in eight runners (mean ± SD; age = 24 ± 3 years) from a series of four exhaustive, constant velocity runs. The RPE, velocity, [Formula: see text], [Formula: see text], f b , EMG AMP, and EMG MPF responses were recorded during runs at the CHR - 5 and CHR + 5. At CHR - 5, RPE, f b, and EMG MPF increased, while velocity, [Formula: see text], [Formula: see text], and EMG AMP decreased. At CHR + 5, RPE and f b increased, velocity, [Formula: see text], [Formula: see text], and EMG AMP decreased, and EMG MPF remained constant. The close association between f b and RPE throughout the run at CHR - 5 and during the last 50 % of the run at CHR + 5 indicated that muscle afferents may have provided feedback from metabolic and mechanical stimuli that contributed to the perceptual responses. In addition, only RPE consistently indicated exhaustion and the current findings supported its use to monitor exercise performed at a constant HR.

  11. 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

  12. 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.

  13. Identifiability of models for time-resolved fluorescence with underlying distributions of rate constants.

    Science.gov (United States)

    Boens, Noël; Van der Auweraer, Mark

    2014-02-01

    The deterministic identifiability analysis of photophysical models for the kinetics of excited-state processes, assuming errorless time-resolved fluorescence data, can verify whether the model parameters can be determined unambiguously. In this work, we have investigated the identifiability of several uncommon models for time-resolved fluorescence with underlying distributions of rate constants which lead to non-exponential decays. The mathematical functions used here for the description of non-exponential fluorescence decays are the stretched exponential or Kohlrausch function, the Becquerel function, the Förster type energy transfer function, decay functions associated with exponential, Gaussian and uniform distributions of rate constants, a decay function with extreme sub-exponential behavior, the Mittag-Leffler function and Heaviside's function. It is shown that all the models are uniquely identifiable, which means that for each specific model there exists a single parameter set that describes its associated fluorescence δ-response function.

  14. Rate constant and possible pressure dependence of the reaction OH + HO2

    Science.gov (United States)

    Demore, W. B.

    1982-01-01

    The technique of laser-induced fluorescence is used to measure steady-state OH concentrations in the photolysis of water vapor at 184.9 nm and 298 K, with O2 added in trace amounts. He or Ar is present at total pressures in the range 75-730 torr. The results are used in deriving the rate-constant ratio of k1 to k5 to the 1/2 power, where k1 and k5 are the rate constants for the reactions OH + HO2 = H2O + O2 and HO2 + HO2 = O2, respectively. When available values of k5 are used, the results give k1 = (1.2 + or - 0.4) x 10 to the -10 cu cm/s at 1-atm pressure, with evidence of a decline of k1 at lower pressures. No water-vapor effect on k1 is observed.

  15. 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......(2) cm(3) mol(-1) s(-1), is consistent with spin-unrestricted density functional theory. Extrapolation to a wider temperature range through ab initio calculations yields the rate constant k(1) = 3.6 x 10(4)T(2.5) exp(-14425[K]/T) cm(3) mol(-1) s(-1). The reaction is probably of minor importance...... in combustion. The present analysis reconciles the batch reactor data of Baldwin et al. with recent high-level theoretical work on the CO + HO2 reaction....

  16. Mechanism and Rate Constants of the Cdc42 GTPase Binding with Intrinsically Disordered Effectors

    OpenAIRE

    Pang, Xiaodong; Zhou, Huan-Xiang

    2016-01-01

    Intrinsically disordered proteins (IDPs) are often involved in signaling and regulatory functions, through binding to cellular targets. Many IDPs undergo disorder-to-order transitions upon binding. Both the binding mechanisms and the magnitudes of the binding rate constants can have functional importance. Previously we have found that the coupled binding and folding of any IDP generally follows a sequential mechanism that we term dock-and-coalesce, whereby one segment of the IDP first docks t...

  17. 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.

  18. A method for computing association rate constants of atomistically represented proteins under macromolecular crowding

    Science.gov (United States)

    Qin, Sanbo; Cai, Lu; Zhou, Huan-Xiang

    2012-12-01

    In cellular environments, two protein molecules on their way to form a specific complex encounter many bystander macromolecules. The latter molecules, or crowders, affect both the energetics of the interaction between the test molecules and the dynamics of their relative motion. In earlier work (Zhou and Szabo 1991 J. Chem. Phys. 95 5948-52), it has been shown that, in modeling the association kinetics of the test molecules, the presence of crowders can be accounted for by their energetic and dynamic effects. The recent development of the transient-complex theory for protein association in dilute solutions makes it possible to easily incorporate the energetic and dynamic effects of crowders. The transient complex refers to a late on-pathway intermediate, in which the two protein molecules have near-native relative separation and orientation, but have yet to form the many short-range specific interactions of the native complex. The transient-complex theory predicts the association rate constant as ka = ka0exp( - ΔG*el/kBT), where ka0 is the ‘basal’ rate constant for reaching the transient complex by unbiased diffusion, and the Boltzmann factors captures the influence of long-range electrostatic interactions between the protein molecules. Crowders slow down the diffusion, therefore reducing the basal rate constant (to kac0), and induce an effective interaction energy ΔGc. We show that the latter interaction energy for atomistic proteins in the presence of spherical crowders is ‘long’-ranged, allowing the association rate constant under crowding to be computed as kac = kac0exp[ - (ΔG*el + ΔG*c)/kBT]. Applications demonstrate that this computational method allows for realistic modeling of protein association kinetics under crowding.

  19. 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.

  20. 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.

  1. 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...... extracts, though possible confounding reactions need to be considered. These kinetic data suggest that small molar excesses of some plant extracts relative to the MPI thiol concentration should afford significant protection against MbFe(IV)=O-mediated oxidation.......Competitive kinetics were applied as a tool to determine apparent rate constants for the reduction of hypervalent haem pigment ferrylmyoglobin (MbFe(IV)=O) by proteins and phenols in aqueous solution of pH 7.4 and I = 1.0 at 25 °C. Reduction of MbFe(IV)=O by a myofibrillar protein isolate (MPI......) from pork resulted in kMPI = 2.2 ± 0.1 × 104 M-1 s-1. Blocking of the protein thiol groups on the MPI by N-ethylmaleimide (NEM) markedly reduced this rate constant to kMPI-NEM = 1.3 ± 0.4 × 103 M-1 s-1 consistent with a key role for the Cys residues on MPI as targets for haem protein-mediated oxidation...

  2. Reaction of hydroxyl radicals with S-nitrosothiols: determination of rate constants and end product analysis.

    Science.gov (United States)

    Manoj, Veleeparambil M; Aravindakumar, Charuvila T

    2003-04-07

    The reaction of the hydroxyl radical (.OH) with S-nitroso derivatives of cysteine, acetylcysteine and glutathione was studied at neutral and acidic pH. The second-order rate constants were determined by a competition kinetic method using a deoxyribose-thiobarbituric acid assay. The rate constants were diffusion controlled and were 2.27, 1.94 and 1.46 x 10(10) dm3 mol-1 s-1, for S-nitrosocysteine, S-nitrosoacetylcysteine and S-nitrosoglutathione respectively, at neutral pH. The major products of the degradation induced by .OH were found to be the corresponding disulfide (-S-S-) and nitrite (NO2-) at neutral pH as well as at pH 3. Simultaneous proton formation has also been observed. A plausible mechanism based on the formation of an intermediate thiol radical (RS.), as a result of electron transfer from the S-nitrosothiols (RSNOs) to .OH, is proposed for the formation of disulfide and nitrite at both pHs. The high rate constant values and the degradation of these compounds demonstrate the potential role of .OH in RSNO metabolism under physiological conditions.

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

    Science.gov (United States)

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

    2017-10-01

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

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    The NH2 + NO2 reaction has been studied experimentally and theoretically. On the basis of laser photolysis/LIF experiments, the total rate constant was determined over the temperature range 295–625 K as k1,exp(T) = 9.5 × 10–7(T/K)−2.05 exp(−404 K/T) cm3 molecule–1 s–1. This value is in the upper...... range of data reported for this temperature range. The reactions on the NH2 + NO2 potential energy surface were studied using high level ab initio transition state theory (TST) based master equation methods, yielding a rate constant of k1,theory(T) = 7.5 × 10–12(T/K)−0.172 exp(687 K/T) cm3 molecule–1 s...... with the measured overall rate constant but tend to overestimate the branching ratio defined as β = k1a/(k1a + k1b) at lower temperatures. Modest adjustments of the attractive potentials for the reaction yield values of k1a = 4.3 × 10–6(T/K)−2.191 exp(−229 K/T) cm3 molecule–1 s–1 and k1b = 1.5 × 10–12(T/K)0.032 exp...

  5. Quantitative structure-reactivity relationships of hydroxyl radical rate constants for linear and cyclic volatile methylsiloxanes.

    Science.gov (United States)

    Kim, Jaeshin; Xu, Shihe

    2017-07-18

    An accurate understanding of the fate of volatile methylsiloxanes (VMS) in air is crucial for determining their persistence and concentrations in the environment. Although oxidation by atmospheric hydroxyl radicals (•OH) is considered as a major degradation mechanism for airborne VMS, the existing bimolecular rate constants with •OH measured and modeled for any given VMS compound varied greatly, depending on the approaches used to generate the data. The objectives of the present study were to measure •OH reaction rate constants for 4 cyclic and 4 linear VMS based on a relative rate method using a newly designed atmospheric chamber and to establish structure-reactivity relationships for the kinetics. In the past, the reaction rate constants for VMS were generally recognized to increase with the number of the methyl groups per molecule, the only differential factor in the existing models. However, the new measurements indicated that molecular structure should also be considered in the prediction of the reaction rates. Better empirical models were developed by simple and multiple linear regressions of the measured values from the present study and the literature. A high correlation existed for the reaction rates with the number of the methyl group attached at 2 distinct siloxane structures (i.e., linear and cyclic VMS). Even better correlations were obtained with one or 2 molecular descriptors that are directly related to the size of VMS, which, in turn, not only depend on the number of methyl groups, but the linear/cyclic structures as well for permethylsiloxanes. Environ Toxicol Chem 2017;9999:1-6. © 2017 SETAC. © 2017 SETAC.

  6. Long-crack growth rate data: Constant amplitude and FALSTAFF loading

    Science.gov (United States)

    Phillips, E. P.

    1988-01-01

    This annex describes test procedures and presents the results from the tests for conventional, long-crack growth rate data. These data were used for comparisons with the short-crack growth rate data. Data were generated in tests with constant stress ratio load sequences (R = -2, -1, 0, and 0.5) and with the FALSTAFF load sequence. Results for long-crack tests with the Gaussian load sequence are discussed. The constant stress ratio tests included decreasing, increasing, and constant load amplitude sequences. All cracks exceeded 6 mm in length when data were taken. All tests were conducted on center-cracked specimens of 2024-T3 aluminum alloy sheet taken from a large stock of this material held at the NASA Langley Research Center for fatigue research programs. The baseline long-crack growth rate data for this AGARD program were generated using 50 mm wide, center-cracked specimens which were cut from some of the same sheets that were used to make the edge-notched, short-crack specimens. At growth rates below about 10 to the -5 mm/cycle, the baseline data were supplemented by data generated using 76 mm wide specimens made from sheets other than those used for the short-crack program. At growth rates above about 10 to the -5 mm/cycle, the baseline data were supplemented by data generated using 305 mm wide specimens made from sheets other than those used for the other two specimen sizes. The results from the 305 mm specimens were published in 1969. All specimen configurations are shown.

  7. 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...... line width diode laser. Experiments were carried out with O2/N2 mixtures at a total pressure of 1 bar, over 748-1323 K. At the lower temperatures single exponential decays of [K] yielded the third-order rate constant for addition, kR1, whereas at higher temperatures equilibration was observed...

  8. 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.

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

    Science.gov (United States)

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

    2017-02-01

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

  10. Rate Constant of the Reaction between CH3O2Radicals 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.

  11. Reconsideration of the rate constant for the reaction of hydroxyl radicals with nitric acid

    Energy Technology Data Exchange (ETDEWEB)

    Brown, S.S.; Talukdar, R.K.; Ravishankara, A.R. [National Oceanic and Atmospheric Administration, Boulder, CO (United States). Aeronomy Lab.]|[Univ. of Colorado, Boulder, CO (United States)

    1999-04-22

    The authors report rate coefficients for the reaction of OH with HNO{sub 3}, k{sub 1}, between 10 and 500 Torr of He, SF{sub 6}, N{sub 2}, and O{sub 2} and at 10 different temperatures between 200 and 375 K. They generated OH via pulsed photolysis of HNO{sub 3} and monitored the [OH] temporal profile via pulsed laser induced fluorescence. Below 300 K the value of k{sub 1} increases rapidly with decreasing temperature and depends on pressure. The pressure dependence of k{sub 1} at low temperature is significantly larger than that obtained by extrapolation of the currently available data. The pressure and temperature dependence is most likely due to a competition between direct abstraction and reactive complex formation. A rate constant expression derived from such a mechanism gives a global fit for k{sub 1} that is applicable to atmospheric conditions. The new rate constant alters the calculated NO{sub 2} to HNO{sub 3} ratio in the lower stratosphere.

  12. Reaction rate constants and mean population percentage for nitrifiers in an alternating oxidation ditch system.

    Science.gov (United States)

    Mantziaras, I D; Katsiri, A

    2011-01-01

    This paper presents a methodology for the determination of reaction rate constants for nitrifying bacteria and their mean population percentage in biomass in an alternating oxidation ditch system. The method used is based on the growth rate equations of the ASM1 model (IWA) (Henze et al. in Activated sludge models ASM1, ASM2, ASM2d, and ASM3. IWA Scientific and Technical Report no. 9, IWA Publishing, London, UK, 2000) and the application of mass balance equations for nitrifiers and ammonium nitrogen in an operational cycle of the ditch system. The system consists of two ditches operating in four phases. Data from a large-scale oxidation ditch pilot plant with a total volume of 120 m(3) within an experimental period of 8 months was used. Maximum specific growth rate for autotrophs (μ(A)) and the half-saturation constant for ammonium nitrogen (K(NH)) were found to be 0.36 day(-1) and 0.65 mgNH(4)-N/l, respectively. Additionally, the average population percentage of the nitrifiers in the biomass was estimated to be around 3%.

  13. Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

    Science.gov (United States)

    Song, Lei; Kästner, Johannes

    2017-12-01

    Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir–Hinshelwood and the Eley–Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ∼80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

  14. 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.

  15. 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...... 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...... consumption management based on the requirements for the video quality....

  16. 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....

  17. 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.

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

    Directory of Open Access Journals (Sweden)

    Fernando M. Botelho

    2011-08-01

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

  19. 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.

  20. Reaction of H2with O2in 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.

  1. Voltage affects the dissociation rate constant of the m2 muscarinic receptor.

    Directory of Open Access Journals (Sweden)

    Yair Ben Chaim

    Full Text Available G-protein coupled receptors (GPCRs comprise the largest protein family and mediate the vast majority of signal transduction processes in the body. Until recently GPCRs were not considered to be voltage dependent. Newly it was shown for several GPCRs that the first step in GPCR activation, the binding of agonist to the receptor, is voltage sensitive: Voltage shifts the receptor between two states that differ in their binding affinity. Here we show that this shift involves the rate constant of dissociation. We used the m2 muscarinic receptor (m2R a prototypical GPCR and measured directly the dissociation of [(3H]ACh from m2R expressed Xenopus oocytes. We show, for the first time, that the voltage dependent change in affinity is implemented by voltage shifting the receptor between two states that differ in their rate constant of dissociation. Furthermore, we provide evidence that suggest that the above shift is achieved by voltage regulating the coupling of the GPCR to its G protein.

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

    Science.gov (United States)

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

    2017-09-01

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

  3. Rate constant for the OH + CO reaction - Pressure dependence and the effect of oxygen

    Science.gov (United States)

    Demore, W. B.

    1984-01-01

    The effect of pressure on the rate constant of the OH + CO reaction has been measured for Ar, N2, and SF6 over the pressure range 200-730 torr. All experiments were at room temperature. The method involved laser-induced fluorescence to measure steady-state OH concentrations in the 184.9 nm photolysis of H2O-CO mixtures in the three carrier gases, combined with supplementary measurements of the CO depletion in these same carrier gases in the presence and absence of competing reference reactants. The effect of O2 on the pressure effect was determined. A pressure enhancement of the rate constant was observed for N2 and SF6, but not for Ar, within an experimental error of about 10 percent. The pressure effect for N2 was somewhat lower than previous literature reports, being about 40 percent at 730 torr. For SF6 a factor of two enhancement was seen at 730 torr. In each case it was found that O2 had no effect on the pressure enhancement. The roles of the radical species HCO and HOCO were evaluated.

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

    Science.gov (United States)

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

    2011-01-01

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

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

    DEFF Research Database (Denmark)

    Pattison, D I; Davies, Michael Jonathan

    2001-01-01

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

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

    Science.gov (United States)

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

    1987-01-01

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

  7. Faster rates with less catalyst in template-directed reactions

    Science.gov (United States)

    Kanavarioti, A.; Baird, E. E.

    1995-01-01

    We have recently shown that the polycytidylic acid-directed polymerization of guanosine 5'-monophosphate 2-methylimidazolide (2-MeImpG) is amenable to kinetic study and that rate determinations as a function of 2-MeImpG concentration can reveal much mechanistic detail (Kanavarioti et al. 1993). Here we report kinetic data which show that, once the reaction has been initiated by the formation of dimers, the elongation of dimers to form longer oligomers is accelerated by decreasing polycytidylate (poly(C)) concentration from 0.05 to 0.002 M. This result is consistent with the previously proposed mechanism. The increase in the observed pseudo-first order rate constant for formation of the trimer, k3', and the corresponding constant for formation of oligomers longer than the trimer, ki' (ki' is independent of oligomer length for i > or = 4), with decreasing template concentration for a given monomer concentration is attributed to an increase in template occupancy as template concentration is reduced.

  8. Allowance for antibody bivalence in the determination of association rate constants by kinetic exclusion assay.

    Science.gov (United States)

    Winzor, Donald J

    2013-10-15

    This investigation completes the amendment of theoretical expressions for the characterization of antigen-antibody interactions by kinetic exclusion assay-an endeavor that has been marred by inadequate allowance for the consequences of antibody bivalence in its uptake by the affinity matrix (immobilized antigen) that is used to ascertain the fraction of free antibody sites in a solution with defined total concentrations of antigen and antibody. A simple illustration of reacted site probability considerations in action confirms that the square root of the fluorescence response ratio, R(Ag)/R₀, needs to be taken in order to determine the fraction of unoccupied antibody sites, which is the parameter employed to describe the kinetics of antigen uptake in the mixture of antigen and antibody with defined initial composition. The approximately 2-fold underestimation of the association rate constant (k(a)) that emanates from the usual practice of omitting the square root factor gives rise to a corresponding overestimate of the equilibrium dissociation constant (K(d))--a situation that is also encountered in the thermodynamic characterization of antigen-antibody interactions by kinetic exclusion assay. Copyright © 2013 Elsevier Inc. All rights reserved.

  9. 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.

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

    Directory of Open Access Journals (Sweden)

    Tay C.C.

    2013-06-01

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

  11. 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...... 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...

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

    Science.gov (United States)

    Bharadvaja, Anand; Kaur, Savinder; Baluja, K. L.

    2017-08-01

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

  13. Ozonation of pharmaceutical compounds: Rate constants and elimination in various water matrices.

    Science.gov (United States)

    Javier Benitez, F; Acero, Juan L; Real, Francisco J; Roldán, Gloria

    2009-09-01

    The ozonation of four pharmaceuticals (metoprolol, naproxen, amoxicillin, and phenacetin) in ultra-pure (UP) water was studied in the pH range between 2.5 and 9. The experiments allowed the determination of the apparent rate constants for the reactions between ozone and the selected compounds. The values obtained varied depending on the pH, and ranged between 239 and 1.27x10(4)M(-1) s(-1) for metoprolol; 2.62x10(4) and 2.97x10(5)M(-1)s(-1) for naproxen; 2.31x10(3) and 1.21x10(7)M(-1)s(-1) for amoxicillin; and 215 and 1.57x10(3)M(-1)s(-1) for phenacetin. Due to the acidic nature of these substances, the degree of dissociation of each pharmaceutical was determined at every pH of work, and the specific rate constants of the neutral and ionic species formed were evaluated. Additionally, the simultaneous ozonation of the pharmaceuticals in different water matrices was carried out by considering a groundwater, a surface water from a public reservoir, and three secondary effluents from municipal wastewater treatment plants. The influence of the operating conditions (initial ozone dose, nature of pharmaceuticals and type of water) on the pharmaceuticals elimination efficiency was established, and a kinetic model was proposed for the evaluation of the partial contribution to the global oxidation of both, the direct ozonation reaction and the radical pathway.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-10-01

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

  15. 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…

  16. 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.

  17. Escape from a cavity through a small window: turnover of the rate as a function of friction constant.

    Science.gov (United States)

    Berezhkovskii, Alexander M; Makhnovskii, Yurii A; Zitserman, Vladimir Yu

    2006-11-21

    To escape from a cavity through a small window the particle has to overcome a high entropy barrier to find the exit. As a consequence, its survival probability in the cavity decays as a single exponential and is characterized by the only parameter, the rate constant. We use simulations to study escape of Langevin particles from a cubic cavity through a small round window in the center of one of the cavity walls with the goal of analyzing the friction dependence of the escape rate. We find that the rate constant shows the turnover behavior as a function of the friction constant, zeta: The rate constant grows at very small zeta, reaches a maximum value which is given by the transition-state theory (TST), and then decreases approaching zero as zeta-->infinity. Based on the results found in simulations and some general arguments we suggest a formula for the rate constant that predicts a turnover of the escape rate for ergodic cavities in which collisions of the particle with the cavity walls are defocusing. At intermediate-to-high friction the formula describes transition between two known results for the rate constant: the TST estimation and the high friction limiting behavior that characterizes escape of diffusing particles. In this range of friction the rate constants predicted by the formula are in good agreement with those found in simulations. At very low friction the rate constants found in simulations are noticeably smaller than those predicted by the formula. This happens because the simulations were run in the cubic cavity which is not ergodic.

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

    Directory of Open Access Journals (Sweden)

    Ali Varmaghani

    2012-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1980-01-01

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

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

    Science.gov (United States)

    Sorvajärvi, Tapio; Viljanen, Jan; Toivonen, Juha; Marshall, Paul; Glarborg, Peter

    2015-04-09

    The addition reaction of potassium atoms with oxygen has been studied using the collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) method. KCl vapor was photolyzed with 266 nm pulses and the absorbance by K atoms at 766.5 nm was measured at various delay times with a narrow line width diode laser. Experiments were carried out with O2/N2 mixtures at a total pressure of 1 bar, over 748-1323 K. At the lower temperatures single exponential decays of [K] yielded the third-order rate constant for addition, kR1, whereas at higher temperatures equilibration was observed in the form of double exponential decays of [K], which yielded both kR1 and the equilibrium constant for KO2 formation. kR1 can be summarized as 1.07 × 10(-30)(T/1000 K)(-0.733) cm(6) molecule(-2) s(-1). Combination with literature values leads to a recommended kR1 of 5.5 × 10(-26)T(-1.55) exp(-10/T) cm(6) molecule(-2) s(-1) over 250-1320 K, with an error limit of a factor of 1.5. A van't 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 with a CCSD(T) extrapolation to the complete basis set limit, with all electrons correlated, of 177.9 kJ mol(-1).

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

    Science.gov (United States)

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

  2. 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.

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

    DEFF Research Database (Denmark)

    Jørgensen, Kåre; Jensen, Anker; Sloth, Jakob

    2006-01-01

    In the study by Liang et al. [2001. Analysis of constant rate period of spray drying of slurry. Chemical Engineering Science 56, 2205-2213] the Darcy flow of liquid through a pore system of primary particles to the surface of a slurry droplet was applied for the constant rate period. Steep primary...... by Liang et al. is unable to predict the formation of hollow particles. (c) 2005 Elsevier Ltd. All rights reserved....

  4. 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...... by Liang et al. is unable to predict the formation of hollow particles....

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

    Science.gov (United States)

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

    2017-05-01

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

  6. Rate constant for the reaction C2H5 + HBr → C2H6 + Br.

    Science.gov (United States)

    Golden, David M; Peng, Jingping; Goumri, A; Yuan, J; Marshall, Paul

    2012-06-21

    RRKM theory has been employed to analyze the kinetics of the title reaction, in particular, the once-controversial negative activation energy. Stationary points along the reaction coordinate were characterized with coupled cluster theory combined with basis set extrapolation to the complete basis set limit. A shallow minimum, bound by 9.7 kJ mol(-1) relative to C(2)H(5) + HBr, was located, with a very small energy barrier to dissociation to Br + C(2)H(6). The transition state is tight compared to the adduct. The influence of vibrational anharmonicity on the kinetics and thermochemistry of the title reaction were explored quantitatively. With adjustment of the adduct binding energy by ∼4 kJ mol(-1), the computed rate constants may be brought into agreement with most experimental data in the literature, including new room-temperature results described here. There are indications that at temperatures above those studied experimentally, the activation energy may switch from negative to positive.

  7. Dose rate constants for the quantity Hp(3) for frequently used radionuclides in nuclear medicine.

    Science.gov (United States)

    Szermerski, Bastian; Bruchmann, Iris; Behrens, Rolf; Geworski, Lilli

    2016-12-01

    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 Hp(3), which is supposed to estimate the dose to the lens of the eye. For this, Hp(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. Copyright © 2015. Published by Elsevier GmbH.

  8. Quantum chemical and conventional TST calculations of rate constants for the OH + alkane reaction

    Energy Technology Data Exchange (ETDEWEB)

    Bravo-Perez, Graciela [Prog. Investig. Medio Ambiente y Seguridad, Instituto Mexicano del Petroleo, Av. Eje Central Lazaro Cardenas 152, 07730, AP 14805 Mexico DF (Mexico)]. E-mail: gbperez@imp.mx; Alvarez-Idaboy, J. Raul [Prog. Investig. Medio Ambiente y Seguridad, Instituto Mexicano del Petroleo, Av. Eje Central Lazaro Cardenas 152, 07730, AP 14805 Mexico DF (Mexico)]. E-mail: jidaboy@imp.mx; Jimenez, Annia Galano [Prog. Investig. Medio Ambiente y Seguridad, Instituto Mexicano del Petroleo, Av. Eje Central Lazaro Cardenas 152, 07730, AP 14805 Mexico DF (Mexico); Cruz-Torres, Armando [Prog. Investig. Medio Ambiente y Seguridad, Instituto Mexicano del Petroleo, Av. Eje Central Lazaro Cardenas 152, 07730, AP 14805 Mexico DF (Mexico)

    2005-04-04

    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{sub 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.

  9. Constant false alarm rate algorithm for the dim-small target detection based on the distribution characteristics of target coordinates

    Science.gov (United States)

    Fei, Xiao-Liang; Ren, Kan; Qian, Wei-xian; Wang, Peng-cheng

    2015-10-01

    CFAR (Constant False Alarm Rate) is a key technology in Infrared dim-small target detection system. Because the traditional constant false alarm rate detection algorithm gets the probability density distribution which is based on the pixel information of each area in the whole image and calculates the target segmentation threshold of each area by formula of Constant false alarm rate, the problems including the difficulty of probability distribution statistics and large amount of algorithm calculation and long delay time are existing. In order to solve the above problems effectively, a formula of Constant false alarm rate based on target coordinates distribution is presented. Firstly, this paper proposes a new formula of Constant false alarm rate by improving the traditional formula of Constant false alarm rate based on the single grayscale distribution which objective statistical distribution features are introduced. So the control of false alarm according to the target distribution information is implemented more accurately and the problem of high false alarm that is caused of the complex background in local area as the cloud reflection and the ground clutter interference is solved. At the same time, in order to reduce the amount of algorithm calculation and improve the real-time characteristics of algorithm, this paper divides the constant false-alarm statistical area through two-dimensional probability density distribution of target number adaptively which is different from the general identifying methods of constant false-alarm statistical area. Finally, the target segmentation threshold of next frame is calculated by iteration based on the function of target distribution probability density in image sequence which can achieve the purpose of controlling the false alarm until the false alarm is down to the upper limit. The experiment results show that the proposed method can significantly improve the operation time and meet the real-time requirements on

  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. 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.

  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. 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.

  14. Temperature-Dependent Rate Constants and Substituent Effects for the Reactions of Hydroxyl Radicals With Three Partially Fluorinated Ethers

    Science.gov (United States)

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

    1995-01-01

    Rate constants and temperature dependencies for the reactions of OH with CF3OCH3 (HFOC-143a), CF2HOCF2H (HFOC-134), and CF3OCF2H (HFOC-125) were studied using a relative rate technique in the temperature range 298-393 K. The following absolute rate constants were derived: HFOC-143a, 1.9E-12 exp(-1555/T); HFOC-134, 1.9E-12 exp(-2006/T); HFOC-125, 4.7E-13 exp(-2095/T). Units are cm(exp 3)molecule(exp -1) s(exp -1). Substituent effects on OH abstraction rate constants are discussed, and it is shown that the CF3O group has an effect on the OH rate constants similar to that of a fluorine atom. The effects are related to changes in the C-H bond energies of the reactants (and thereby the activation energies) rather than changes in the preexponential factors. On the basis of a correlation of rate constants with bond energies, the respective D(C-H) bond strengths in the three ethers are found to be 102, 104, and 106 kcal/mol, with an uncertainty of about 1 kcal/mol.

  15. Applications of Cell-Ratio Constant False-Alarm Rate Method in Coherent Doppler Wind Lidar

    Directory of Open Access Journals (Sweden)

    Hao Zhu

    2016-12-01

    Full Text Available A cell-ratio constant false-alarm rate (CR-CFAR method for detecting the Doppler frequency shift is proposed to improve the accuracy of velocity measured by coherent Doppler wind lidar (CWL in low signal-to-noise ratio (SNR environments. The method analyzes the spectrum to solve issues of weak signal submergence in noise encountered in the widely used periodogram method. This characteristic is that the signal region slope is larger than the noise region slope in the frequency spectrum. We combined the ratio and CFAR to propose the CR-CFAR method. The peak area is discriminated from the spectrum using this method. By removing background noise, the peak signal is obtained along with the Doppler shift. To verify the CR-CFAR method, a campaign experiment using both CWL and a commercial Doppler lidar was performed in Hami, China (42°32′ N, 94°03′ E during 1–7 June 2016. The results showed that the proposed method significantly improved the reliability of CWL data under low SNR conditions. The height—at which both horizontal wind speed correlativity and horizontal wind direction correlativity exceeded 0.99—increased by 65 m. The relative deviation of the horizontal wind speed at 120 m decreased from 40.37% to 11.04%. We used the CR-CFAR method to analyze continuous data. A greater number of wind field characteristics were obtained during observation compared to those obtained using the common wind field inversion method.

  16. Evaluating the methane generation rate constant (k value) of low-organic waste at Danish landfills.

    Science.gov (United States)

    Mou, Zishen; Scheutz, Charlotte; Kjeldsen, Peter

    2015-01-01

    The methane (CH4) generation rate constant (k value, yr(-1)) is an essential parameter when using first-order decay (FOD) landfill gas (LFG) generation models to estimate CH4 generation from landfills. Four categories of waste (street cleansing, mixed bulky, shredder, and sludge waste) with a low-organic content, as well as temporarily stored combustible waste, were sampled from four Danish landfills. Anaerobic degradation experiments were set up in duplicate for all waste samples and incubated for 405 days, while the cumulative CH4 generation was continuously monitored. Applying FOD equations to the experimental results, half-life time values (t½, yr) and k values of various waste categories were determined. In general, similar waste categories obtained from different Danish landfills showed similar results. Sludge waste had the highest k values, which were in the range 0.156-0.189 yr(-1). The combustible and street cleansing waste showed k values of 0.023-0.027 yr(-1) and 0.073-0.083 yr(-1), respectively. The lowest k values were obtained for mixed bulky and shredder wastes ranging from 0.013 to 0.017 yr(-1). Most low-organic waste samples showed lower k values in comparison to the default numeric values in current FOD models (e.g., IPCC, LandGEM, and Afvalzorg). Compared with the k values reported in the literature, this research determined low-organic waste for the first time via reliable large-scale and long-term experiments. The degradation parameters provided in this study are valuable when using FOD LFG generation models to estimate CH4 generation from modern landfills that receive only low-organic waste. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. 100 kV/2A three-phase constant-current repetitive-rate charging equipment

    CERN Document Server

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

    2002-01-01

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

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

    DEFF Research Database (Denmark)

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

    1996-01-01

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

  19. 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.

  20. Reaction pathway and rate-determining step of the Schmidt rearrangement/fragmentation: a kinetic study.

    Science.gov (United States)

    Akimoto, Ryo; Tokugawa, Takehiro; Yamamoto, Yutaro; Yamataka, Hiroshi

    2012-04-20

    The Schmidt rearrangement of substituted 3-phenyl-2-butanone with trimethylsilyl azide in 90% (v/v) aqueous TFA gave two types of product, fragmentation and rearrangement, the ratio of which depends on the substituent: more fragmentation for a more electron-donating substituent. Rate measurements by azotometry indicated the presence of an induction period, and the pseudo-first-order rate constants showed saturation kinetics with respect to the azide concentration. It was indicated that the reaction proceeds through pre-equilibrium in the formation of iminodiazonium (ID) ion and that the N(2) liberation from the ID ion is rate-determining. Under high azide concentration conditions, where the effective reactant is the ID ion, the reaction gave a linear Hammett plot with a ρ value of -0.50. The observed substituent effects on the rate and the product selectivity imply that path bifurcation on the way from the rate-determining TS to the product states occurs, as suggested by previous molecular dynamics simulations, in a similar manner to the analogous Beckmann rearrangement/fragmentation reactions. © 2012 American Chemical Society

  1. 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.

  2. 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.

  3. Pressure dependence of the absolute rate constant for the reaction OH + C2H2 from 228 to 413 K

    Science.gov (United States)

    Michael, J. V.; Nava, D. F.; Payne, W. A.; Stief, L. J.; Borkowski, R. P.

    1980-01-01

    The pressure dependence of the absolute rate constant for the reaction of the hydroxyl radical with acetylene, important in both atmospheric and combustion chemistry, is determined for temperatures between 228 and 413 K. The flash photolysis-resonance fluorescence technique was employed at five temperatures over wide ranges of pressure and acetylene concentrations, with the OH produced by water photolysis and hydroxyl resonance fluorescent photons measured by multiscaling techniques. Results indicate that, except at the lowest temperature, the bimolecular rate constant for the reaction depends strongly on total pressure, with the pressure effect becoming more pronounced with increasing temperature. At limiting high pressures, the rate constant is found to be equal to 6.83 + or - 1.19 x 10 to the -12th exp (-646 + or - 47/T) cu cm/molecule per sec, where T is the temperature. Results thus demonstrate the importance of environmental conditions in theoretical studies of atmospheric and combustion product compositions

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

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Grace; Earl, Matthew A; Yu, Cedric X [Department of Radiation Oncology, University of Maryland School of Medicine, Baltimore, MD (United States)], E-mail: cyu002@umaryland.edu

    2009-11-07

    Single-arc intensity-modulated arc therapy (IMAT) has gained worldwide interest in both research and clinical implementation due to its superior plan quality and delivery efficiency. Single-arc IMAT techniques such as the Varian RapidArc(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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-10-15

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

  6. Absolute rate constants for the reaction of NO3 radicals with a series of dienes at 295 K

    DEFF Research Database (Denmark)

    Ellermann, T.; Nielsen, O.J.; Skov, H.

    1992-01-01

    The rate constants for the reaction of NO3 radicals with a series of 7 dienes, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, trans-1,3-pentadiene, cis-1,3-pentadiene, trans,trans-2,4-hexadiene, and 1,3-cyclohexadiene, were measured at 295 K and at a total pressure of 1 atm. The rate constant...... were obtained using the absolute technique of pulse radiolysis combined with kinetic UV-VIS spectroscopy. The results are discussed in terms of reactivity trends and previous literature data....

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

    Science.gov (United States)

    Nguyen, Thanh Lam; Stanton, John F.

    2017-10-01

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

  8. Polychlorinated ethane reaction with zero-valent zinc: pathways and rate control

    Science.gov (United States)

    Arnold, William A.; Ball, William P.; Roberts, A. Lynn

    1999-12-01

    Efficient design of zero-valent metal permeable `barriers' for the reduction of organohalides requires information regarding the pertinent reaction rates as well as an understanding of the resultant distribution of products. In this study, the pathways and kinetics for reaction of polychlorinated ethanes with Zn(0) have been examined in batch reactors. Reductive β-elimination was the only route through which hexachloroethane (HCA), 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), 1,1,2-trichloroethane (1,1,2-TCA) and 1,2-dichloroethane (1,2-DCA) reacted. Pentachloroethane (PCA) reacted via concurrent reductive β-elimination (93%) and hydrolysis (7%). As previously demonstrated, 1,1,1-trichloroethane (1,1,1-TCA) and 1,1-dichloroethane (1,1-DCA) reacted predominantly via reductive α-elimination. Attempts to correlate BET surface area-normalized rate constants ( kSA-BET) with one-electron reduction potential ( E1) met with limited success, as HCA, PCA, 1,1,1,2-TeCA, and 1,1,1-TCA reacted at nearly identical rates despite substantial differences in E1 values. Comparison of the pseudo-first-order rate constants ( kobs) for these species with rate constants ( kLa) obtained from a correlation for mass transfer to suspended particles revealed that the reaction of these species was mass transfer limited even though reaction rates were unaffected by mixing speed. Calculations suggest that mass transfer limitations may also play a role in the design of treatment systems for highly reactive species, with overall rate constants predicted to increase with flow velocity.

  9. 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.

  10. Clinical evaluation of the efficacy and safety of a constant rate infusion of dexmedetomidine for postoperative pain management in dogs

    NARCIS (Netherlands)

    Valtolina, C.|info:eu-repo/dai/nl/412503034; Robben, J.H.|info:eu-repo/dai/nl/266740790; Uilenreef, J.J.|info:eu-repo/dai/nl/30483095X; Murrell, J.C.; Aspegrén, J.; McKusick, B.C.; Hellebrekers, L.J.|info:eu-repo/dai/nl/073499234

    2009-01-01

    Vet Anaesth Analg. 2009 Jul;36(4):369-83. Epub 2009 May 12. Clinical evaluation of the efficacy and safety of a constant rate infusion of dexmedetomidine for postoperative pain management in dogs. Valtolina C, Robben JH, Uilenreef J, Murrell JC, Aspegrén J, McKusick BC, Hellebrekers LJ. Department

  11. Fluorescence anisotropy-based measurement of Pseudomonas aeruginosa penicillin-binding protein 2 transpeptidase inhibitor acylation rate constants.

    Science.gov (United States)

    Shapiro, Adam B; Gao, Ning; Gu, Rong-Fang; Thresher, Jason

    2014-10-15

    High-molecular-weight penicillin-binding proteins (PBPs) are essential integral membrane proteins of the bacterial cytoplasmic membrane responsible for biosynthesis of peptidoglycan. They are the targets of antibacterial β-lactam drugs, including penicillins, cephalosporins, and carbapenems. β-Lactams covalently acylate the active sites of the PBP transpeptidase domains. Because β-lactams are time-dependent inhibitors, quantitative assessment of the inhibitory activity of these compounds ideally involves measurement of their second-order acylation rate constants. We previously described a fluorescence anisotropy-based assay to measure these rate constants for soluble constructs of PBP3 (Anal. Biochem. 439 (2013) 37-43). Here we report the expression and purification of a soluble construct of Pseudomonas aeruginosa PBP2 as a fusion protein with NusA. This soluble PBP2 was used to measure second-order acylation rate constants with the fluorescence anisotropy assay. Measurements were obtained for mecillinam, which reacts specifically with PBP2, and for several carbapenems. The assay also revealed that PBP2 slowly hydrolyzed mecillinam and was used to measure the rate constant for this deacylation reaction. Copyright © 2014 Elsevier Inc. All rights reserved.

  12. Quantitative correlation of absolute hydroxyl radical rate constants with non-isolated effluent organic matter bulk properties in water.

    Science.gov (United States)

    Rosario-Ortiz, Fernando L; Mezyk, Stephen P; Doud, Devin F R; Snyder, Shane A

    2008-08-15

    Absolute second-order rate constants for the reaction between the hydroxyl radical (*OH) and eight water samples containing non-isolated effluent organic matter (EfOM) collected at different wastewater and reclamation sites were measured by electron pulse radiolysis. The measured rate constants ranged from 0.27 to 1.21 x 10(9) Mc(-1) s(-1), with an average value of 0.86 (+/-0.35) x 10(9) Mc(-1) s(-1). These absolute values were 3-5 times faster than previously reported values using natural organic matter and wastewater isolates. The obtained rate constants were correlated (R2 > 0.99) to bulk EfOM properties through an empirical equation that included terms relating to the polarity, apparent molecular weight, and fluorescence index of the effluent organic matter. The obtained data were used to model steady state *OH concentrations during UV advanced oxidation. The steady-state *OH concentration was lower than that obtained using previously reported values for the reaction with dissolved organic matter, indicating that accurate measurement of reaction rate constants at specific sites would greatly improve the design and prediction of the removal of organic contaminants. These results will improve the ability of researchers to accurately model scavenging capacities during the advanced oxidation processtreatment of wastewaters.

  13. 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.

  14. Real-time association rate constant measurement using combination tapered fiber-optic biosensor (CTFOB) dip-probes

    Science.gov (United States)

    Simmonds, Boris; Wang, Chun-Wei; Kapoor, Rakesh

    2010-02-01

    This document reports a novel method of measuring association rate constant (ka) for antibody-antigen interaction using evanescent wave-based combination tapered fiber-optic biosensor (CTFOB) dip-probes. The method was demonstrated by measuring association rate constant for bovine serum albumin (BSA) and anti-BSA antibody interaction. "Direct method" was used for detection; goat anti-BSA "capture" antibodies were immobilized on the probe surfaces while the antigen (BSA) was directly labeled with Alexa 488 dye. The probes were subsequently submerged in 3nM Labeled BSA in egg albumin (1 mg/ml). The fluorescence signal recorded was proportional to BSA anti-BSA conjugates and continuous signal was acquired suing a fiber optic spectrometer (Ocean Optics, Inc.). A 476 nm diode laser was use as an excitation source. Association constant was estimated from a plot of signal as a function of time. Measured association rate constant ka for the binding of BSA with anti-BSA at room temperature is (8.33 +/- 0.01) x 104 M-1s-1.

  15. 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

  16. Theoretical evaluation of non-uniform skin effect on aquifer response under constant rate pumping

    Science.gov (United States)

    Chen, Chia-Shyun; Chang, Chien-Chieh

    2006-02-01

    Under field conditions, well skin may be non-uniformly distributed over the screen section. To investigate such non-uniform skin effect on aquifer response, a model is developed where the non-uniform skin effect is represented by an arbitrary piecewise continuous skin function Sk( z) imposed on the boundary of the pumping well. Wellbore storage is taken into account in the pumping well. Due to Sk( z) the model solutions are in terms of non-orthonormal functions, and the Gram-Schmidt method is employed to determine them. It is found that the wellbore flux distribution of the pumping well Qw( z, t) is inversely related to the variation of Sk( z), creating three dimensional flow in the vicinity of the pumping well. This three dimensional flow exists even when wellbore storage is absent in the pumping well, which is different from the fact that uniform skin effect can influence aquifer drawdown only when wellbore storage exists in the pumping well. However, the three dimensional flow evolves to radial flow at farther distances, where the non-uniform skin effect is transformed into a uniform one that can be represented by a constant skin factor equal to the vertical average of Sk( z) weighted by Qw( z, t). The conventional well hydraulics models of a constant skin factor can thus be used to deal with non-uniform skin problems in the radial flow regime or when vertically average drawdown is concerned.

  17. 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.

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

    Science.gov (United States)

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

    2016-05-26

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

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

    NARCIS (Netherlands)

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

    2014-01-01

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

  20. Temperature dependence of the rate constant for the bimolecular recombination of Cl-2 in water—A pulse radiolysis study

    Science.gov (United States)

    Szala-Bilnik, J.; Pierscieniewska, P.; Wolszczak, M.; Swiatla-Wojcik, D.

    2014-04-01

    The rate constant for the disproportionation of Cl-2 in water has been determined for the temperature range 22-87 °C using pulse radiolysis of 0.1 M NaCl+1 mM HClO4 aqueous solution. The rate constant for the decay of Cl-2 has been found to be 2×(7.35±0.53)×108 M-1 s-1 at 22 °C (at zero ionic strength). The determined activation energy, Ea=10.89±0.37 kJ mol-1, is less than expected for diffusion-controlled reactions. A good fit to the Noyes equation (1/kobs=1/kdiff+1/kreact) has been obtained assuming the reaction step is activationless with kreact=A‧T.

  1. Equilibrium Fermi's Golden Rule Charge Transfer Rate Constants in the Condensed Phase: The Linearized Semiclassical Method vs Classical Marcus Theory.

    Science.gov (United States)

    Sun, Xiang; Geva, Eitan

    2016-05-19

    In this article, we present a comprehensive comparison between the linearized semiclassical expression for the equilibrium Fermi's golden rule rate constant and the progression of more approximate expressions that lead to the classical Marcus expression. We do so within the context of the canonical Marcus model, where the donor and acceptor potential energy surface are parabolic and identical except for a shift in both the free energies and equilibrium geometries, and within the Condon region. The comparison is performed for two different spectral densities and over a wide range of frictions and temperatures, thereby providing a clear test for the validity, or lack thereof, of the more approximate expressions. We also comment on the computational cost and scaling associated with numerically calculating the linearized semiclassical expression for the rate constant and its dependence on the spectral density, temperature, and friction.

  2. Comparison of calculated and experimentally resolved rate constants for excitation energy transfer in C-phycocyanin. 2. Trimers

    Energy Technology Data Exchange (ETDEWEB)

    Debreczeny, M.F.; Sauer, K. [Lawrence Berkeley Lab., CA (United States); Zhou, J.; Bryant, D.A. [Pennsylvania State Univ., University Park, PA (United States)

    1995-05-18

    Resolution of the absorption spectrum of the {beta}{sub 155} chromophore in C-phycocyanin (PC) trimers is achieved by comparison of the steady state absorption spectra of ({alpha}{sup PC}{beta}{sup PC}){sub 3} and ({alpha}{sup PC}{beta}{sup *}){sub 3}. Comparison of the anisotropy decays of ({alpha}{sup PC}{beta}{sup PC}){sub 3} and ({alpha}{sup PC}{beta}{sup *}){sub 3} also greatly aids in the assignment of the dominant kinetic processes in PC trimers. A comparison is made of calculated Foerster rate constants for energy transfer with those rate constants resolved experimentally in the PC trimers. 35 refs.., 10 figs., 2 tabs.

  3. Comparison of calculated and experimentally resolved rate constants for excitation energy transfer in C-phycocyanin. 1. Monomers

    Energy Technology Data Exchange (ETDEWEB)

    Debreczeny, M.P.; Sauer, K. [Lawrence Berkeley Lab., CA (United States); Zhou, J.; Bryant, D.A. [Pennsylvania State Univ., University Park, PA (United States)

    1995-05-18

    Rate constants for excitation energy transfer in light-harvesting protein, C-phycocyanin (PC), in the monomeric aggregation state, isolated from the cyanobacterium cynechococcus sp. PCC 7002, are calculated, using Foerster theory and compared with the results of time-resolved fluorescence measurements. The assignments of the energy-transfer rate constants in PC monomers are confirmed here by time-resolved fluorescence anisotropy measurements of the PC monomers isolated from both the wild-type and a mutant strain (cpcB/C155S) whose PC is missing the {beta}{sub 155} chromophore. It is concluded that the Foerster model of resonant energy transfer in the weak coupling limit successfully describes the dominant energy-transfer processes in this protein in the monomeric state. 31 refs., 3 figs., 4 tabs.

  4. 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...

  5. Stability analysis of 4-species Aβaggregation model: A novel approach to obtaining physically meaningful rate constants.

    Science.gov (United States)

    Ghag, G; Ghosh, P; Mauro, A; Rangachari, V; Vaidya, A

    2013-11-01

    Protein misfolding and concomitant aggregation towards amyloid formation is the underlying biochemical commonality among a wide range of human pathologies. Amyloid formation involves the conversion of proteins from their native monomeric states (intrinsically disordered or globular) to well-organized, fibrillar aggregates in a nucleation-dependent manner. Understanding the mechanism of aggregation is important not only to gain better insight into amyloid pathology but also to simulate and predict molecular pathways. One of the main impediments in doing so is the stochastic nature of interactions that impedes thorough experimental characterization and the development of meaningful insights. In this study, we have utilized a well-known intermediate state along the amyloid- β peptide aggregation pathway called protofibrils as a model system to investigate the molecular mechanisms by which they form fibrils using stability and perturbation analysis. Investigation of protofibril aggregation mechanism limits both the number of species to be modeled (monomers, and protofibrils), as well as the reactions to two (elongation by monomer addition, and protofibril-protofibril lateral association). Our new model is a reduced order four species model grounded in mass action kinetics. Our prior study required 3200 reactions, which makes determining the reaction parameters prohibitively difficult. Using this model, along with a linear perturbation argument, we rigorously determine stable ranges of rate constants for the reactions and ensure they are physically meaningful. This was accomplished by finding the ranges in which the perturbations dieout in a five-parameter sweep, which includes the monomer and protofibril equilibrium concentrations and three of the rate constants. The results presented are a proof-of-concept method in determining meaningful rate constants that can be used as a bonafide way for determining accurate rate constants for other models involving complex

  6. Quantum wave packet calculation of reaction probabilities, cross sections, and rate constants for the C(1D) + HD reaction

    Science.gov (United States)

    Gogtas, Fahrettin; Bulut, Niyazi; Akpinar, Sinan

    The time-dependent real wave packet method has been used to study the C(1D) + HD reaction. The state-to-state and state-to-all reactive scattering probabilities for a broad range of energies are calculated at zero total angular momentum. The probabilities for J > 0 are estimated from accurately computed J = 0 probabilities by using the J-shifting approximation. The integral cross sections for a large energy range, and thermal rate constants are calculated.

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

    Science.gov (United States)

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

    2016-07-01

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

  8. Structure-activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase

    Science.gov (United States)

    Doussin, J.-F.; Monod, A.

    2013-12-01

    In the atmosphere, one important class of reactions occurs in the aqueous phase in which organic compounds are known to undergo oxidation towards a number of radicals, among which OH radicals are the most reactive oxidants. In 2008, Monod and Doussin have proposed a new structure-activity relationship (SAR) to calculate OH-oxidation rate constants in the aqueous phase. This estimation method is based on the group-additivity principle and was until now limited to alkanes, alcohols, acids, bases and related polyfunctional compounds. In this work, the initial SAR is extended to carbonyl compounds, including aldehydes, ketones, dicarbonyls, hydroxy carbonyls, acidic carbonyls, their conjugated bases, and the hydrated form of all these compounds. To do so, only five descriptors have been added and none of the previously attributed descriptors were modified. This extension leads now to a SAR which is based on a database of 102 distinct compounds for which 252 experimental kinetic rate constants have been gathered and reviewed. The efficiency of this updated SAR is such that 58% of the rate constants could be calculated within ±20% of the experimental data and 76% within ±40% (respectively 41 and 72% for the carbonyl compounds alone).

  9. Channel specific rate constants for reactions of O(1D) with HCl and HBr

    Science.gov (United States)

    Wine, P. H.; Wells, J. R.; Ravishankara, A. R.

    1986-01-01

    The absolute rate coefficients and product yields for reactions of O(1D) with HCl(1) and HBr(2) at 287 K are presently determined by means of the time-resolved resonance fluorescence detection of O(3P) and H(2S) in conjunction with pulsed laser photolysis of O3/HX/He mixtures. Total rate coefficients for O(1D) removal are found to be, in units of 10 to the -10th cu cm/molecule per sec, k(1) = 1.50 + or - 0.18 and k(2) 1.48 + or - 0.16; the absolute accuracy of these rate coefficients is estimated to be + or - 20 percent.

  10. 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.

  11. 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.

  12. Constant Flux Proxies and Pleistocene Sediment Accumulation Rates on the Juan de Fuca Ridge in the Northeast Pacific

    Science.gov (United States)

    Middleton, J. L.; Mukhopadhyay, S.; Langmuir, C. H.; Costa, K.; McManus, J. F.; d'Almeida, M.; Huybers, P. J.; Winckler, G.

    2016-12-01

    Mass accumulation rates of marine sediments are often employed to constrain deposition rates of important proxies such as terrigenous dust, carbonate, and biogenic opal to quantitatively examine variations in continental aridity, atmospheric transport, and biologic productivity across changing climatic conditions. However, deposition rates that are estimated using traditional mass accumulation rates calculated from sediment core age models can be subject to bias from lateral sediment transport and limited age model resolution. Constant flux proxies, such as extraterrestrial helium-3 (3HeET) and excess thorium-230 (230ThXS), can be used to calculate vertical sediment accumulation rates that are independent of age model uncertainties and the effects of lateral sediment transport. While a short half-life limits analyses of 230ThXS to the past 500 ka, 3HeET is stable and could be used to constrain sedimentary fluxes during much of the Cenozoic. Despite the vast paleoceanographic potential of constant flux proxies, few studies have directly compared the behavior of 230ThXS and 3HeET using measurements from the same samples. Sediment grain size fractionation and local scavenging effects may differentially bias one or both proxy systems and complicate the interpretation of 230ThXS or 3HeET data. We will present a new record of vertical sediment accumulation rates spanning the past 600 ka in the Northeast Pacific constrained using analyses of both 3HeET and 230ThXS in two sediment cores from cruise AT26-19 on the Juan de Fuca Ridge. Such a record allows for intercomparison of both constant flux proxies in the mid-ocean ridge environment and examination of sedimentary behavior across multiple glacial cycles. The 230ThXS-derived accumulation rates typically range from 0.5 to 2 g cm-2 ka-1 over the past 450 ka, with periods of maximum deposition coinciding with glacial maxima. Preliminary results of samples analyzed with both 3HeET and 230ThXS indicate relative consistency

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

    DEFF Research Database (Denmark)

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

    2010-01-01

    It is well known that face/core debond crack propagation is governed by the critical energy release rate (fracture toughness) and mode-mixity at the crack tip. Thus, the current study focuses on the developing of a methodology to perform fatigue crack growth experiments of debonded sandwich...... and better control of loading conditions at the crack tip will be the most relevant outcomes of using the proposed fatigue test method....... structures under well controlled cyclic energy release rate and mode-mixity. The proposed methodology uses the mixed mode bending (MMB) sandwich specimen and MMB test rig. Crack length measurements are based on an analytically available compliance expression. Accurate fatigue crack growth measurements...

  14. A Simple Formula for Local Burnup and Isotope Distributions Based on Approximately Constant Relative Reaction Rate

    Directory of Open Access Journals (Sweden)

    Cenxi Yuan

    2016-01-01

    Full Text Available A simple and analytical formula is suggested to solve the problems of the local burnup and the isotope distributions. The present method considers two extreme conditions of neutrons penetrating the fuel rod. Based on these considerations, the formula is obtained to calculate the reaction rates of 235U, 238U, and 239Pu and straightforward the local burnup and the isotope distributions. Starting from an initial burnup level, the parameters of the formula are fitted to the reaction rates given by a Monte Carlo (MC calculation. Then the present formula independently gives very similar results to the MC calculation from the starting to high burnup level but takes just a few minutes. The relative reaction rates are found to be almost independent of the radius (except (n,γ of  238U and the burnup, providing a solid background for the present formula. A more realistic examination is also performed when the fuel rods locate in an assembly. A combination of the present formula and the MC calculation is expected to have a nice balance between the numerical accuracy and time consumption.

  15. An Effective Continuum Model for the Liquid-to-Gas Phase Change in a Porous Medium Driven by Solute Diffusion: I. Constant Pressure Decline Rates

    Energy Technology Data Exchange (ETDEWEB)

    Tsimpanogiannis, Ioannis N.; Yortsos, Yanis C.

    2001-08-15

    This report, focuses on the isothermal gas phase growth from a supersaturated, slightly compressible, binary liquid in a porous medium. This is driven by mass transfer, the extent of which is controlled by the application of either a constant-rate decline of the system pressure or the withdrawal of the liquid at a constant rate. This report deals with the first process. Pressure depletion due to constant-rate liquid withdrawal is analyzed in a companion report .

  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

    It is a well known fact, that water plays an important part in almost all biological systems and that inclusion of solvation effects might therefore be of utmost importance in studies of radiation damage to DNA. In the present investigation we have studied the effect of different solvation models...... 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...

  17. Using Data Assimilation Methodology to Estimate Spatially-Variable Denitrification Rate Constants in an Irrigated Agricultural Aquifer System

    Science.gov (United States)

    Bailey, R. T.; Bau, D. A.; Gates, T. K.

    2011-12-01

    With numerical models being increasingly used to assess groundwater quality through the simulation of the fate and transport of reactive solutes in aquifer systems, it has become paramount to accurately estimate parameters, such as chemical reaction rates, that govern the subsistence of these solutes in groundwater. Such an effort is required especially in models applied to regional aquifer systems, where environmental conditions vary substantially over the spatial extent. As part of an overall effort to estimate spatially-variable parameters in chemically-active aquifer systems, we present the use of a data assimilation scheme, the Ensemble Smoother (ES), to improve estimates of spatially-variable first-order kinetic denitrification rate constants within an irrigated agricultural river-aquifer system, in light of the fact that these rates often dictate the migration of nitrate (NO3) within agricultural watersheds. Based on the Kalman Filter methodology, the ES combines (or merges) together prior uncertain parameter values, associated forecast model results, and measurement data to provide an updated, corrected model state that approaches the system state from which the measurements were taken. In this study, (NO3) concentration data are used to condition the denitrification rate constants using the correlation between rate constants and groundwater (NO3) concentration as established through the reactive transport model. As a fundamental step in eventually applying the ES scheme to an aquifer system within Colorado's Lower Arkansas River Basin, we evaluate the scheme for a synthetic aquifer system with hydrologic and chemical complexities similar to the real-world system. Complexities include heterogeneously distributed hydraulic conductivity, cropping/fallowing patterns, deep percolation, canal seepage, groundwater flows to the river, heterotrophic and autotrophic denitrification simulated using a dual-Monod approach, and leaching concentrations assigned to both

  18. Reactions of electronically excited boron atoms. Quenching rate constants and the radiative lifetime of the 4p 2P state

    Science.gov (United States)

    Yang, Xuefeng; Dagdigian, Paul J.

    1992-12-01

    Collisional quenching and radiative decay of the 4p 2P level of the boron atom has been studied in a cell experiment, in which B atoms are prepared by 266 nm multiphoton dissociation of BBr 3 and the 4p 2P level is prepared by sequential 2-photon absorption through the 3s 2S level. A radiative lifetime of 360 ± 50 ns is derived for B (4p 2P) by extrapolation of the measured decay rates versus BBr 3 partial pressure in several Torr helium buffer gas. Bimolecular quenching rate constants were also determined for a number of atomic and molecular species from the dependence of the B (4p 2P) decay rate on the quencher gas partial pressure. The quenching rate constants for the molecular species were quite large (≈(1-2)×10 -9 molecule -1 cm 3 s -1), presumably reflecting the small B (4p 2P) ionization potential and the rapid removal of the excited state by chemical reaction.

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

    Science.gov (United States)

    Dateo, Christopher E.

    1994-01-01

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

  20. The role of relative rate constants in determining surface state phenomena at semiconductor-liquid interfaces.

    Science.gov (United States)

    Iqbal, Asif; Hossain, Md Sazzad; Bevan, Kirk H

    2016-10-26

    In this work, we present a theoretical study of surface state occupation statistics at semiconductor-liquid interfaces, as it pertains to the evolution of H 2 and O 2 through water splitting. Our approach combines semiclassical charge transport and electrostatics at the semiconductor-liquid junction, with a master rate equation describing surface state mediated electron/hole transfer. As a model system we have studied the TiO 2 -water junction in the absence of illumination, where it is shown that surface states might not always equilibrate with the semiconductor. Non-trivial electrostatics, for example including a shifting of the Mott-Schottky plateau in capacitive measurements, are explored when deep-level surface states partially equilibrate with the liquid. We also endeavor to explain observations of non-linearity present in Mott-Schottky plots, as they pertain to surface state occupation statistics. In general, it is intended that the results of this work will serve to further the use and development of quantitative device modeling techniques in the description of H 2 evolution at semiconductor-liquid junctions.

  1. 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.

  2. 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

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

    Science.gov (United States)

    Cannon, William R.; Baker, Scott E.

    2017-10-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-06-01

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

  5. Determination of Chemical Kinetic Rate Constants of a Model for Carbothermal Processing of Lunar Regolith Simulant Using Methane

    Science.gov (United States)

    Balasubramaniam, R; Gokoglu, S.; Hegde, U.

    2009-01-01

    We have previously developed a chemical conversion model of the carbothermal processing of lunar regolith using methane to predict the rate of production of carbon monoxide. In this carbothermal process, gaseous methane is pyrolyzed as it flows over the hot surface of a molten zone of lunar regolith and is converted to carbon and hydrogen. Hydrogen is carried away by the exiting stream of gases and carbon is deposited on the melt surface. The deposited carbon mixes with the melt and reacts with the metal oxides in it to produce carbon monoxide that bubbles out of the melt. In our model, we assume that the flux of carbon deposited is equal to the product of the surface reaction rate constant gamma and the concentration of methane adjacent to the melt surface. Similarly, the rate of consumption of carbon per unit volume in the melt is equal to the product of the melt reaction rate constant k and the concentrations of carbon and metal oxide in the melt. In this paper, we describe our effort to determine gamma and k by comparison of the predictions from our model with test data obtained by ORBITEC (Orbital Technologies Corporation). The concentration of methane adjacent to the melt surface is a necessary input to the model. It is inferred from the test data by a mass balance of methane, adopting the usual assumptions of the continuously-stirred-tank-reactor model, whereby the average concentration of a given gaseous species equals its exit concentration. The reaction rates gamma and k have been determined by a non-linear least-squares fit to the test data for the production of carbon monoxide and the fraction of the incoming methane that is converted. The comparison of test data with our model predictions using the determined chemical kinetic rate constants provides a consistent interpretation of the process over the full range of temperatures, pressures, and methane flow rates used in the tests, thereby increasing our confidence to use the model for scale-up purposes.

  6. Relation between electrical percolation and rate constant for exchange of material between droplets in water in oil microemulsions

    Energy Technology Data Exchange (ETDEWEB)

    Jada, A.; Lang, J.; Zana, R. (Institut Charles Sadron, Strasbourg (France))

    1989-01-12

    The rate constant k{sub e} associated with the exchange of material upon collisions between droplets in ternary water in oil microemulsions stabilized by ionic surfactants has been determined by a time-resolved fluorescence method. The electrical conductivity of the same systems has been investigated. It appears that percolative conduction occurs only in systems where k{sub e} is larger than (1-2) {times} 10{sup 9} M{sup {minus}1} s{sup {minus}1}. This result supports the hypothesis that above percolation threshold the conductivity is mainly due to the motion of counterions through water channels or fusion between droplets in droplet clusters.

  7. 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.

  8. 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)

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

    Science.gov (United States)

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

    2017-04-01

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

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

    Science.gov (United States)

    Dail, Michelle K; Mezyk, Stephen P

    2010-08-19

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

  11. Rationale choosing interval of a piecewise-constant approximation of input rate of non-stationary queue system

    Science.gov (United States)

    Korelin, Ivan A.; Porshnev, Sergey V.

    2018-01-01

    The paper demonstrates the possibility of calculating the characteristics of the flow of visitors to objects carrying out mass events passing through checkpoints. The mathematical model is based on the non-stationary queuing system (NQS) where dependence of requests input rate from time is described by the function. This function was chosen in such way that its properties were similar to the real dependencies of speed of visitors arrival on football matches to the stadium. A piecewise-constant approximation of the function is used when statistical modeling of NQS performing. Authors calculated the dependencies of the queue length and waiting time for visitors to service (time in queue) on time for different laws. Time required to service the entire queue and the number of visitors entering the stadium at the beginning of the match were calculated too. We found the dependence for macroscopic quantitative characteristics of NQS from the number of averaging sections of the input rate.

  12. The effects of molecular weight on the single lap shear creep and constant strain rate behavior of thermoplastic polyimidesulfone adhesive

    Science.gov (United States)

    Dembosky, Stanley K.; Sancaktar, Erol

    1985-01-01

    The bonded shear creep and constant strain rate behaviors of zero, one, and three percent endcapped thermoplastic polyimidesulfone adhesive were examined at room and elevated temperatures. Endcapping was accomplished by the addition of phthalic anhydrides. The primary objective was to determine the effects of molecular weight on the mechanical properties of the adhesive. Viscoelastic and nonlinear elastic constitutive equations were utilized to model the adhesive. Ludwik's and Crochet's relations were used to describe the experimental failure data. The effects of molecular weight changes on the above mentioned mechanical behavior were assessed. The viscoelastic Chase-Goldsmith and elastic nonlinear relations gave a good fit to the experimental stress strain behavior. Crochet's relations based on Maxwell and Chase-Goldsmith models were fit to delayed failure data. Ludwik's equations revealed negligible rate dependence. Ultimate stress levels and the safe levels for creep stresses were found to decrease as molecular weight was reduced.

  13. 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).

  14. Solar photocatalytic degradation of mono azo methyl orange and diazo reactive green 19 in single and binary dye solutions: adsorbability vs photodegradation rate.

    Science.gov (United States)

    Ong, Soon-An; Min, Ohm-Mar; Ho, Li-Ngee; Wong, Yee-Shian

    2013-05-01

    The objective of this study was to examine the effects of adsorbability and number of sulfonate group on solar photocatalytic degradation of mono azo methyl orange (MO) and diazo Reactive Green 19 (RG19) in single and binary dye solutions. The adsorption capacity of MO and RG19 onto the TiO₂ was 16.9 and 26.8 mg/g, respectively, in single dye solution, and reduced to 5.0 and 23.1 mg/g, respectively, in the binary dye solution. The data obtained for photocatalytic degradation of MO and RG19 in single and binary dye solution were well fitted with the Langmuir-Hinshelwood kinetic model. The pseudo-first-order rate constants of diazo RG19 were significant higher than the mono azo MO either in single or binary dye solutions. The higher number of sulfonate group in RG19 contributed to better adsorption capacity onto the surface of TiO₂ than MO indicating greater photocatalytic degradation rate.

  15. Effect of application rate on fumigant degradation in five agricultural soils.

    Science.gov (United States)

    Qin, Ruijun; Gao, Suduan; Ajwa, Husein; Hanson, Bradley D

    2016-01-15

    Soil fumigation is an important pest management tool for many high value crops. To address the knowledge gap of how fumigant concentration in soil impacts dissipation, and thereby efficacy, this research determined the degradation characteristics of four fumigants as affected by application rate. Laboratory incubation experiments were conducted to determine degradation rates of 1,3-dichloropropene (both cis- and trans isomers), chloropicrin (CP), dimethyl disulfide (DMDS), and methyl iodide (MeI) in five agricultural soils. Fitted to pseudo first-order kinetics, the degradation rate constant (k) of CP, DMDS, and MeI decreased significantly as application rate increased while the 1,3-D isomers were the least affected by rate. Half-lives increased 12, 17, and 6-fold for CP, DMDS, and MeI, respectively, from the lowest to the highest application rate. At low application rates, the degradation rate of all fumigants in the Hueneme sandy loam soil was reduced by 50-95% in sterilized soil compared to the biologically active controls. However, this difference became much smaller or disappeared at high application rates indicating that biodegradation dominates at low concentrations but chemical degradation is more important at high concentrations. When co-applied, CP degradation was enhanced with biodegradation remained above 50%, while 1,3-D degradation was either reduced or not changed. Among the fumigants tested, the relative importance of biodegradation was DMDS>CP>MeI>1,3-D. These results are useful for determining effective fumigation rates and for informing regulatory decisions on emission controls under different fumigation scenarios. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. The Multicenter Aerobic Iron Respiratory Chain of Acidithiobacillus ferrooxidans Functions as an Ensemble with a Single Macroscopic Rate Constant.

    Science.gov (United States)

    Li, Ting-Feng; Painter, Richard G; Ban, Bhupal; Blake, Robert C

    2015-07-24

    Electron transfer reactions among three prominent colored proteins in intact cells of Acidithiobacillus ferrooxidans were monitored using an integrating cavity absorption meter that permitted the acquisition of accurate absorbance data in suspensions of cells that scattered light. The concentrations of proteins in the periplasmic space were estimated to be 350 and 25 mg/ml for rusticyanin and cytochrome c, respectively; cytochrome a was present as one molecule for every 91 nm(2) in the cytoplasmic membrane. All three proteins were rapidly reduced to the same relative extent when suspensions of live bacteria were mixed with different concentrations of ferrous ions at pH 1.5. The subsequent molecular oxygen-dependent oxidation of the multicenter respiratory chain occurred with a single macroscopic rate constant, regardless of the proteins' in vitro redox potentials or their putative positions in the aerobic iron respiratory chain. The crowded electron transport proteins in the periplasm of the organism constituted an electron conductive medium where the network of protein interactions functioned in a concerted fashion as a single ensemble with a standard reduction potential of 650 mV. The appearance of product ferric ions was correlated with the reduction levels of the periplasmic electron transfer proteins; the limiting first-order catalytic rate constant for aerobic respiration on iron was 7,400 s(-1). The ability to conduct direct spectrophotometric studies under noninvasive physiological conditions represents a new and powerful approach to examine the extent and rates of biological events in situ without disrupting the complexity of the live cellular environment. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  17. The Multicenter Aerobic Iron Respiratory Chain of Acidithiobacillus ferrooxidans Functions as an Ensemble with a Single Macroscopic Rate Constant*

    Science.gov (United States)

    Li, Ting-Feng; Painter, Richard G.; Ban, Bhupal; Blake, Robert C.

    2015-01-01

    Electron transfer reactions among three prominent colored proteins in intact cells of Acidithiobacillus ferrooxidans were monitored using an integrating cavity absorption meter that permitted the acquisition of accurate absorbance data in suspensions of cells that scattered light. The concentrations of proteins in the periplasmic space were estimated to be 350 and 25 mg/ml for rusticyanin and cytochrome c, respectively; cytochrome a was present as one molecule for every 91 nm2 in the cytoplasmic membrane. All three proteins were rapidly reduced to the same relative extent when suspensions of live bacteria were mixed with different concentrations of ferrous ions at pH 1.5. The subsequent molecular oxygen-dependent oxidation of the multicenter respiratory chain occurred with a single macroscopic rate constant, regardless of the proteins' in vitro redox potentials or their putative positions in the aerobic iron respiratory chain. The crowded electron transport proteins in the periplasm of the organism constituted an electron conductive medium where the network of protein interactions functioned in a concerted fashion as a single ensemble with a standard reduction potential of 650 mV. The appearance of product ferric ions was correlated with the reduction levels of the periplasmic electron transfer proteins; the limiting first-order catalytic rate constant for aerobic respiration on iron was 7,400 s−1. The ability to conduct direct spectrophotometric studies under noninvasive physiological conditions represents a new and powerful approach to examine the extent and rates of biological events in situ without disrupting the complexity of the live cellular environment. PMID:26041781

  18. Bevacizumab reduces the growth rate constants of renal carcinomas: a novel algorithm suggests early discontinuation of bevacizumab resulted in a lack of survival advantage.

    Science.gov (United States)

    Stein, Wilfred D; Yang, James; Bates, Susan E; Fojo, Tito

    2008-10-01

    To hasten cancer drug development, new paradigms are needed to assess therapeutic efficacy. In a randomized phase II study in patients with renal cell carcinoma, 10 microg/kg bevacizumab (Avastin; Genentech, Inc., South San Francisco, CA) administered every 2 weeks resulted in a longer time to progression but a statistically significant difference in overall survival could not be demonstrated. We developed a novel two-phase equation to estimate concomitant rates of tumor regression (regression rate constant) and tumor growth (growth rate constant). This method allows us to assess therapeutic efficacy using tumor measurements gathered while a patient receives therapy in a clinical trial. The growth rate constants of renal cell carcinomas were significantly lower during therapy with 10 microg/kg bevacizumab than those of tumors in patients receiving placebo. In all cohorts the tumor growth rate constants were correlated with survival. That a survival advantage was not demonstrated with bevacizumab appears to have been a result of early discontinuation of bevacizumab. Single-agent bevacizumab significantly affects the growth rate constants of renal cell carcinoma. Extrapolating from the growth rate constants, we conclude that the failure to demonstrate a survival advantage in the original study was a result of premature discontinuation of bevacizumab. The mathematical model described herein has applications to many tumor types and should aid in evaluating the relative efficacies of different therapies. Quantitating tumor growth rate constants using data gathered while patients are enrolled in a clinical trial, as in the present study, may streamline and assist in drug development.

  19. SU-F-T-33: Air-Kerma Strength and Dose Rate Constant by the Full Monte Carlo Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Tsuji, S [Kawasaki Medical School, Kurashiki, Okayama (Japan); Oita, M [Graduate School of Health Sciences, Okayama University, Okayama, Okayama (Japan); Narihiro, N [Kawasaki College of Allied Health Professions, Kurashiki, Okayama (Japan)

    2016-06-15

    Purpose: In general, the air-kerma strength (Sk) has been determined by the energy weighting the photon energy fluence and the corresponding mass-energy absorption coefficient or mass-energy transfer coefficient. Kerma is an acronym for kinetic energy released per unit mass, defined as the sum of the initial kinetic energies of all the charged particles. Monte Carlo (MC) simulations can investigate the kinetic energy of the charged particles after photo interactions and sum the energy. The Sk of {sup 192}Ir source is obtained in the full MC simulation and finally the dose rate constant Λ is determine. Methods: MC simulations were performed using EGS5 with the microSelectron HDR v2 type of {sup 192}Ir source. The air-kerma rate obtained to sum the electron kinetic energy after photoelectric absorption or Compton scattering for transverse-axis distance from 1 to 120 cm with a 10 m diameter air phantom. Absorbed dose in water is simulated with a 30 cm diameter water phantom. The transport cut-off energy is 10 keV and primary photons from the source need two hundred and forty billion in the air-kerma rate and thirty billion in absorbed dose in water. Results: Sk is multiplied by the square of the distance in air-kerma rate and determined by fitting a linear function. The result of Sk is (2.7039±0.0085)*10-{sup −11} µGy m{sup 2} Bq{sup −1} s{sup −1}. Absorbed dose rate in water at 1 cm transverse-axis distance D(r{sub 0}, θ{sub 0}) is (3.0114±0.0015)*10{sup −11} cGy Bq{sup −1} s{sup −1}. Conclusion: From the results, dose rate constant Λ of the microSelectron HDR v2 type of {sup 192}Ir source is (1.1137±0.0035) cGy h{sup −1} U{sup −1} by the full MC simulations. The consensus value conΛ is (1.109±0.012) cGy h{sup −1} U{sup −1}. The result value is consistent with the consensus data conΛ.

  20. The power of size. 2. Rate constants and equilibrium ratios for accumulation of inorganic substances related to species weight.

    Science.gov (United States)

    Hendriks, A J; Heikens, A

    2001-07-01

    Most of the thousands of substances and species that risk assessment has to deal with are not investigated empirically because of financial, practical, and ethical constraints. To facilitate extrapolation, we have developed a model for concentration kinetics of inorganic substances as a function of the exposure concentration of the chemical and the weight and trophic level of the species. The ecological parameters and the resistances that substances encounter during diffusion in water layers were obtained from previous reviews. The other chemical parameters (the resistances for permeation of lipid layers) were calibrated in the present study on 1,062 rate constants for absorption from water, for assimilation from food, and for elimination. Data on all elements and species were collected, but most applied to aquatic species, in particular mollusks and fish, and to transition metals, in particular group IIB (Zn, Cd, Hg). Their ratio was validated on 92 regressions and nine geometric averages, representing thousands of (near-)equilibrium accumulation ratios from laboratory and field studies. Rate constants for absorption and elimination decreased with species weight at an exponent of about -0.25, known from ecological allometry. On average, uptake-rate constants decreased with about the reciprocal square root of the exposure concentration. About 71 and 30% of the variation in absorption and elimination was explained by the model, respectively. The efficiency for assimilation of elements from food appeared to be determined mainly by the food digestibility and the distribution over egested and digested fractions. (Near-)equilibrium accumulation and magnification ratios also decreased with the reciprocal square root of the exposure concentration. The level of the organism-solids concentrations ratios roughly varied between one and two orders of magnitude, depending on the number of elements and species groups investigated. Metal concentrations did not increase at higher

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

  2. Temperature dependence of the rate constant and product channels for the BrO + ClO reaction

    OpenAIRE

    Hills, AJ; Cicerone, RJ; Calvert, JG; Birks, JW

    1988-01-01

    We have measured the rate constant for the reactions BrO + ClO → Br + OClO (6a), BrO + ClO → Br + Cl + O 2 (6b), and BrO + ClO → BrCl + O 2 (6c) over the temperature range 241-408 K and found k 6 = (8.2 ± 1.0) × 10 -12 cm 3 molecule -1 s independent of temperature. Measurement of the individual product branching ratios yielded values for channels 6a, 6b, and 6c equal to 0.55 ± 0.10, 0.45 ± 0.10, and < 0.02, respectively. Measurements of ozone in the stratosphere over Antarctica have s...

  3. 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...... of hydrated electron with H2PO4- was determined to k(20-degrees-C) = 1.5 x 10(7) M-1 s-1 and E(A) = 7.4 kJ mol-1 (1.8 kcal mol-1) in the temperature range 20-200-degrees-C....

  4. 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.

  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. Other paradigms: growth rate constants and tumor burden determined using computed tomography data correlate strongly with the overall survival of patients with renal cell carcinoma.

    Science.gov (United States)

    Stein, Wilfred D; Huang, Hui; Menefee, Michael; Edgerly, Maureen; Kotz, Herb; Dwyer, Andrew; Yang, James; Bates, Susan E

    2009-01-01

    In solid tumors, where curative therapies still elude oncologists, novel paradigms are needed to assess the efficacy of new therapies and those already approved. We used radiologic measurements obtained in patients with metastatic renal cell carcinoma enrolled in a phase II study of the epothilone B analog, ixabepilone (Ixempra), to address this issue. Using a novel 2-phase mathematical equation, we used the radiologic measurements to estimate the concomitant rates of tumor regression and growth (regression and growth rate constants). Eighty-one patients were enrolled on the ixabepilone trial at the time of this analysis. Growth rate constants were determined using computed tomography measurements obtained exclusively while a patient was enrolled on study. The growth rate constants of renal cell carcinomas treated with ixabepilone were significantly reduced compared with those of tumors in patients who received placebo in a previous trial. Furthermore, a correlation with overall survival was found for both the growth rate constant and the initial tumor burden; and this correlation was even stronger when both the growth rate constant and the initial tumor burden were combined. The readily amenable mathematical model described herein has potential applications to many tumor types that can be assessed with imaging modalities. Because the growth rate constant seems to be a surrogate for survival, assessment could aid in the evaluation of relative efficacies of different therapies and perhaps in assessing the potential individual benefit of an experimental therapy.

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

    Science.gov (United States)

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

  8. Dynamics of chest wall volume regulation during constant work rate exercise in patients with chronic obstructive pulmonary disease

    Energy Technology Data Exchange (ETDEWEB)

    Takara, L.S.; Cunha, T.M.; Barbosa, P.; Rodrigues, M.K.; Oliveira, M.F.; Nery, L.E. [Setor de Função Pulmonar e Fisiologia Clínica do Exercício, Disciplina de Pneumologia, Departamento de Medicina, Universidade Federal de São Paulo, São Paulo, SP (Brazil); Neder, J.A. [Setor de Função Pulmonar e Fisiologia Clínica do Exercício, Disciplina de Pneumologia, Departamento de Medicina, Universidade Federal de São Paulo, São Paulo, SP (Brazil); Division of Respiratory and Critical Care Medicine, Department of Medicine, Queen' s University, Kingston, ON (Canada)

    2012-10-15

    This study evaluated the dynamic behavior of total and compartmental chest wall volumes [(V{sub CW}) = rib cage (V{sub RC}) + abdomen (V{sub AB})] as measured breath-by-breath by optoelectronic plethysmography during constant-load exercise in patients with stable chronic obstructive pulmonary disease. Thirty males (GOLD stages II-III) underwent a cardiopulmonary exercise test to the limit of tolerance (Tlim) at 75% of peak work rate on an electronically braked cycle ergometer. Exercise-induced dynamic hyperinflation was considered to be present when end-expiratory (EE) V{sub CW} increased in relation to resting values. There was a noticeable heterogeneity in the patterns of V{sub CW} regulation as EEV{sub CW} increased non-linearly in 17/30 “hyperinflators” and decreased in 13/30 “non-hyperinflators” (P < 0.05). EEV{sub AB} decreased slightly in 8 of the “hyperinflators”, thereby reducing and slowing the rate of increase in end-inspiratory (EI) V{sub CW} (P < 0.05). In contrast, decreases in EEV{sub CW} in the “non-hyperinflators” were due to the combination of stable EEV{sub RC} with marked reductions in EEV{sub AB}. These patients showed lower EIV{sub CW} and end-exercise dyspnea scores but longer Tlim than their counterparts (P < 0.05). Dyspnea increased and Tlim decreased non-linearly with a faster rate of increase in EIV{sub CW} regardless of the presence or absence of dynamic hyperinflation (P < 0.001). However, no significant between-group differences were observed in metabolic, pulmonary gas exchange and cardiovascular responses to exercise. Chest wall volumes are continuously regulated during exercise in order to postpone (or even avoid) their migration to higher operating volumes in patients with COPD, a dynamic process that is strongly dependent on the behavior of the abdominal compartment.

  9. Dynamics of chest wall volume regulation during constant work rate exercise in patients with chronic obstructive pulmonary disease

    Directory of Open Access Journals (Sweden)

    L.S. Takara

    2012-12-01

    Full Text Available This study evaluated the dynamic behavior of total and compartmental chest wall volumes [(V CW = rib cage (V RC + abdomen (V AB] as measured breath-by-breath by optoelectronic plethysmography during constant-load exercise in patients with stable chronic obstructive pulmonary disease. Thirty males (GOLD stages II-III underwent a cardiopulmonary exercise test to the limit of tolerance (Tlim at 75% of peak work rate on an electronically braked cycle ergometer. Exercise-induced dynamic hyperinflation was considered to be present when end-expiratory (EE V CW increased in relation to resting values. There was a noticeable heterogeneity in the patterns of V CW regulation as EEV CW increased non-linearly in 17/30 "hyperinflators" and decreased in 13/30 "non-hyperinflators" (P < 0.05. EEV AB decreased slightly in 8 of the "hyperinflators", thereby reducing and slowing the rate of increase in end-inspiratory (EI V CW (P < 0.05. In contrast, decreases in EEV CW in the "non-hyperinflators" were due to the combination of stable EEV RC with marked reductions in EEV AB. These patients showed lower EIV CW and end-exercise dyspnea scores but longer Tlim than their counterparts (P < 0.05. Dyspnea increased and Tlim decreased non-linearly with a faster rate of increase in EIV CW regardless of the presence or absence of dynamic hyperinflation (P < 0.001. However, no significant between-group differences were observed in metabolic, pulmonary gas exchange and cardiovascular responses to exercise. Chest wall volumes are continuously regulated during exercise in order to postpone (or even avoid their migration to higher operating volumes in patients with COPD, a dynamic process that is strongly dependent on the behavior of the abdominal compartment.

  10. SU-E-T-421: Feasibility Study of Volumetric Modulated Arc Therapy with Constant Dose Rate for Endometrial Cancer

    Energy Technology Data Exchange (ETDEWEB)

    Yang, R; Wang, J [Peking University Third Hospital, Beijing, Beijing (China)

    2014-06-01

    Purpose: To investigate the feasibility, efficiency, and delivery accuracy of volumetric modulated arc therapy with constant dose rate (VMAT-CDR) for whole-pelvic radiotherapy (WPRT) of endometrial cancer. Methods: The nine-Field intensity-modulated radiotherapy (IMRT), VMAT with variable dose-rate (VMAT-VDR), and VMAT-CDR plans were created for 9 patients with endometrial cancer undergoing WPRT. The dose distribution of planning target volume (PTV), organs at risk (OARs), and normal tissue (NT) were compared. The monitor units (MUs) and treatment delivery time were also evaluated. For each VMAT-CDR plan, a dry Run was performed to assess the dosimetric accuracy with MatriXX from IBA. Results: Compared with IMRT, the VMAT-CDR plans delivered a slightly greater V20 of the bowel, bladder, pelvis bone, and NT, but significantly decreased the dose to the high-dose region of the rectum and pelvis bone. The MUs Decreased from 1105 with IMRT to 628 with VMAT-CDR. The delivery time also decreased from 9.5 to 3.2 minutes. The average gamma pass rate was 95.6% at the 3%/3 mm criteria with MatriXX pretreatment verification for 9 patients. Conclusion: VMAT-CDR can achieve comparable plan quality with significant shorter delivery time and smaller number of MUs compared with IMRT for patients with endometrial cancer undergoing WPRT. It can be accurately delivered and be an alternative to IMRT on the linear accelerator without VDR capability. This work is supported by the grant project, National Natural; Science Foundation of China (No. 81071237)

  11. Rate constants and branching ratios for the reaction of CH radicals with NH3: a combined experimental and theoretical study.

    Science.gov (United States)

    Blitz, Mark A; Talbi, Dahbia; Seakins, Paul W; Smith, Ian W M

    2012-06-21

    The reaction between CH radicals and NH(3) molecules is known to be rapid down to at least 23 K {at which temperature k = (2.21 ± 0.17) × 10(-10) cm(3) molecule(-1) s(-1): Bocherel ; et al. J. Phys. Chem. 1996, 100, 3063}. However, there have been only limited theoretical investigations of this reaction and its products are not known. This paper reports (i) ab initio quantum chemical calculations on the energy paths that lead to various reaction products, (ii) calculations of the overall rate constant and branching ratios to different products using transition state and master equation methods, and (iii) an experimental determination of the H atom yield from the reaction. The ab initio calculations show that reaction occurs predominantly via the initial formation of a datively bound HC-NH(3) complex and reveal low energy pathways to three sets of reaction products: H(2)CNH + H, HCNH(2) + H, and CH(3) + NH. The transition state calculations indicate the roles of "outer" and "inner" transition states and yield rate constants between 20 and 320 K that are in moderate agreement with the experimental values. These calculations and those using the master equation approach show that the branching ratio for the most exothermic reaction, to H(2)CNH + H, is ca. 96% throughout the temperature range covered by the calculations, with those to HCNH(2) + H and CH(3) + NH being (4 ± 3)% and <0.3%, respectively. In the experiments, multiple photon dissociation of CHBr(3) was used to generate CH radicals and laser-induced fluorescence at 121.56 nm (VUV-LIF) was employed to observe H atoms. By comparing signals from CH + NH(3) with those from CH + CH(4), where the yield of H atoms is known to be unity, it is possible to estimate that the yield of H atoms from CH + NH(3) is equal to 0.89 ± 0.07 (2σ), in satisfactory agreement with the theoretical estimate.

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

    Science.gov (United States)

    Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

    2014-05-22

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

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

    Science.gov (United States)

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

    2015-01-01

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

  14. Theoretical study on the rate constants for the C2H5 + HBr --> C2H6 + Br reaction.

    Science.gov (United States)

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

    2004-02-01

    The reaction C(2)H(5) + HBr --> C(2)H(6) + Br has been theoretically studied over the temperature range from 200 to 1400 K. The electronic structure information is calculated at the BHLYP/6-311+G(d,p) and QCISD/6-31+G(d) levels. With the aid of intrinsic reaction coordinate theory, the minimum energy paths (MEPs) are obtained at the both levels, and the energies along the MEP are further refined by performing the single-point calculations at the PMP4(SDTQ)/6-311+G(3df,2p)//BHLYP and QCISD(T)/6-311++G(2df,2pd)//QCISD levels. The calculated ICVT/SCT rate constants are in good agreement with available experimental values, and the calculate results further indicate that the C(2)H(5) + HBr reaction has negative temperature dependence at T 850 K. The current work predicts that the kinetic isotope effect for the title reaction is inverse in the temperature range from 200 to 482 K, i.e., k(HBr)/k(DBr) < 1. Copyright 2003 Wiley Periodicals, Inc.

  15. Using a Family of Dividing Surfaces Normal to the Minimum EnergyPath for Quantum Instanton Rate Constants

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yimin; Miller, Wlliam H.

    2006-02-22

    One of the outstanding issues in the quantum instanton (QI) theory (or any transition state-type theory) for thermal rate constants of chemical reactions is the choice of an appropriate ''dividing surface'' (DS) that separates reactants and products. (In the general version of the QI theory, there are actually two dividing surfaces involved.) This paper shows one simple and general way for choosing DS's for use in QI Theory, namely using the family of (hyper) planes normal to the minimum energy path (MEP) on the potential energy surface at various distances s along it. Here the reaction coordinate is not one of the dynamical coordinates of the system (which will in general be the Cartesian coordinates of the atoms), but rather simply a parameter which specifies the DS. It is also shown how this idea can be implemented for an N-atom system in 3d space in a way that preserves overall translational and rotational invariance. Numerical application to a simple system (the colliner H + H{sub 2} reaction) is presented to illustrate the procedure.

  16. Low-pressure effective fluorescence lifetimes and photo-physical rate constants of one- and two-ring aromatics

    Science.gov (United States)

    Benzler, Thorsten; Faust, Stephan; Dreier, Thomas; Schulz, Christof

    2015-12-01

    One- and two-ring aromatics such as toluene and naphthalene are frequently used molecular tracer species in laser-induced fluorescence (LIF) imaging diagnostics. Quantifying LIF signal intensities requires knowledge of the photo-physical processes that determine the fluorescence quantum yield. Collision-induced and intramolecular energy transfer processes in the excited electronic state closely interact under practical conditions. They can be separated through experiments at variable low pressures. Effective fluorescence lifetimes of gaseous toluene, 1,2,4-trimethylbenzene, anisole, naphthalene, and 1-methylnaphthalene diluted in CO2 were measured after picosecond laser excitation at 266 nm and time-resolved detection of fluorescence intensities. Measurements in an optically accessible externally heated cell between 296 and 475 K and 0.010-1 bar showed that effective fluorescence lifetimes generally decrease with temperature, while the influence of the bath-gas pressure depends on the respective target species and temperature. The results provide non-radiative and fluorescence rate constants and experimentally validate the effect of photo-induced cooling.

  17. SP-A binds alpha1-antitrypsin in vitro and reduces the association rate constant for neutrophil elastase

    Directory of Open Access Journals (Sweden)

    Carrabino Natalia

    2005-12-01

    Full Text Available Abstract Background α1-antitrypsin and surfactant protein-A (SP-A are major lung defense proteins. With the hypothesis that SP-A could bind α1-antitrypsin, we designed a series of in vitro experiments aimed at investigating the nature and consequences of such an interaction. Methods and results At an α1-antitrypsin:SP-A molar ratio of 1:1, the interaction resulted in a calcium-dependent decrease of 84.6% in the association rate constant of α1-antitrypsin for neutrophil elastase. The findings were similar when SP-A was coupled with the Z variant of α1-antitrypsin. The carbohydrate recognition domain of SP-A appeared to be a major determinant of the interaction, by recognizing α1-antitrypsin carbohydrate chains. However, binding of SP-A carbohydrate chains to the α1-antitrypsin amino acid backbone and interaction between carbohydrates of both proteins are also possible. Gel filtration chromatography and turnover per inactivation experiments indicated that one part of SP-A binds several molar parts of α1-antitrypsin. Conclusion We conclude that the binding of SP-A to α1-antitrypsin results in a decrease of the inhibition of neutrophil elastase. This interaction could have potential implications in the physiologic regulation of α1-antitrypsin activity, in the pathogenesis of pulmonary emphysema, and in the defense against infectious agents.

  18. Rate constants of nine C6-C9 alkanes with OH from 230 to 379 K: chemical tracers for [OH].

    Science.gov (United States)

    Sprengnether, Michele M; Demerjian, Kenneth L; Dransfield, Timothy J; Clarke, James S; Anderson, James G; Donahue, Neil M

    2009-04-30

    We report absolute rate-constant measurements for the reactions of nine C(6)-C(9) alkanes with OH in 8-10 torr of nitrogen from 230 to 379 K in the Harvard University High-Pressure Flow System. Hydroxyl concentrations were measured using laser-induced fluorescence, and alkane concentrations were measured using Fourier transform infrared Spectroscopy. Ethane's reactivity was simultaneously measured as a test of experimental performance. Results were fit to a modified Arrhenius equation based on transition state theory (ignoring tunneling), k(T) = Be(-E(a)/T)/(T(1 - e(- 1.44nu(1)/T))(2)(1 - e(- 1.44nu(2)/T)), with nu(1) and nu(2) bending frequencies, set to 280 and 500 cm(-1). Results were as follows for B (10(-9) K cm(3) s(-1)), E(a) (K), and k(298) (10(-12) cm(3) s(-1)): cyclohexane, 3.24 +/- 0.14, 332 +/- 12, 7.13; cyclo-octane, 3.47 +/- 0.30, 149 +/- 26, 14.1; 2-methylhexane, 1.45 +/- 0.08, 110 +/- 15, 6.72; 3-methylhexane, 1.50 +/- 0.08, 128 +/- 16, 6.54; methylcyclopentane, 1.65 +/- 0.07, 109 +/- 13, 7.65; methylcyclohexane, 1.86 +/- 0.09, 83 +/- 14, 9.43; methylcycloheptane, 3.45 +/- 0.45, 142 +/- 36, 14.4; n-propylcyclohexane, 2.83 +/- 0.14, 112 +/- 15, 13.0; isopropylcyclohexane, 1.79 +/- 0.11, -44 +/- 34, 13.9. Uncertainties are one sigma results from linear regression fits and are likely underestimated. Room temperature rate coefficients of reaction are accurate to within 10% at two sigma. A comprehensive fit to 17 separate studies including the present work for cyclohexane gives good agreement with the present results: terms as above, 3.09 +/- 0.12, 326 +/- 12, 6.96. Five of these compounds are routinely measured in urban air within a suite of atmospheric nonmethane hydrocarbons and reach parts per billion levels. The remaining four are C8-C9 cycloalkanes with low anthropogenic emissions. Because of their high, specific reactivity with OH, their concentration decays may be used as an indirect measurement of [OH] in the atmosphere or laboratory. This data

  19. Sensitivity of ozone concentrations to rate constants in a modified SAPRC90 chemical mechanism used for Canadian lower Fraser Valley ozone studies

    Science.gov (United States)

    Jiang, Weimin; Singleton, Donald L.; Mclaren, Robert; Hedley, Mark

    The SAPRC90 chemical mechanism implemented in CALGRID is modified and updated for the specific emissions and applications of the Lower Fraser Valley (LFV) of British Columbia, Canada. Explicit reactions related to biogenic emissions and alternative fuels are added. The sensitivity of ozone formation to rate parameters in the mechanism is determined for an episode specific trajectory which originates under relatively clean marine conditions and passes over the urban core of Vancouver during the morning rush hour. Of the 137 reactions in the modified mechanism, the rate constants of 44 reactions are found to have a high sensitivity on ozone formation. The 44 reactions are further divided into general sensitive reactions, for which rate constant changes near the base case values have observable effects on maximum ozone concentrations, and limit-sensitive reactions, for which rate constant changes of more than an order of magnitude are required to have an observable impact on ozone concentrations. For the sensitive reactions, both ozone sensitivity coefficients for small changes (20%) in the rate constants and effects on ozone caused by large rate constant changes (factors of 0, 0.5, and 2) are calculated. Of note is the importance of several photolysis reactions and the reactions of OH with a class of reactive aromatics, including xylenes, on ozone concentrations in the LFV.

  20. Interaction of rare gas metastable atoms. [Differential and total cross sections, elastic scattering, ionization, potential scattering, phase shifts, rate constants

    Energy Technology Data Exchange (ETDEWEB)

    Wang, A.Z.F.

    1977-11-01

    The physical and chemical properties of metastable rare gas atoms are discussed and summarized. This is followed by a detailed examination of the various possible pathways whereby the metastable's excess electronic energy can be dissipated. The phenomenon of chemi-ionization is given special emphasis, and a theoretical treatment based on the use of complex (optical) potential is presented. This is followed by a discussion on the unique advantages offered by elastic differential cross section measurements in the apprehension of the fundamental forces governing the ionization process. The methodology generally adopted to extract information about the interaction potential for scattering data is also systematically outlined. Two widely studied chemi-ionization systems are then closely examined in the light of accurate differential cross section measurements obtained in this work. The first system is He(2/sup 3/S) + Ar for which one can obtain an interaction potential which is in good harmony with the experimental results of other investigators. The validity of using the first-order semiclassical approximation for the phase shifts calculation in the presence of significant opacities is also discussed. The second reaction studied is He*+D/sub 2/ for which measurements were made on both spin states of the metastable helium. A self-consistent interaction potential is obtained for the triplet system, and reasons are given for not being able to do likewise for the singlet system. The anomalous hump proposed by a number of laboratories is analyzed. Total elastic and ionization cross sections as well as rate constants are calculated for the triplet case. Good agreement with experimental data is found. Finally, the construction and operation of a high power repetitively pulsed nitrogen laser pumped dye laser system is described in great details. Details for the construction and operation of a flashlamp pumped dye laser are likewise given.

  1. Titration of the plasma effect site equilibrium rate constant of propofol; a link method of 'Concentration-Probability-Time'.

    Science.gov (United States)

    Kim, Jong-Yeop; Park, Sung-Yong; Park, Sun-Kyung; Kim, Jin-Soo; Min, Sang-Kee

    2010-03-01

    The plasma effect-site equilibrium rate constant (k(e0)) of propofol has been reported in various pharmacodynamic studies; however, it is not desirable to apply k(e0) for the link with pharmacokinetic models that were separately investigated. Thus, we titrated k(e0) for the pharmacokinetic model, which is known as the multiple covariates adjusted model of propofol. Ninety female patients scheduled for gynecologic surgery were randomly assigned to three groups targeting different plasma concentrations of 5.4, 8.1, and 10.8 microg/ml. Target-controlled infusions (TCI) were provided by a computer-assisted continuous infusion system. Time to loss of responsiveness (LOR) was measured by a blind investigator; effect-site concentrations (C(e)) for LOR were then calculated with simulation of TCI using different k(e0)s. We determined the k(e0) minimizing total discrepancy (TD) between the inputted and calculated k(e0) from the t(1/2)k(e0)s for a given probability of LOR of the C(e), and also obtained the k(e0) for the minimal TD between the median C(e), which were compared to the known k(e0). K(e0)s from these two methods were 0.3692 and 0.3788/min. C(e)s for LOR with these k(e0)s were significantly different from those with Schnider's k(e0). We proposed a method for titration of the k(e0) of propofol. The k(e0)s of propofol was lower than Schnider's k(e0). An adequate k(e0) for the specific pharmacokinetic model and a certain population would be useful for prediction of an accurate C(e), and could be used for calculation of accurate dosing during targeting of the effect site.

  2. Determination of equilibrium and rate constants for complex formation by fluorescence correlation spectroscopy supplemented by dynamic light scattering and Taylor dispersion analysis.

    Science.gov (United States)

    Zhang, Xuzhu; Poniewierski, Andrzej; Jelińska, Aldona; Zagożdżon, Anna; Wisniewska, Agnieszka; Hou, Sen; Hołyst, Robert

    2016-10-04

    The equilibrium and rate constants of molecular complex formation are of great interest both in the field of chemistry and biology. Here, we use fluorescence correlation spectroscopy (FCS), supplemented by dynamic light scattering (DLS) and Taylor dispersion analysis (TDA), to study the complex formation in model systems of dye-micelle interactions. In our case, dyes rhodamine 110 and ATTO-488 interact with three differently charged surfactant micelles: octaethylene glycol monododecyl ether C12E8 (neutral), cetyltrimethylammonium chloride CTAC (positive) and sodium dodecyl sulfate SDS (negative). To determine the rate constants for the dye-micelle complex formation we fit the experimental data obtained by FCS with a new form of the autocorrelation function, derived in the accompanying paper. Our results show that the association rate constants for the model systems are roughly two orders of magnitude smaller than those in the case of the diffusion-controlled limit. Because the complex stability is determined by the dissociation rate constant, a two-step reaction mechanism, including the diffusion-controlled and reaction-controlled rates, is used to explain the dye-micelle interaction. In the limit of fast reaction, we apply FCS to determine the equilibrium constant from the effective diffusion coefficient of the fluorescent components. Depending on the value of the equilibrium constant, we distinguish three types of interaction in the studied systems: weak, intermediate and strong. The values of the equilibrium constant obtained from the FCS and TDA experiments are very close to each other, which supports the theoretical model used to interpret the FCS data.

  3. Quantum state-to-state rate constants for the rotationally inelastic collision of CH(B2Sigma(-), nu=0, N-->N') with Ar.

    Science.gov (United States)

    Chao, Sheng Der; Lin, Sheng Hsien; Alexander, Millard H

    2005-11-15

    We have calculated the state-to-state integral cross sections and rate constants for the rotationally inelastic collision of CH(B (2)Sigma(-), nu=0, N-->N') with Ar using the quantum coupled-state and close-coupling methods on an ab initio potential-energy surface constructed by Alexander et al. [J. Chem. Phys. 101, 4547 (1994)]. Overall the calculated rate constants are in good agreements with the three available experimental results. The rate constants are comparable to the usual gas kinetic and decrease with increasing N and DeltaN. For the multiquantum transition cases, the theory underestimates the experiment. We discuss some possible causes to the discrepancies among the theory and the experiments.

  4. Evaluation of a romifidine constant rate infusion protocol with or without butorphanol for dentistry and ophthalmologic procedures in standing horses.

    Science.gov (United States)

    Marly, Charlotte; Bettschart-Wolfensberger, Regula; Nussbaumer, Paeivi; Moine, Sebastien; Ringer, Simone K

    2014-09-01

    To compare the clinical usefulness of constant rate infusion (CRI) protocols of romifidine with or without butorphanol for sedation of horses. Prospective 'blinded' controlled trial using block randomization. Forty healthy Freiberger stallions. The horses received either intravenous (IV) romifidine (loading dose: 80 μg kg(-1) ; infusion: 30 μg kg(-1)  hour(-1) ) (treatment R, n = 20) or romifidine combined with butorphanol (romifidine loading: 80 μg kg(-1) ; infusion: 29 μg kg(-1)  hour(-1) , and butorphanol loading: 18 μg kg(-1) ; infusion: 25 μg kg(-1)  hour(-1) ) (treatment RB, n = 20). Twenty-one horses underwent dentistry and ophthalmic procedures, while 19 horses underwent only ophthalmologic procedure and buccal examination. During the procedure, physiologic parameters and occurrence of head/muzzle shaking or twitching and forward movement were recorded. Whenever sedation was insufficient, additional romifidine (20 μg kg(-1) ) was administered IV. Recovery time was evaluated by assessing head height above ground. At the end of the procedure, overall quality of sedation for the procedure was scored by the dentist and anaesthetist using a visual analogue scale. Statistical analyses used two-way anova or linear mixed models as relevant. Sedation quality scores as assessed by the anaesthetist were R: median 7.55, range: 4.9-9.0 cm, RB: 8.8, 4.7-10.0 cm, and by the dentist R: 6.6, 3.0-8.2 cm, RB: 7.9, 6.6-8.8 cm. Horses receiving RB showed clinically more effective sedation as demonstrated by fewer poor scores and a tendency to reduced additional drug requirements. More horses showed forward movement and head shaking in treatment RB than treatment R. Three horses (two RB, one R) had symptoms of colic following sedation. The described protocols provide effective sedation under clinical conditions but for dentistry procedures, the addition of butorphanol is advantageous. © 2014 Association of Veterinary Anaesthetists and the

  5. Comparison of bolus injection and constant infusion methods for measuring muscle protein fractional synthesis rate in humans.

    Science.gov (United States)

    Tuvdendorj, Demidmaa; Chinkes, David L; Bahadorani, John; Zhang, Xiao-jun; Sheffield-Moore, Melinda; Killewich, Lois A; Wolfe, Robert R

    2014-12-01

    The use of stable isotope tracer techniques to measure muscle protein fractional synthesis rate (FSR) has been well established and widely used. The most common method that has been utilized so far is a primed constant infusion (CI) method, which requires 3-4 h of tracer infusion. However, recently our group has developed a bolus injection (BI) method, which requires an injection of bolus of tracer and can be completed within 1 h. In this study, we compared calf (gastrocnemius) muscle protein FSR measured using these two different methods--CI and BI. FSRs were measured in eight people (5 men and 3 women; age: 62.3±6.9 years (mean±SD); body weight: 75.4±21.5 kg) at basal, postabsorptive state using L-[ring-2H5]-phenylalanine. In the CI protocol, a primed continuous infusion was given for 4 h, and muscle biopsies were taken at 120 and 240 min; in the BI, a bolus injection of the tracer was given at 0 min and biopsies were taken at 5 and 60 min. Tracer enrichments in blood and muscle tissue were determined by gas chromatography-mass spectrometry. Data are expressed as mean±SE; t-test, linear regression and Levene Median equal variance test analyses were performed. CI FSR was 0.066±0.006%/h, whereas BI FSR was 0.058±0.008%/h, p=NS. The linear regression analysis showed a significant relationship between BI and CI, p=0.038. The intra-class correlation coefficient was 0.83. The standard deviation of the differences in the measurements was 0.015%/h. The Levene Median equal variance test demonstrated no difference in variance between the CI and BI measurements (p=0.722). No difference could be detected in calf muscle protein FSR measured by CI and BI methods; the BI method can be used for the measurement of muscle protein FSR in humans. Copyright © 2014 Elsevier Inc. All rights reserved.

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

    NARCIS (Netherlands)

    Bijlsma, S.; Smilde, A. K.

    2000-01-01

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

  7. 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.

  8. Structure-activity relationship for the estimation of OH-oxidation rate constants of aliphatic organic compounds in the aqueous phase: alkanes, alcohols, organic acids and bases

    National Research Council Canada - National Science Library

    Monod, A; Doussin, J.F

    2008-01-01

    ...-initiated oxidation of organic compounds have been determined experimentally, but a robust estimation method would be of high benefit to a wide community. Different methods have been explored so far. One method consists of correlations between the rate constant and the Bond Dissociation Energy (BDE), based on the method developed by Evans and Polanyi ...

  9. Numerical counting ratemeter with large time constant for very low count rates - operational results; Ictometre numerique a grande constante de temps pour tres faible taux de comptage - resultats d'exploitation

    Energy Technology Data Exchange (ETDEWEB)

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

    1967-07-01

    The use of an analogue ictometer poses technical problems for measuring low count rates. These latter call for time constants of up to 1000 sec. The numerical technique is better adapted and makes it possible to increase the time constant to 1000 sec. or over. The equipment described consists of 6 numerical ictometers fitted in a 3 U 3 drawer. By means of a clock it is possible to vary the counting time from 1 second to 1000 seconds, using values at 5, 10, 50, 100 and 500 seconds. The corresponding values of the frequency are 500 c/sec, 100, 50 10. 5. 1 and 0.5 c/sec with a resolving power of 0.2 per cent. The result appears on an indicator panel (galvanometer) and is available in the form of an analogue voltage suitable for a 50 mV MECI recorder. (author) [French] En utilisant un ictometre analogique, la mesure des taux de comptages faibles pose des problemes techniques. Les faibles taux de comptage exigent des constantes de temps allant jusqu'a 1000 s. La technique numerique se montre mieux adaptee et permet d'augmenter la constante de temps a 1000 s ou plus. L'ensemble decrit comporte 6 ictometres numeriques loges dans un tiroir 3 U 3. Une horloge permet de varier le temps de comptage de 1 seconde a 1000 secondes, passant par 5, 10, 50, 100, 500 secondes. Les gammes de frequences correspondantes sont 500, 100, 50, 10, 5, 1, 0,5 c/s avec une resolution de 2 pour 1000. Le resultat est affiche par un indicateur de tableaux (galvanometre) et est disponible en tension analogique pour l'enregistrement sur MECI (50 mV). (auteur)

  10. Absolute rate constant and O(3P yield for the O(1D+N2O reaction in the temperature range 227 K to 719 K

    Directory of Open Access Journals (Sweden)

    S. A. Carl

    2008-10-01

    Full Text Available The absolute rate constant for the reaction that is the major source of stratospheric NOx, O(1D+N2O → products, has been determined in the temperature range 227 K to 719 K, and, in the temperature range 248 K to 600 K, the fraction of the reaction that yields O(3P. Both the rate constants and product yields were determined using a recently-developed chemiluminescence technique for monitoring O(1D that allows for higher precision determinations for both rate constants, and, particularly, O(3P yields, than do other methods. We found the rate constant, kR1, to be essentially independent of temperature between 400 K and 227 K, having a value of (1.37±0.11×10−10 cm3 s−1, and for temperatures greater than 450 K a marked decrease in rate constant was observed, with a rate constant of only (0.94±0.11×10−10 cm3 s−1 at 719 K. The rate constants determined over the 227 K–400 K range show very low scatter and are significantly greater, by 20% at room temperature and 15% at 227 K, than the current recommended values. The fraction of O(3P produced in this reaction was determined to be 0.002±0.002 at 250 K rising steadily to 0.010±0.004 at 600 K, thus the channel producing O(3P can be entirely neglected in atmospheric kinetic modeling calculations. A further result of this study is an expression of the relative quantum yields as a function of temperature for the chemiluminescence reactions (kCL1C2H + O(1D → CH(A + CO and (kCL2C2H + O(3P → CH(A + CO, both followed by CH(A → CH(X + hν, as kCL1(T/kCL2(T=(32.8T−3050/(6.29T+398.

  11. 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

  12. Modelling and experimental checking of the influence of substrate concentration on the first order kinetic constant in photo-processes.

    Science.gov (United States)

    Gómez, M; Murcia, M D; Gómez, E; Ortega, S; Sánchez, A; Thaikovskaya, O; Briantceva, N

    2016-12-01

    Most photoprocesses follow a pseudo first order kinetic law and, commonly, the kinetic parameter depends on the initial concentration of the substrate. In this work, a kinetic model, which explains this dependence on the substrate concentration and on the other operational variables, has been developed. In the model, mass transfer of substrate from the bulk solution to the wall of the photoreactor was assumed as the step determining the rate of the process. To check the model, methylene blue (MB) has been used as model substrate and photodegradation experiments have been carried out in an exciplex KrCl flow-through photoreactor, It was observed that the methylene blue conversion improved with a decrease in its initial concentration, in good agreement with the model. Also, by fitting the experimental data to the model, high correlation coefficients and a high degree of agreement between experimental and calculated conversion was obtained, which validates the model. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2013-10-01

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

  14. Smoluchowski Equations for Agglomeration in Conditions of Variable Temperature and Pressure and a New Scaling of Rate Constants: Application to Nozzle-Beam Expansion.

    Science.gov (United States)

    Chaiken, J; Goodisman, J; Kornilov, O

    2015-07-09

    The Smoluchowski equations provide a rigorous and efficient means for including multiple kinetic pathways when modeling coalescence growth systems. Originally written for a constant temperature and volume system, the equations must be modified if temperature and pressure vary during the coalescence time. In this paper, the equations are generalized, and adaptations appropriate to the situation presented by supersonic nozzle beam expansions are described. Given rate constants for all the cluster-cluster reactions, solution of the Smoluchowski equations would yield the abundances of clusters of all sizes at all times. This is unlikely, but we show that if these rate constants scale with the sizes of the reacting partners, the asymptotic (large size and large time) form of the cluster size distribution can be predicted. Experimentally determined distributions for He fit the predicted asymptotic distribution very well. Deviations between predicted and observed distributions allow identification of special cluster sizes that is, magic numbers. Furthermore, fitting an observed distribution to the theoretical form yields the base agglomeration cross section, from which all cluster-cluster rate constants may be obtained by scaling. Comparing the base cross section to measures of size and reactivity gives information about the coalescence process.

  15. 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.

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

    Science.gov (United States)

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

    2015-06-01

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

  17. A mathematical model to determine molecular kinetic rate constants under non-steady state conditions using fluorescence recovery after photobleaching (FRAP).

    Science.gov (United States)

    Lele, Tanmay P; Ingber, Donald E

    2006-03-01

    Fluorescence recovery after photobleaching (FRAP) analyses of binding and unbinding of molecules that interact with insoluble scaffolds, such as the cytoskeleton and nuclear matrix, in living cells commonly assume that this process is at equilibrium over the time scale of fluorescence recovery. This assumption breaks down for relatively fast intracellular processes like focal adhesion assembly at the leading edge of a migrating cell, or changes of transcriptional activation in the nucleus, that can occur in a matter of a few minutes. In this paper, we formulate a mathematical model that permits FRAP to be used to determine kinetic rate constants of molecules that interact with insoluble cellular structures under non-steady state conditions. We show that unlike steady state FRAP, fluorescence recovery time scales under these unsteady conditions are determined not only by unbinding rates, but also by the overall assembly and disassembly dynamics of the structural scaffold which supports these binding interactions. Experimental data from FRAP analysis and quantification of scaffold assembly dynamics may be combined and used with our mathematical model to estimate kinetic rate constants, as well as the apparent rate constant of scaffold assembly and disassembly.

  18. State-to-state rotational relaxation rate constants for CO+Ne from IR-IR double-resonance experiments: comparing theory to experiment.

    Science.gov (United States)

    Hostutler, David A; Smith, Tony C; Hager, Gordon D; McBane, George C; Heaven, Michael C

    2004-04-22

    IR-IR double-resonance experiments were used to study the state-to-state rotational relaxation of CO with Ne as a collision partner. Rotational levels in the range Ji=2-9 were excited and collisional energy transfer of population to the levels Jf=2-8 was monitored. The resulting data set was analyzed by fitting to numerical solutions of the master equation. State-to-state rate constant matrices were generated using fitting law functions. Fitting laws based on the modified exponential gap (MEG) and statistical power exponential gap (SPEG) models were used; the MEG model performed better than the SPEG model. A rate constant matrix was also generated from scattering calculations that employed the ab initio potential energy surface of McBane and Cybulski [J. Chem. Phys. 110, 11 734 (1999)]. This theoretical rate constant matrix yielded kinetic simulations that agreed with the data nearly as well as the fitted MEG model and was unique in its ability to reproduce both the rotational energy transfer and pressure broadening data for Ne-CO. The theoretical rate coefficients varied more slowly with the energy gap than coefficients from either of the fitting laws. (c) 2004 American Institute of Physics

  19. Low temperature rate constants for the N(4S) + CH(X2Πr) reaction. Implications for N2 formation cycles in dense interstellar clouds.

    Science.gov (United States)

    Daranlot, Julien; Hu, Xixi; Xie, Changjian; Loison, Jean-Christophe; Caubet, Philippe; Costes, Michel; Wakelam, Valentine; Xie, Daiqian; Guo, Hua; Hickson, Kevin M

    2013-09-07

    Rate constants for the potentially important interstellar N((4)S) + CH(X(2)Πr) reaction have been measured in a continuous supersonic flow reactor over the range 56 K ≤T≤ 296 K using the relative rate technique employing both the N((4)S) + OH(X(2)Πi) and N((4)S) + CN(X(2)Σ(+)) reactions as references. Excess concentrations of atomic nitrogen were produced by the microwave discharge method upstream of the Laval nozzle and CH and OH radicals were created by the in situ pulsed laser photolysis of suitable precursor molecules. In parallel, quantum dynamics calculations of the title reaction have been performed based on accurate global potential energy surfaces for the 1(3)A' and 1(3)A'' states of HCN and HNC, brought about through a hierarchical construction scheme. Both adiabatic potential energy surfaces are barrierless, each one having two deep potential wells suggesting that this reaction is dominated by a complex-forming mechanism. The experimental and theoretical work are in excellent agreement, predicting a positive temperature dependence of the rate constant, in contrast to earlier experimental work at low temperature. The effects of the new low temperature rate constants on interstellar N2 formation are tested using a dense cloud model, yielding N2 abundances 10-20% lower than previously predicted.

  20. New ab initio potential energy surface for BrH2 and rate constants for the H + HBr → H2 + Br abstraction reaction.

    Science.gov (United States)

    Jiang, Bin; Xie, Changjian; Xie, Daiqian

    2011-03-21

    A global potential energy surface (PES) for the electronic ground state of the BrH(2) system was constructed based on the multireference configuration interaction (MRCI) method including the Davidson's correction using a large basis set. In addition, the spin-orbit correction were computed using the Breit-Pauli Hamiltonian and the unperturbed MRCI wavefunctions in the Br + H(2) channel and the transition state region. Adding the correction to the ground state potential, the lowest spin-orbit correlated adiabatic potential was obtained. The characters of the new potential are discussed. Accurate initial state specified rate constants for the H + HBr → H(2) + Br abstraction reaction were calculated using a time-dependent wave packet method. The predicted rate constants were found to be in excellent agreement with the available experimental values and much better than those obtained from a previous PES.

  1. Upper limits for the rate constants of the reactions of CF3O2 and CF3O radicals with ozone at 295 K

    DEFF Research Database (Denmark)

    Nielsen, O.J.; Sehested, J.

    1993-01-01

    Using the pulse radiolysis UV absorption technique and subsequent simulations of experimental absorption transients at 254 and 276 nm, upper limits of the rate constants for the reactions of CF3O2 and CF3O radicals with ozone were determined at 295 K, CF3O2+O3-->CF3O+2O2 (4), CF3O+O3-->CF3O2+O2 (......). The upper limits were derived as k4 ozone depletion by hydrofluorocarbons.......Using the pulse radiolysis UV absorption technique and subsequent simulations of experimental absorption transients at 254 and 276 nm, upper limits of the rate constants for the reactions of CF3O2 and CF3O radicals with ozone were determined at 295 K, CF3O2+O3-->CF3O+2O2 (4), CF3O+O3-->CF3O2+O2 (5...

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

    Science.gov (United States)

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

    1994-01-01

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

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

    OpenAIRE

    Martínez Aguilar, Susana; de Anda Montañez, Juan Antonio; Arreguín Sánchez, Francisco; Cisneros Mara, Miguel Angel

    2009-01-01

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

  4. Energy disposal and thermal rate constants for the OH + HBr and OH + DBr reactions: quasiclassical trajectory calculations on an accurate potential energy surface.

    Science.gov (United States)

    de Oliveira-Filho, Antonio G S; Ornellas, Fernando R; Bowman, Joel M

    2014-12-26

    We report reaction cross sections, energy disposal, and rate constants for the OH + HBr → Br + H2O and OH + DBr → Br + HDO reactions from quasiclassical trajectory calculations using an ab initio potential energy surface [ de Oliveira-Filho , A. G. S. ; Ornellas , F. R. ; Bowman , J. M. J. Phys. Chem. Lett. 2014 , 5 , 706 - 712 ]. Comparison with available experiments are made and generally show good agreement.

  5. 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...

  6. Rate constant for the H˙ + H2O → ˙OH + H2reaction 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.

  7. 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

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

    KAUST Repository

    Sudhakaran, Sairam

    2013-03-01

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

  9. Laboratory Measurement of the Gas-Phase Rate Constant for Formation of Nitric Acid from the Reaction of OH and NO2

    Science.gov (United States)

    Mollner, A. K.; Feng, L.; Sprague, M. K.; Okumura, M.; Vallavudasan, S.; Sander, S. P.; Martien, P. T.; Harley, R. A.; McCoy, A. B.

    2007-12-01

    The rate constant for the reaction OH + NO2 + M → HONO2 + M is among the most influential parameters affecting air pollution levels. There remains significant uncertainty about this rate, due to lack of laboratory data at 1 atm and to the unknown yield of a secondary channel forming peroxynitrous acid (HOONO). New experimental measurements of both the kinetics and HOONO/HONO2 branching ratios at 760 Torr are presented. The results are compared with current recommendations; when incorporated in models, the new parameters lead to significantly higher modeled ozone levels and reduced formation of nitric acid.

  10. Reaction rate constant of CH2O + H = HCO + H2 revisited: a combined study of direct shock tube measurement and transition state theory calculation.

    Science.gov (United States)

    Wang, Shengkai; Dames, Enoch E; Davidson, David F; Hanson, Ronald K

    2014-11-06

    The rate constant of the H-abstraction reaction of formaldehyde (CH2O) by hydrogen atoms (H), CH2O + H = H2 + HCO, has been studied behind reflected shock waves with use of a sensitive mid-IR laser absorption diagnostic for CO, over temperatures of 1304-2006 K and at pressures near 1 atm. C2H5I was used as an H atom precursor and 1,3,5-trioxane as the CH2O precursor, to generate a well-controlled CH2O/H reacting system. By designing the experiments to maintain relatively constant H atom concentrations, the current study significantly boosted the measurement sensitivity of the target reaction and suppressed the influence of interfering reactions. The measured CH2O + H rate constant can be expressed in modified Arrhenius from as kCH2O+H(1304-2006 K, 1 atm) = 1.97 × 10(11)(T/K)(1.06) exp(-3818 K/T) cm(3) mol(-1)s(-1), with uncertainty limits estimated to be +18%/-26%. A transition-state-theory (TST) calculation, using the CCSD(T)-F12/VTZ-F12 level of theory, is in good agreement with the shock tube measurement and extended the temperature range of the current study to 200-3000 K, over which a modified Arrhenius fit of the rate constant can be expressed as kCH2O+H(200-3000 K) = 5.86 × 10(3)(T/K)(3.13) exp(-762 K/T) cm(3) mol(-1)s(-1).

  11. Rate constants for collisional quenching of NO (A(2)Σ(+), v = 0) by He, Ne, Ar, Kr, and Xe, and infrared emission accompanying rare gas and impurity quenching.

    Science.gov (United States)

    Few, Julian; Hancock, Gus

    2014-06-14

    The quenching rates of NO (A(2)Σ(+), v = 0) with He, Ne, Ar, Kr and Xe have been studied at room temperature by measurements of the time dependence of the fluorescence decay following laser excitation. The rates are slow, with upper limits of rate constants determined as between 1.2 and 2.0 × 10(-14) cm(3) molecule(-1) s(-1), considerably lower than those reported before in the literature. Such slow rates can be markedly influenced by impurities such as O2 and H2O which have quenching rate constants close to gas kinetic values. Time resolved Fourier transform infrared emission has been used to observe the products of the quenching processes with the rare gases and with impurities. For He, Ne Ar and Kr there is no difference within experimental error of the populations in NO (X(2)Π v ≥ 2) produced with and without rare gas present, but the low quantum yields of such quenching (of the order of 5% for an atmosphere of rare gas) preclude quantitative information on the quantum states being obtained. For quenching by Xe the collisional formation of electronically excited Xe atoms dominates the emission at early times. Vibrationally excited NO (X(2)Π, v) and products of reactive quenching are observed in the presence of O2 and H2O.

  12. Learning rates and known-to-unknown flash-card ratios: comparing effectiveness while holding instructional time constant.

    Science.gov (United States)

    Forbes, Bethany E; Skinner, Christopher H; Black, Michelle P; Yaw, Jared; Booher, Joshua; Delisle, Jean

    2013-12-01

    Using alternating treatments designs, we compared learning rates across 2 computer-based flash-card interventions (3 min each): a traditional drill intervention with 15 unknown words and an interspersal intervention with 12 known words and 3 unknown words. Each student acquired more words under the traditional drill intervention. Discussion focuses on the need to account for instructional time when learning procedures are evaluated and compared. © Society for the Experimental Analysis of Behavior.

  13. Quantum instanton calculation of rate constant for CH4 + OH → CH3 + H2O reaction: torsional anharmonicity and kinetic isotope effect.

    Science.gov (United States)

    Wang, Wenji; Zhao, Yi

    2012-12-07

    Thermal rate constants for the title reaction are calculated by using the quantum instanton approximation within the full dimensional Cartesian coordinates. The results reveal that the quantum effect is remarkable for the reaction at both low and high temperatures, and the obtained rates are in good agreement with experimental measurements at high temperatures. Compared to the harmonic approximation, the torsional anharmonic effect of the internal rotation has a little influence on the rates at low temperatures, however, it enhances the rate by about 20% at 1000 K. In addition, the free energy barriers for the isotopic reactions and the temperature dependence of kinetic isotope effects are also investigated. Generally speaking, for the title reaction, the replacement of OH with OD will reduce the free energy barrier, while substituting D for H (connected to C) will increase the free energy barrier.

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

    Directory of Open Access Journals (Sweden)

    Petros Damos

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

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

    Science.gov (United States)

    Damos, Petros; Soulopoulou, Polyxeni

    2015-01-01

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

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

    Science.gov (United States)

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

    2016-02-01

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

  17. Download this PDF file

    African Journals Online (AJOL)

    of four acids of different acid strengths, pseudo-first-order rate constants were obtained, and the reaction was found to be follow third order kinetics, first order in triazine, and second order in acid. The kinetic ... constant (36.7 at 25°), and its aprotic nature make it particularly useful for acid-base studies, and a good solvent for ...

  18. Using Optical Oxygen Sensors and Injection Experiments to Determine in situ Microbial Rate Constants for Methane Oxidation and Heterotrophic Respiration in a Boreal Bog and Fen

    Science.gov (United States)

    Waldo, N.; Moorberg, C.; Waldrop, M. P.; Turetsky, M. R.; Neumann, R. B.

    2015-12-01

    Wetlands are the largest natural source of methane to the atmosphere, and play a key role in feedback cycles to climate change. In recognition of this, many researchers are developing process-based models of wetland methane emissions at various scales. In these models, the three key biogeochemical reactions are methane production, methane oxidation, and heterotrophic respiration, and they are modeled using Michaelis-Menten kinetics. The majority of Michaelis-Menten rate constants used in models are based on experiments involving slurries of peat incubated in vials. While these slurries provide a highly controlled setting, they are different from in situ conditions in multiple ways; notably they lack live plants and the centimeter-scale heterogeneities that exist in the field. To determine rate constants in a system more representative of in situ conditions, we extracted peat cores intact from a bog and fen located in the Bonanza Creek Experimental Forest near Fairbanks, Alaska and part of the Alaska Peatland Experiment (APEX) research program. Into those cores we injected water with varying concentrations of methane and oxygen at multiple depths. We used planar oxygen sensors installed on the peat cores to collect high resolution, two dimensional oxygen concentration data during the injections and used oxygen consumption rates under various conditions to calculate rate constants. Results were compared to a similar but smaller set of injection experiments conducted against planar oxygen sensors installed in the bog. Results will inform parametrization of microbial processes in wetland models, improving estimates of methane emissions both under current climate conditions and in the future.

  19. Effect of a constant rate infusion of cytosine arabinoside on mortality in dogs with meningoencephalitis of unknown origin.

    Science.gov (United States)

    Lowrie, M; Thomson, S; Smith, P; Garosi, L

    2016-07-01

    Administration of cytosine arabinoside (CA) by continuous rate infusion (CRI) has pharmacokinetic and pharmacodynamic advantages over traditional intermittent dosing. Whether these advantages translate into clinical efficacy remains unknown. The aim of this study was to assess the efficacy and safety of CRI of CA in dogs with meningoencephalitis of unknown origin (MUO) and to compare outcomes with a group of historical control dogs treated with conventional intermittent subcutaneous (SC) administration of CA; both groups received adjunctive prednisolone. It was hypothesised that a CRI of CA for 24 h at 100 mg/m(2) would improve survival and lesion resolution compared with conventional SC delivery of 50 mg/m(2) every 12 h for 48 h. Eighty dogs with suspected MUO were recruited from consecutive dogs presenting with suspected MUO from 2006 to 2015. All dogs underwent routine clinical evaluation, magnetic resonance imaging of the brain and cerebrospinal fluid analysis. There were 39 dogs in the SC group and 41 dogs in the CRI group; baseline characteristics were similar in both groups. Survival at 3 months was 22/39 (44%) with SC delivery versus 37/41 (90%) with CRI. No dose-limiting toxicities were noted for either group. The resolution rate of magnetic resonance imaging and cerebrospinal fluid abnormalities at the 3 month re-examination were substantially improved in the CRI group versus the SC group. The CRI regimen produced a survival advantage over the SC route of administration without clinically significant toxicity. These data supports the routine use of CRI at first presentation for the treatment of MUO in dogs. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.

  20. Comparison of the effects of xylazine bolus versus medetomidine constant rate infusion on cardiopulmonary function and depth of anesthesia in horses anesthetized with isoflurane.

    Science.gov (United States)

    Creighton, Catherine M; Lemke, Kip A; Lamont, Leigh A; Horney, Barbara S; Riley, Christopher B

    2012-04-15

    To compare the effects of xylazine bolus versus medetomidine constant rate infusion (MCRI) on cardiopulmonary function and depth of anesthesia in dorsally recumbent, spontaneously breathing, isoflurane-anesthetized horses. Prospective, randomized crossover study. 10 healthy adult Standardbreds. Horses were premedicated with xylazine or medetomidine IV. Anesthesia was induced with diazepam and ketamine and maintained with isoflurane for 150 minutes. For the xylazine treatment, end-tidal isoflurane concentration was maintained at 1.7%, and xylazine (0.2 mg/kg [0.09 mg/lb], IV) was administered as a bolus at the end of anesthesia. For the MCRI treatment, end-tidal isoflurane concentration was maintained at 1.4%, and medetomidine (0.005 mg/kg/h [0.0023 mg/lb/h], IV) was infused throughout anesthesia. Physiologic data (ie, heart rate, respiratory rate, rectal temperature, bispectral index, and electromyographic values) were compared between treatments with xylazine bolus versus MCRI. Heart rate was lower, but mean arterial blood pressure was higher from 20 to 40 minutes with MCRI treatment, compared with conventional treatment with xylazine. Respiratory rate and rectal temperature were greater with MCRI treatment. Bispectral index was lower with MCRI treatment from 80 to 150 minutes, and electromyographic values were lower with MCRI treatment from 30 to 150 minutes. In isoflurane-anesthetized horses, premedication with medetomidine followed by administration of medetomidine as a constant rate infusion resulted in decreased heart rate, higher arterial blood pressure from 20 through 40 minutes after induction of anesthesia, and better preserved body temperature, compared with conventional treatment with xylazine. Greater depth of anesthesia and muscle relaxation were seen with MCRI treatment, despite the lower isoflurane concentration.

  1. Nonmonotonic Temperature Dependence of the Pressure-Dependent Reaction Rate Constant and Kinetic Isotope Effect of Hydrogen Radical Reaction with Benzene Calculated by Variational Transition-State Theory.

    Science.gov (United States)

    Zhang, Hui; Zhang, Xin; Truhlar, Donald G; Xu, Xuefei

    2017-11-30

    The reaction between H and benzene is a prototype for reactions of radicals with aromatic hydrocarbons. Here we report calculations of the reaction rate constants and the branching ratios of the two channels of the reaction (H addition and H abstraction) over a wide temperature and pressure range. Our calculations, obtained with an accurate potential energy surface, are based on variational transition-state theory for the high-pressure limit of the addition reaction and for the abstraction reaction and on system-specific quantum Rice-Ramsperger-Kassel theory calibrated by variational transition-state theory for pressure effects on the addition reaction. The latter is a very convenient way to include variational effects, corner-cutting tunneling, and anharmonicity in falloff calculations. Our results are in very good agreement with the limited experimental data and show the importance of including pressure effects in the temperature interval where the mechanism changes from addition to abstraction. We found a negative temperature effect of the total reaction rate constants at 1 atm pressure in the temperature region where experimental data are missing and accurate theoretical data were previously missing as well. We also calculated the H + C 6 H 6 /C 6 D 6 and D + C 6 H 6 /C 6 D 6 kinetic isotope effects, and we compared our H + C 6 H 6 results to previous theoretical data for H + toluene. We report a very novel nonmonotonic dependence of the kinetic isotope effect on temperature. A particularly striking effect is the prediction of a negative temperature dependence of the total rate constant over 300-500 K wide temperature ranges, depending on the pressure but generally in the range from 600 to 1700 K, which includes the temperature range of ignition in gasoline engines, which is important because aromatics are important components of common fuels.

  2. Direct measurements of the total rate constant of the reaction NCN + H and implications for the product branching ratio and the enthalpy of formation of NCN.

    Science.gov (United States)

    Fassheber, Nancy; Dammeier, Johannes; Friedrichs, Gernot

    2014-06-21

    The overall rate constant of the reaction (2), NCN + H, which plays a key role in prompt-NO formation in flames, has been directly measured at temperatures 962 K rate constants are best represented by the combination of two Arrhenius expressions, k2/(cm(3) mol(-1) s(-1)) = 3.49 × 10(14) exp(-33.3 kJ mol(-1)/RT) + 1.07 × 10(13) exp(+10.0 kJ mol(-1)/RT), with a small uncertainty of ±20% at T = 1600 K and ±30% at the upper and lower experimental temperature limits.The two Arrhenius terms basically can be attributed to the contributions of reaction channel (2a) yielding CH + N2 and channel (2b) yielding HCN + N as the products. A more refined analysis taking into account experimental and theoretical literature data provided a consistent rate constant set for k2a, its reverse reaction k1a (CH + N2 → NCN + H), k2b as well as a value for the controversial enthalpy of formation of NCN, ΔfH = 450 kJ mol(-1). The analysis verifies the expected strong temperature dependence of the branching fraction ϕ = k2b/k2 with reaction channel (2b) dominating at the experimental high-temperature limit. In contrast, reaction (2a) dominates at the low-temperature limit with a possible minor contribution of the HNCN forming recombination channel (2d) at T < 1150 K.

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

    Science.gov (United States)

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

    2017-03-02

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

  4. Influence of pH and ionic strength on electrostatic properties of ferredoxin, FNR, and hydrogenase and the rate constants of their interaction

    Science.gov (United States)

    Diakonova, A. N.; Khrushchev, S. S.; Kovalenko, I. B.; Riznichenko, G. Yu; Rubin, A. B.

    2016-10-01

    Ferredoxin (Fd) protein transfers electrons from photosystem I (PSI) to ferredoxin:NADP+-reductase (FNR) in the photosynthetic electron transport chain, as well as other metabolic pathways. In some photosynthetic organisms including cyanobacteria and green unicellular algae under anaerobic conditions Fd transfers electrons not only to FNR but also to hydrogenase—an enzyme which catalyzes reduction of atomic hydrogen to H2. One of the questions posed by this competitive relationship between proteins is which characteristics of thylakoid stroma media allow switching of the electron flow between the linear path PSI-Fd-FNR-NADP+ and the path PSI-Fd-hydrogenase-H2. The study was conducted using direct multiparticle simulation approach. In this method protein molecules are considered as individual objects that experience Brownian motion and electrostatic interaction with the surrounding media and each other. Using the model we studied the effects of pH and ionic strength (I) upon complex formation between ferredoxin and FNR and ferredoxin and hydrogenase. We showed that the rate constant of Fd-FNR complex formation is constant in a wide range of physiologically significant pH values. Therefore it can be argued that regulation of FNR activity doesn’t involve pH changes in stroma. On the other hand, in the model rate constant of Fd-hydrogenase interaction dramatically depends upon pH: in the range 7-9 it increases threefold. It may seem that because hydrogenase reduces protons it should be more active when pH is acidic. Apparently, regulation of hydrogenase’s affinity to both her reaction partners (H+ and Fd) is carried out by changes in its electrostatic properties. In the dark, the protein is inactive and in the light it is activated and starts to interact with both Fd and H+. Therefore, we can conclude that in chloroplasts the rate of hydrogen production is regulated by pH through the changes in the affinity between hydrogenase and ferredoxin.

  5. 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.

  6. 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.

  7. Beyond transition state theory: accurate description of nuclear quantum effects on the rate and equilibrium constants of chemical reactions using Feynman path integrals.

    Science.gov (United States)

    Vanícek, Jirí

    2011-01-01

    Nuclear tunneling and other nuclear quantum effects have been shown to play a significant role in molecules as large as enzymes even at physiological temperatures. I discuss how these quantum phenomena can be accounted for rigorously using Feynman path integrals in calculations of the equilibrium and kinetic isotope effects as well as of the temperature dependence of the rate constant. Because these calculations are extremely computationally demanding, special attention is devoted to increasing the computational efficiency by orders of magnitude by employing efficient path integral estimators.

  8. 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. PMID:19730752

  9. 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.

  10. Rate constants for the thermal decomposition of ethanol and its bimolecular reactions with OH and D : reflected shock tube and theoretical studies.

    Energy Technology Data Exchange (ETDEWEB)

    Sivaramakrishnan, R.; Su, M.-C.; Michael, J. V.; Klippenstein, S. J.; Harding, L. B.; Ruscic, B. (Chemical Sciences and Engineering Division)

    2010-09-09

    The thermal decomposition of ethanol and its reactions with OH and D have been studied with both shock tube experiments and ab initio transition state theory-based master equation calculations. Dissociation rate constants for ethanol have been measured at high T in reflected shock waves using OH optical absorption and high-sensitivity H-atom ARAS detection. The three dissociation processes that are dominant at high T are: C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 4} + H{sub 2}O; C{sub 2}H{sub 5}OH {yields} CH{sub 3} + CH{sub 2}OH; C{sub 2}H{sub 5}OH {yields} C{sub 2}H{sub 5} + OH. The rate coefficient for reaction C was measured directly with high sensitivity at 308 nm using a multipass optical White cell. Meanwhile, H-atom ARAS measurements yield the overall rate coefficient and that for the sum of reactions B and C, since H-atoms are instantaneously formed from the decompositions of CH{sub 2}OH and C{sub 2}H{sub 5} into CH{sub 2}O + H and C{sub 2}H{sub 4} + H, respectively. By difference, rate constants for reaction 1 could be obtained. One potential complication is the scavenging of OH by unreacted ethanol in the OH experiments, and therefore, rate constants for OH + C{sub 2}H{sub 5}OH {yields} products were measured using tert-butyl hydroperoxide (tBH) as the thermal source for OH. The present experiments can be represented by the Arrhenius expression k = (2.5 {+-} 0.43) x 10{sup -11} exp(- 911 {+-} 191 K/T) cm{sup 3} molecule{sup -1} s{sup -1} over the T range 857-1297 K. For completeness, we have also measured the rate coefficient for the reaction of D atoms with ethanol D + C{sub 2}H{sub 5}OH {yields} products whose H analogue is another key reaction in the combustion of ethanol. Over the T range 1054-1359 K, the rate constants from the present experiments can be represented by the Arrhenius expression, k = (3.98 {+-} 0.76) x 10{sup -10} exp(- 4494 {+-} 235 K/T) cm{sup 3} molecule{sup -1} s{sup -1}. The high-pressure rate coefficients for reactions B and C

  11. Calculated rate constants of the chemical reactions involving the main byproducts SO2F, SOF2, SO2F2 of SF6 decomposition in power equipment

    Science.gov (United States)

    Fu, Yuwei; Rong, Mingzhe; Yang, Kang; Yang, Aijun; Wang, Xiaohua; Gao, Qingqing; Liu, Dingxin; Murphy, Anthony B.

    2016-04-01

    SF6 is widely used in electrical equipment as an insulating gas. In the presence of an electric arc, partial discharge (PD) or spark, SF6 dissociation products (such as SF2, SF3 and SF4) react with the unavoidable gas impurities (such as water vapor and oxygen), electrodes and surrounding solid insulation materials, forming several toxic and corrosive byproducts. The main stable decomposition products are SO2F, SO2F2 and SOF2, which have been confirmed experimentally to have a direct relationship with discharge faults, and are thus expected to be useful in the fault diagnosis of power equipment. Various studies have been performed of the main SF6 decomposition species and their concentrations under different types of faults. However, most of the experiments focused on the qualitative analysis of the relationship between the stable products and discharge faults. Although some theoretical research on the formation of main SF6 derivatives have been carried out using chemical kinetics models, the basic data (chemical reactions and their rate constants) adopted in the model are inaccurate and incomplete. The complex chemical reactions of SF6 with the impurities are ignored in most cases. The rate constants of some reactions obtained at ambient temperature or in a narrow temperature range are adopted in the models over a far greater range, for example up to 12 000 K, due to the difficulty in the experimental measurement and theoretical estimation of rate coefficients, particularly at high temperatures. Therefore, improved theoretical models require not only the consideration of additional SF6 decomposition reactions in the presence of impurities but also on improved values of rate constants. This paper is devoted to determining the rate constants of the chemical reactions relating to the main byproducts of SF6 decomposition in SF6 gas-insulated power equipment: SO2F, SOF2 and SO2F2. Quantum chemistry calculations with density functional theory, conventional

  12. MATHEMATICAL CONSTANTS.

    Energy Technology Data Exchange (ETDEWEB)

    Robinson, H.P.; Potter, Elinor

    1971-03-01

    This collection of mathematical data consists of two tables of decimal constants arranged according to size rather than function, a third table of integers from 1 to 1000, giving some of their properties, and a fourth table listing some infinite series arranged according to increasing size of the coefficients of the terms. The decimal values of Tables I and II are given to 20 D.

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

    Science.gov (United States)

    Bulut, Niyazi; Kłos, Jacek; Roncero, Octavio

    2015-06-07

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

  14. Thermal rate constants for the O(3P) + HBr and O(3P) + DBr reactions: transition-state theory and quantum mechanical calculations.

    Science.gov (United States)

    de Oliveira-Filho, Antonio G S; Ornellas, Fernando R; Peterson, Kirk A; Mielke, Steven L

    2013-12-05

    The O((3)P) + HBr → OH + Br and O((3)P) + DBr → OD + Br reactions are studied on a recent high-quality ab initio-based potential energy surface. Thermal rate constants over the 200-1000 K temperature range, calculated using variational transition-state theory (VTST) with the small-curvature tunneling (SCT) correction and quantum mechanical methods with the J-shifting approximation (QM/JS) for zero total angular momentum (J = 0), are reported. These results are compared to the available experimental data, which lie in the ranges of 221-554 and 295-419 K for O + HBr and O + DBr, respectively. The rate constants, in cm(3) molecule(-1) s(-1) and at 298 K, for the O + HBr reaction are 3.66 × 10(-14) for VTST, 3.80 × 10(-14) for QM/JS, and 3.66 × 10(-14) for the average of eight experimental measurements.

  15. Effects of maintenance of propofol-ketamine anesthesia with repeat bolus and constant rate infusion of propofol on physiological, biochemical, anesthetic and analgesic indices in dogs

    Directory of Open Access Journals (Sweden)

    Njoku Uchechukwu Njoku

    2015-12-01

    Full Text Available The research work was aimed at investigating physiological, biochemical, analgesic and anesthetic indices of dogs anesthetized with propofol-ketamine and maintained with repeat bolus and constant infusions of propofol. Eight dogs, assigned to two groups (n=4, were used in this study. All dogs were pre-medicated with atropine (at 0.03 mg/kg bwt and xylazine (at 2 mg/kg bwt. Anesthesia was induced by a concurrent administration of propofol (at 4 mg/kg bwt and ketamine (at 2.5 mg/kg bwt. Maintenance of anesthesia in Group 1 was done with a repeat bolus of propofol (at 2 mg/kg bwt, while in Group 2 it was done with a constant infusion of propofol (at 0.2 mg/kg bwt/min. Gastrotomy was performed in both groups, and anesthesia was maintained for 60 min. Physiological, analgesic, anesthetic parameters and plasma glucose concentration were measured. There was no significant (P>0.05 difference found in the analgesia and pedal reflex scores, durations of analgesia and recumbency, recovery time and standing time between the groups. The heart rate, respiratory rate and rectal temperature reduced significantly (P0.05 between the groups. In conclusion, both maintenance protocols are suitable for dogs, although the repeat bolus technique produces marked cardiopulmonary depression.

  16. Mechanism and Kinetics of Methane Combustion, Part I: Thermal Rate Constants for Hydrogen-Abstraction Reaction of CH4 + O(3P).

    Science.gov (United States)

    Peng, Ya; Jiang, Zhong'an; Chen, Jushi

    2017-03-23

    The mechanism and kinetics of gas-phase hydrogen-abstraction by the O(3P) from methane are investigated using ab initio calculations and dynamical methods. Not only are the electronic structure properties including the optimized geometries, relative energies, and vibrational frequencies of all the stationary points obtained from state-averaged complete active space self-consistent field calculations, but also the single-point energies for all points on the intrinsic reaction coordinate are evaluated using the internally contracted multireference configuration interaction approach with modified optimized cc-pCVDZ basis sets. Our calculations give a fairly accurate description of the regions around the 3A″ transition state in the O(3P) attacking a near-collinear H-CH3 direction with a barrier height of 12.53 kcal/mol, which is lower than those reported before. Subsequently, thermal rate constants for this hydrogen-abstraction are calculated using the canonical unified statistical theory method with the temperature ranging from 298 K to 1000 K. These calculated rate constants are in agreement with experiments. The present work reveals the reaction mechanism of hydrogen-abstraction by the O(3P) from methane, and it is helpful for the understanding of methane combustion.

  17. On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

    Science.gov (United States)

    Marcus, R. A.

    1962-01-01

    Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

  18. A quantum method for thermal rate constant calculations from stationary phase approximation of the thermal flux-flux correlation function integral.

    Science.gov (United States)

    Aieta, Chiara; Ceotto, Michele

    2017-06-07

    This paper presents a quantum mechanical approximation to the calculation of thermal rate constants. The rate is derived from a suitable stationary phase approximation to the time integral of the thermal flux-flux correlation function. The goal is to obtain an expression that barely depends on the position of the flux operators, i.e., of the dividing surfaces, so that it can be applied also to complex systems by arbitrarily locating the dividing surfaces. The approach is tested on one and two dimensional systems where quantum effects are predominant over a wide range of temperatures. The results are quite accurate, i.e., within a few percent of the exact values for a reasonable range of dividing surface positions.

  19. KINETICS OF SUBSTITUTION OF CIS-BIS(MALONATO ...

    African Journals Online (AJOL)

    Preferred Customer

    Effect of concentration of amino acids. The pseudo-first order rate constants were evaluated from the straight line plot of log (A∞-At) vs. time by using KINTOB software procedure. The rate of the reaction increases with increase in the concentration of amino acids (Table 1). In the amino acid variation studies the pH was kept.

  20. Kinetics of Oxidation of Aliphatic Alcohols by Potassium Dichromate ...

    African Journals Online (AJOL)

    The pseudo-first-order rate constants were found to be independent of concentration of the oxidant. The presence of TX-100 enhanced the rate of the reaction for all alcohols. Negative salt effects were observed with addition of KCl to the reaction mixture. A suitable mechanism for the reaction was suggested which agrees ...

  1. 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.

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

    Science.gov (United States)

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

    1995-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-15

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

  4. Ab initio study of the HO2+NO reaction: Prediction of the total rate constant and product branching ratios for the forward and reverse processes

    Science.gov (United States)

    Zhu, R. S.; Lin, M. C.

    2003-11-01

    The mechanisms for HO2+NO and its reverse reactions have been investigated by ab initio molecular orbital and transition-state theory calculations. The species involved have been optimized at the B3LYP/6-311+G(3df,2p) level and their energies refined by single-point calculations with the highest scheme of the modified Gaussian-2 method. Ab initio results show that formation of HO+NO2 from HO2+NO by the direct fragmentation of the peroxynitrous acid, HOONO intermediate, is predominant; the alternative path occurring by the isomerization of HOONO to HONO2 is 5.2 kcal/mol less favorable. The stepwise formation of HNO+O2 from HOONO is energetically unfavorable; the barriers for the direct H abstract reactions via singlet and triplet paths are found to be rather high also. Rate constant calculations show that the forward reaction is pressure independent below 10 atm; the reverse OH+NO2 reactions producing HONO2 and HOONO appear to be strongly pressure dependent; below 1 atm, the yield of HOONO from HO+NO2 is <2.5% at 300-400 K, it reaches 12.2% and 9.1%, respectively, at 300 and 400 K at 3.8×104 Torr pressure. The low- and high-pressure rate constants with He as a third-body for the formation of HOONO and HONO2 from the HO+NO2 reaction can be expressed by k0 (HOONO)=3.15×102 T-12.3 exp(-585/T), k0 (HONO2)=3.32×10-6 T-8.8 exp(-1569/T)cm6 molecule-2 s-1 and k∞ (HOONO)=1.71×10-10 T-0.24 exp(100/T) and k∞ (HONO2)=4.74×10-9T-0.82 exp(21/T) cm3 molecule-1 s-1, respectively, in the temperature range of 200-2000 K. The unimolecular decomposition rate constant (in Ar) of HNO3 can be expressed as kd∞ (HNO3)=2.30×1023T-2.27 exp(-26317/T) s-1 and kd0 (HNO3)=1.27×1015 T-6.55exp(-26038/T) cm3 molecule-1 s-1, respectively. The predicted values are all in close agreement with experimental data for both forward and reverse processes.

  5. Rate constant for the reaction of OH with methyl iodide, a re-determination by flash photolysis of water vapour and time resolved resonance fluorescence of OH

    Science.gov (United States)

    Zhang, Shaoliang; Strekowski, Rafal; Zetzsch, Cornelius

    2010-05-01

    Methyl iodide is a major source gas for atmospheric iodine, and it is mainly emitted from the ocean. Aqueous-phase reactions, such as hydrolysis and exchange reactions with chloride control its emissions to the atmosphere, where its lifetime is limited to less than a week, mainly by photolysis. A minor contribution to the loss processes in the troposphere is the gas-phase reaction with OH radicals, that has been investigated by several authors. On the other hand, this reaction turned out to be uncertain in spite of interest in nuclear safety after the International Phebus Fission Product programme, initiated in 1988. Some of the most important observed phenomena with regard to the chemistry of iodine were not predicted, clearly showing the need for carrying out rate constant determinations for the reactions of I2 and CH3I with OH, which is a major oxidant product from the air radiolysis under accident conditions. We have measured the rate constant for the reaction OH + CH3I - H2O + CH2I in He at 260 mbar in the temperature range from 298 to 362 K. OH radicals were produced by flash photolysis of H2O in the vacuum-UV at wavelengths > 115 nm using a Xe flash lamp with a MgF2 window. Time profiles of OH radicals are monitored by resonance fluorescence of the A2 Σ - X2 Π transition at 308 nm, induced by the emission from a microwave discharge of a flow of He and H2O, a few Torr each. The signal is monitored by photon counting and multichannel scaling, collecting the counts from 50 flashes each, obtaind by pulsed photolysis of various mixtures of H2O and CH3I under slow-flow conditions. Decays of OH in the presence of CH3I are observed to be exponential, and the decay rates are found to be linearly dependent on the concentration of CH3I. Rate constants, k ± 2σ (in units of 10-14 cm3 s-1) of 4.14±0.20, 6.33±0.68, 7.31±1.18 and 8.24±1.60 at 298, 326, 352 and 362 K, respectively, are obtained from linear regressions and lead to an Arrhenius expression of k = 1.5

  6. 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

    Eoa,(OH/OH-) were determined by means of kf and k,, the equilibrium constant of 03- + O2 + 0-, the pK of the hydroxyl radical, A&Oa, of 030, 2a,n d OH-i n aqueous solution, and E0,,(C1O2/C1O2-) = 0.934 V determined in the present work. Apoa,(OH) = 26.8 * 1 kJ mol-' and Eoao(OH/OH-) = 1.91 * 0.01 V......The rate constants of the following reactions were determined by pulse radiolysis and stopped-flow experiments: C102- + O3 + C102 + 03-(k f= (4 f 1) X lo6 dm3 mol-' s-', k, = (1.8 f 0.2) X lo5 dm3 mol-' s-]); C102 + OH - C103- + H+ (k = (4.0 * 0.4) X lo9 dm3 mol-' s-l); C102 + 0- - C103- (k = (2...

  7. Estimation of Slow Crack Growth Parameters for Constant Stress-Rate Test Data of Advanced Ceramics and Glass by the Individual Data and Arithmetic Mean Methods

    Science.gov (United States)

    Choi, Sung R.; Salem, Jonathan A.; Holland, Frederic A.

    1997-01-01

    The two estimation methods, individual data and arithmetic mean methods, were used to determine the slow crack growth (SCG) parameters (n and D) of advanced ceramics and glass from a large number of room- and elevated-temperature constant stress-rate ('dynamic fatigue') test data. For ceramic materials with Weibull modulus greater than 10, the difference in the SCG parameters between the two estimation methods was negligible; whereas, for glass specimens exhibiting Weibull modulus of about 3, the difference was amplified, resulting in a maximum difference of 16 and 13 %, respectively, in n and D. Of the two SCG parameters, the parameter n was more sensitive to the estimation method than the other. The coefficient of variation in n was found to be somewhat greater in the individual data method than in the arithmetic mean method.

  8. Radiosensitization of DNA by Cisplatin Adducts Results from an Increase in the Rate Constant for the Reaction with Hydrated Electrons and Formation of Pt(I).

    Science.gov (United States)

    Behmand, B; Marignier, J-L; Mostafavi, M; Wagner, J R; Hunting, D J; Sanche, L

    2015-07-30

    Pulse radiolysis measurements of the decay of hydrated electrons in solutions containing different concentrations of the oligonucleotide GTG with and without a cisplatin adduct show that the presence of a cisplatin moiety accelerates the reaction between hydrated electrons and the oligonucleotide. The rate constant of the reaction is found to be 2.23 × 10(10) mol(-1) L s(-1), which indicates that it is diffusion controlled. In addition, we show for the first time the formation of a Pt(I) intermediate as a result of the reaction of hydrated electrons with GTG-cisplatin. A putative reaction mechanism is proposed, which may form the basis of the radiosensitization of cancer cells in concomitant chemoradiation therapy with cisplatin.

  9. 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

  10. Precise Determination of the Strong Coupling Constant at NNLO in QCD from the Three-Jet Rate in Electron-Positron Annihilation at LEP

    Science.gov (United States)

    Dissertori, G.; Gehrmann-Deridder, A.; Gehrmann, T.; Glover, E. W. N.; Heinrich, G.; Stenzel, H.

    2010-02-01

    We present the first determination of the strong coupling constant from the three-jet rate in e+e- annihilation at LEP, based on a next-to-next-to-leading-order (NNLO) perturbative QCD prediction. More precisely, we extract αs(MZ) by fitting perturbative QCD predictions at O(αs3) to data from the ALEPH experiment at LEP. Over a large range of the jet-resolution parameter ycut, this observable is characterized by small nonperturbative corrections and an excellent stability under renormalization scale variation. We find αs(MZ)=0.1175±0.0020(expt)±0.0015(theor), which is more accurate than the values of αs(MZ) from e+e- event-shape data currently used in the world average.

  11. Comparison of the effects of xylazine bolus versus medetomidine constant rate infusion on the stress response, urine production, and anesthetic recovery characteristics in horses anesthetized with isoflurane.

    Science.gov (United States)

    Creighton, Catherine M; Lemke, Kip A; Lamont, Leigh A; Horney, Barbara S; Doyle, Aimie J

    2012-04-15

    To compare the effect of xylazine bolus versus medetomidine constant rate infusion (MCRI) on serum cortisol and glucose concentrations, urine production, and anesthetic recovery characteristics in dorsally recumbent, spontaneously breathing, isoflurane-anesthetized horses. Prospective, randomized crossover study. 10 healthy Standardbreds. Horses were premedicated with xylazine or medetomidine IV. Anesthesia was induced with diazepam and ketamine and maintained with isoflurane for 150 minutes. For the xylazine treatment, end-tidal isoflurane concentration was maintained at 1.7% and xylazine (0.2 mg/kg [0.09 mg/lb]), IV) was administered as a bolus at the end of anesthesia. For the MCRI treatment, end-tidal isoflurane concentration was maintained at 1.4% and medetomidine (0.005 mg/kg/h [0.0023 mg/lb/h], IV) was infused throughout anesthesia. Serum cortisol and glucose concentrations were measured before, during, and after anesthesia. Urine specific gravity and volume were measured during anesthesia. Unassisted anesthetic recoveries were recorded by a digital video camera for later evaluation by 2 observers who were blinded to treatment. Serum cortisol concentration was lower and serum glucose concentration was higher with MCRI treatment, compared with xylazine treatment. Time to sternal recumbency was longer with MCRI treatment, but no difference was seen between treatments for times to extubation, first movement, or standing. Objective (mean attempt interval) and subjective (visual analog score) recovery scores were significantly better with MCRI treatment, compared with xylazine treatment. In isoflurane-anesthetized horses, premedication and administration of medetomidine as a constant rate infusion resulted in decreased serum cortisol concentration, increased serum glucose concentration, and superior anesthetic recovery characteristics, compared with conventional treatment with xylazine.

  12. Electron attachment to POCl3: Measurement and theoretical analysis of rate constants and branching ratios as a function of gas pressure and temperature, electron temperature, and electron energy

    Science.gov (United States)

    Van Doren, Jane M.; Friedman, Jeffery F.; Miller, Thomas M.; Viggiano, A. A.; Denifl, S.; Scheier, P.; Märk, T. D.; Troe, J.

    2006-03-01

    Two experimental techniques, electron swarm and electron beam, have been applied to the problem of electron attachment to POCl3, with results indicating that there is a competition between dissociation of the resonant POCl3-* state and collisional stabilization of the parent anion. In the electron beam experiment at zero electron energy, the fragment ion POCl2- is the dominant ion product of attachment (96%), under single-collision conditions. Small amounts (˜2% each) of POCl3- and Cl - were observed. POCl3- and POCl2- ion products were observed only at zero electron energy, but higher-energy resonances were recorded for POCl-, Cl-, and Cl2- ion products. In the electron swarm experiment, which was carried out in 0.4-7Torr of He buffer gas, the parent anion branching ratio increased significantly with pressure and decreased with temperature. The electron attachment rate constant at 297K was measured to be (2.5±0.6)×10-7cm3s-1, with ion products POCl2- (71%) and POCl3- (29%) in 1Torr of He gas. The rate constant decreased as the electron temperature was increased above 1500K. Theory is developed for (a) the unimolecular dissociation of the nascent POCl3-* and (b) a stepladder collisional stabilization mechanism using the average energy transferred per collision as a parameter. These ideas were then used to model the experimental data. The modeling showed that D0o(Cl -POCl2-) and EA(POCl3) must be the same within ±0.03eV.

  13. Tunable Yb-doped fiber laser based on a FBG array and a theta ring resonator ensuring a constant repetition rate (Conference Presentation)

    Science.gov (United States)

    Tiess, Tobias; Becker, Martin; Rothhardt, Manfred; Bartelt, Hartmut; Jäger, Matthias L.

    2017-03-01

    Fiber lasers provide the perfect basis to develop broadly tunable lasers with high efficiency, excellent beam quality and user-friendly operation as they are increasingly demanded by applications in biophotonics and spectroscopy. Recently, a novel tuning scheme has been presented using fiber Bragg grating (FBG) arrays as fiber-integrated spectral filters containing many standard FBGs with different feedback wavelengths. Based on the discrete spectral sampling, these reflective filters uniquely enable tailored tuning ranges and broad bandwidths to be implemented into fiber lasers. Even though the first implementation of FBG arrays in pulsed tunable lasers based on a sigma ring resonators works with good emission properties, the laser wavelength is tuned by a changing repetition rate, which causes problems with applications in synchronized environments. In this work, we present a modified resonator scheme to maintain a constant repetition rate over the tuning range and still benefit from the advantages of FBG arrays as filters. With a theta ring cavity and two counter propagating filter passes, the distributed feedback of the FBG array is compensated resulting in a constant pulse round trip time for each filter wavelength. Together with an adapted gating scheme controlling the emission wavelength with a modulator, the tuning principle has been realized based on a Ytterbium-doped fiber laser. We present first experimental results demonstrating a tuning range of 25nm, high signal contrast and pulse durations of about 10ns. With the prospect of tailored tuning ranges, this pulsed fiber-integrated laser may be the basis to tackle challenging applications in spectroscopy.

  14. Direct determination of rate constants for coupling between aromatic radical anions and alkyl and benzyl radicals by laser-flash photolysis

    DEFF Research Database (Denmark)

    Lund, T.; Christensen, P.; Wilbrandt, Robert Walter

    2003-01-01

    Coupling rates between the radicals methyl, n-, sec-, tert-butyl and benzyl (R-.) and the aromatic radical anions of 1,4-dicyanonaphthalene, 9,10-dicyanoanthracene and fluorenone (A(-.)) have been obtained using a new laser-flash photolysis method. The radicals R-. and the radical anions A(-.) we...... of the radicals and the structure and standard potentials of the aromatic radical anions.......Coupling rates between the radicals methyl, n-, sec-, tert-butyl and benzyl (R-.) and the aromatic radical anions of 1,4-dicyanonaphthalene, 9,10-dicyanoanthracene and fluorenone (A(-.)) have been obtained using a new laser-flash photolysis method. The radicals R-. and the radical anions A(-.) were...... generated by a photoinduced electron transfer reaction between the aromatic compound A and the alkyl or benzyl triphenylborate anion RB(Ph)(3)(-). For the first time the rate constants of the coupling reaction between methyl and benzyl radicals with aromatic radical anions have been obtained. For all...

  15. SYNTHESIS AND HYDROLYSIS OF NEW ASPIRIN-DERIVED AND TRIFLUSAL-DERIVED ORTHO ESTERS AND ANHYDRIDES

    DEFF Research Database (Denmark)

    FALBORG, L; SENNING, A

    1993-01-01

    Ten new 2-substituted 2-methyl-2-oxy-4H-1,3-benzodioxin-4-ones, 4a-i and 6, have been synthesized and their rate constants of pseudo-first-order non-enzymatic hydrolysis determined. One of the compounds, 2-(2-acetoxybenzoyloxy)-2-methyl-4H-1,3-benzodioxin-4-one, 6, is a new anhydride of aspirin...

  16. Counterion Binding Effects on the Micellar Catalysis of the Base ...

    African Journals Online (AJOL)

    The effects of counterion binding on micellar catalysis of the base hydrolysis of FE(phen) has been investaged. Pseudo first order rate constant, k , incrases with increase in the concentrations of ME NCI and (But) NC1 at any fixed Sodium dodecyl sulphate (SDS) concentration while the reserve is the case with NH CL.

  17. Photoelectrocatalytic removal of color from water using TiO 2 and ...

    African Journals Online (AJOL)

    In all cases, the kinetics of the photo catalytic oxidation of methyl orange followed a pseudo first order model and the apparent rate constant may depend on several factors such as, the nature and concentration of the organic compound, radiant flux, the solution pH and the presence of other organic substances.

  18. An Analogy Using Pennies and Dimes to Explain Chemical Kinetics Concepts

    Science.gov (United States)

    Cortes-Figueroa, Jose E.; Perez, Wanda I.; Lopez, Jose R.; Moore-Russo, Deborah A.

    2011-01-01

    In this article, the authors present an analogy that uses coins and graphical analysis to teach kinetics concepts and resolve pseudo-first-order rate constants related to transition-metal complexes ligand-solvent exchange reactions. They describe an activity that is directed to upper-division undergraduate and graduate students. The activity…

  19. Cinética de sinterização para sistemas à base de SnO2 por taxa de aquecimento constante Sintering kinetics for SnO2-based systems by constant heating rate

    Directory of Open Access Journals (Sweden)

    S. M. Tebcheran

    2003-04-01

    in small concentrations as densifying aids for this oxide. In the present study the sintering kinetics of tin oxide was studied considering the effect of sintering atmosphere and of the MnO2 concentration. SnO2-MnO2 systems were prepared from the polymeric precursors method and the obtained powders were characterized by surface area by the BET method. SnO2 powders with varied MnO2 concentrations were pressed in cylindrical shape, and sintered in a dilatometer furnace with constant heating rate and controlled atmospheres. Sintered samples were characterized by scanning electron microscopy. The influence of atmosphere (argon, air or CO2 as well as of the MnO2 concentrations on the sintering kinetics was determined. The kinetics data of linear shrinkage were analyzed in terms of kinetic models for the initial stage of sintering (Woolfrey and Bannister as well as for the global sintering (Su e Johnson allowing the determination of the apparent activation energy. Following the determination of the master sintering curve the apparent activation energy of all sintering process were determined as well as its dependence with the atmosphere and manganese concentrations. Based on these values and on the n exponent, determined by the classical grain growth equation, it was concluded that the most probable sintering mechanism is grain boundary diffusion with surface redistribution controlling the kinetics.

  20. Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K

    Science.gov (United States)

    Thorn, R. Peyton, Jr.; Payne, Walter A., Jr.; Chillier, Xavier D. F.; Stief, Louis J.; Nesbitt, Fred L.; Tardy, D. C.

    2000-01-01

    The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.

  1. 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

  2. Radical scavenging ability of gallic acid toward OH and OOH radicals. Reaction mechanism and rate constants from the density functional theory.

    Science.gov (United States)

    Marino, Tiziana; Galano, Annia; Russo, Nino

    2014-09-04

    Gallic acid is a ubiquitous compound, widely distributed in the vegetal kingdom and frequently found in the human diet. In the present work, its primary antioxidant activity has been investigated using the density functional theory (DFT), and the quantum mechanics-based test for overall free radical scavenging activity (QM-ORSA) protocol. It was found that gallic acid is a better antioxidant than the reference compound, Trolox, regardless of the polarity of the environment. In addition, gallic acid is predicted to be among the best peroxyl radical scavengers identified so far in nonpolar (lipid) media. This compound is capable of scavenging hydroxyl radicals at diffusion-limited rates, and hydroperoxyl radicals with rate constants in the order of 10(5) M(-1) s(-1). The deprotonation of gallic acid, in aqueous solution, is predicted to increase the protective action of this compound against oxidative stress. Gallic acid was also identified as a versatile scavenger, capable of rapidly deactivating a wide variety of reactive oxygen species (ROS) and reactive nitrogen species (RNS) via electron transfer at physiological pH.

  3. A comparison of methods to estimate anaerobic capacity: Accumulated oxygen deficit and W' during constant and all-out work-rate profiles.

    Science.gov (United States)

    Muniz-Pumares, Daniel; Pedlar, Charles; Godfrey, Richard; Glaister, Mark

    2017-12-01

    This study investigated (i) whether the accumulated oxygen deficit (AOD) and curvature constant of the power-duration relationship (W') are different during constant work-rate to exhaustion (CWR) and 3-min all-out (3MT) tests and (ii) the relationship between AOD and W' during CWR and 3MT. Twenty-one male cyclists (age: 40 ± 6 years; maximal oxygen uptake [V̇O2max]: 58 ± 7 ml · kg(-1) · min(-1)) completed preliminary tests to determine the V̇O2-power output relationship and V̇O2max. Subsequently, AOD and W' were determined as the difference between oxygen demand and oxygen uptake and work completed above critical power, respectively, in CWR and 3MT. There were no differences between tests for duration, work, or average power output (P ≥ 0.05). AOD was greater in the CWR test (4.18 ± 0.95 vs. 3.68 ± 0.98 L; P = 0.004), whereas W' was greater in 3MT (9.55 ± 4.00 vs. 11.37 ± 3.84 kJ; P = 0.010). AOD and W' were significantly correlated in both CWR (P W' in CWR and 3MT, between-test differences in the magnitude of AOD and W', suggest that both measures have different underpinning mechanisms.

  4. Rate and equilibrium constant of the reaction of 1-methylvinoxy radicals with O2: CH3COCH2 + O2 CH3COCH2O2.

    Science.gov (United States)

    Hassouna, Melynda; Delbos, Eric; Devolder, Pascal; Viskolcz, Bela; Fittschen, Christa

    2006-06-01

    The reaction of 1-methylvinoxy radicals, CH3COCH2, with molecular oxygen has been investigated by experimental and theoretical methods as a function of temperature (291-520 K) and pressure (0.042-10 bar He). Experiments have been performed by laser photolysis coupled to a detection of 1-methylvinoxy radicals by laser-induced fluorescence LIF. The potential energy surface calculations were performed using ab inito molecular orbital theory at the G3MP2B3 and CBSQB3 level of theory based on the density function theory optimized geometries. Derived molecular properties of the characteristic points of the potential energy surface were used to describe the mechanism and kinetics of the reaction under investigation. At 295 K, no pressure dependence of the rate constant for the association reaction has been observed: k(1,298K) = (1.18 +/- 0.04) x 10(-12) cm3 s(-1). Biexponential decays have been observed in the temperature range 459-520 K and have been interpreted as an equilibrium reaction. The temperature-dependent equilibrium constants have been extracted from these decays and a standard reaction enthalpy of deltaH(r,298K) = -105.0 +/- 2.0 kJ mol(-1) and entropy of deltaS(r,298K) = -143.0 +/- 4.0 J mol(-1) K(-1) were derived, in excellent agreement with the theoretical results. Consistent heats of formation for the vinoxy and the 1-methylvinoxy radical as well as their O2 adducts are recommended based on our complementary experimental and theoretical study deltaH(f,298K) = 13.0 +/- 2.0, -32. 9+/- 2.0, -85.9 +/- 4.0, and -142.1 +/- 4.0 kJ mol(-1) for CH2CHO, CH3COCH2 radicals, and their adducts, respectively.

  5. Modeling the pH and temperature dependence of aqueousphase hydroxyl radical reaction rate constants of organic micropollutants using QSPR approach.

    Science.gov (United States)

    Gupta, Shikha; Basant, Nikita

    2017-11-01

    Designing of advanced oxidation process (AOP) requires knowledge of the aqueous phase hydroxyl radical ( ● OH) reactions rate constants (k OH ), which are strictly dependent upon the pH and temperature of the medium. In this study, pH- and temperature-dependent quantitative structure-property relationship (QSPR) models based on the decision tree boost (DTB) approach were developed for the prediction of k OH of diverse organic contaminants following the OECD guidelines. Experimental datasets (n = 958) pertaining to the k OH values of aqueous phase reactions at different pH (n = 470; 1.4 × 10 6 to 3.8 × 10 10  M -1  s -1 ) and temperature (n = 171; 1.0 × 10 7 to 2.6 × 10 10  M -1  s -1 ) were considered and molecular descriptors of the compounds were derived. The Sanderson scale electronegativity, topological polar surface area, number of double bonds, and halogen atoms in the molecule, in addition to the pH and temperature, were found to be the relevant predictors. The models were validated and their external predictivity was evaluated in terms of most stringent criteria parameters derived on the test data. High values of the coefficient of determination (R 2 ) and small root mean squared error (RMSE) in respective training (> 0.972, ≤ 0.12) and test (≥ 0.936, ≤ 0.16) sets indicated high generalization and predictivity of the developed QSPR model. Other statistical parameters derived from the training and test data also supported the robustness of the models and their suitability for screening new chemicals within the defined chemical space. The developed QSPR models provide a valuable tool for predicting the ● OH reaction rate constants of emerging new water contaminants for their susceptibility to AOPs.

  6. Reaction kinetics of resveratrol with tert-butoxyl radicals

    Science.gov (United States)

    Džeba, Iva; Pedzinski, Tomasz; Mihaljević, Branka

    2012-09-01

    The rate constant for the reaction of t-butoxyl radicals with resveratrol was studied under pseudo-first order conditions. The rate constant was determined by measuring the phenoxyl radical formation rate at 390 nm as function of resveratrol concentration in acetonitrile. The rate constant was determined to be 6.5×108 M-1s-1. This high value indicates the high reactivity consistent with the strong antioxidant activity of resveratrol.

  7. Calculations with spectroscopic accuracy for energies, transition rates, hyperfine interaction constants, and Landé gJ-factors in nitrogen-like Kr XXX

    Science.gov (United States)

    Wang, K.; Li, S.; Jönsson, P.; Fu, N.; Dang, W.; Guo, X. L.; Chen, C. Y.; Yan, J.; Chen, Z. B.; Si, R.

    2017-01-01

    Extensive self-consistent multi-configuration Dirac-Fock (MCDF) calculations and second-order many-body perturbation theory (MBPT) calculations are performed for the lowest 272 states belonging to the 2s22p3, 2s2p4, 2p5, 2s22p23l, and 2s2p33l (l=s, p, d) configurations of N-like Kr XXX. Complete and consistent data sets of level energies, wavelengths, line strengths, oscillator strengths, lifetimes, AJ, BJ hyperfine interaction constants, Landé gJ-factors, and electric dipole (E1), magnetic dipole (M1), electric quadrupole (E2), magnetic quadrupole (M2) transition rates among all these levels are given. The present MCDF and MBPT results are compared with each other and with other available experimental and theoretical results. The mean relative difference between our two sets of level energies is only about 0.003% for these 272 levels. The accuracy of the present calculations are high enough to facilitate identification of many observed spectral lines. These accurate data can be served as benchmark for other calculations and can be useful for fusion plasma research and astrophysical applications.

  8. Accurate quantum mechanical calculations of differential and integral cross sections and rate constant for the O+OH reaction using an ab initio potential energy surface.

    Science.gov (United States)

    Lin, Shi Ying; Guo, Hua; Honvault, Pascal; Xu, Chuanxiu; Xie, Daiqian

    2008-01-07

    The authors report accurate quantum mechanical studies of the O+OH reaction on the improved Xu-Xie-Zhang-Lin-Guo potential energy surface. The differential cross section was obtained at several energies near the reaction threshold using a time-independent method. The dominant forward and backward peaks in the angular distribution are consistent with a complex-forming mechanism, which is also confirmed by the extensive rotational excitation in the O2 product. However, the asymmetry of these peaks suggests a significant nonstatistical component. The initial state (upsilon i=0, j i=0) specified integral cross section, which was calculated up to 1.15 eV of collision energy using the Chebyshev wave packet method, shows no energy threshold and decreases with the increasing collision energy, consistent with the barrierless nature of the reaction. The resulting rate constant exhibits a negative temperature dependence for T>100 K and decays as the temperature is lowered, in qualitative agreement with available experimental data.

  9. Toward the Development of a Fundamentally Based Chemical Model for Cyclopentanone: High-Pressure-Limit Rate Constants for H Atom Abstraction and Fuel Radical Decomposition.

    Science.gov (United States)

    Zhou, Chong-Wen; Simmie, John M; Pitz, William J; Curran, Henry J

    2016-09-15

    Theoretical aspects of the development of a chemical kinetic model for the pyrolysis and combustion of a cyclic ketone, cyclopentanone, are considered. Calculated thermodynamic and kinetic data are presented for the first time for the principal species including 2- and 3-oxo-cyclopentyl radicals, which are in reasonable agreement with the literature. These radicals can be formed via H atom abstraction reactions by Ḣ and Ö atoms and ȮH, HȮ2, and ĊH3 radicals, the rate constants of which have been calculated. Abstraction from the β-hydrogen atom is the dominant process when ȮH is involved, but the reverse holds true for HȮ2 radicals. The subsequent β-scission of the radicals formed is also determined, and it is shown that recent tunable VUV photoionization mass spectrometry experiments can be interpreted in this light. The bulk of the calculations used the composite model chemistry G4, which was benchmarked in the simplest case with a coupled cluster treatment, CCSD(T), in the complete basis set limit.

  10. Reaction rate and isomer-specific product branching ratios of C2H + C4H8: 1-butene, cis-2-butene, trans-2-butene, and isobutene at 79 K.

    Science.gov (United States)

    Bouwman, Jordy; Fournier, Martin; Sims, Ian R; Leone, Stephen R; Wilson, Kevin R

    2013-06-20

    The reactions of C2H radicals with C4H8 isomers 1-butene, cis-2-butene, trans-2-butene, and isobutene are studied by laser photolysis-vacuum ultraviolet mass spectrometry in a Laval nozzle expansion at 79 K. Bimolecular-reaction rate constants are obtained by measuring the formation rate of the reaction product species as a function of the reactant density under pseudo-first-order conditions. The rate constants are (1.9 ± 0.5) × 10(-10), (1.7 ± 0.5) × 10(-10), (2.1 ± 0.7) × 10(-10), and (1.8 ± 0.9) × 10(-10) cm(3) s(-1) for the reaction of C2H with 1-butene, cis-2-butene, trans-2-butene, and isobutene, respectively. Bimolecular rate constants for 1-butene and isobutene compare well to values measured previously at 103 K using C2H chemiluminescence. Photoionization spectra of the reaction products are measured and fitted to ionization spectra of the contributing isomers. In conjunction with absolute-ionization cross sections, these fits provide isomer-resolved product branching fractions. The reaction between C2H and 1-butene yields (65 ± 10)% C4H4 in the form of vinylacetylene and (35 ± 10)% C5H6 in the form of 4-penten-1-yne. The cis-2-butene and trans-2-butene reactions yield solely 3-penten-1-yne, and no discrimination is made between cis- and trans-3-penten-1-yne. Last, the isobutene reaction yields (26 ± 15)% 3-penten-1-yne, (35 ± 15)% 2-methyl-1-buten-3-yne, and (39 ± 15)% 4-methyl-3-penten-1-yne. The branching fractions reported for the C2H and butene reactions indicate that these reactions preferentially proceed via CH3 or C2H3 elimination rather than H-atom elimination. Within the experimental uncertainties, no evidence is found for the formation of cyclic species.

  11. Evaluation of gastric emptying time, gastrointestinal transit time, sedation score, and nausea score associated with intravenous constant rate infusion of lidocaine hydrochloride in clinically normal dogs.

    Science.gov (United States)

    Johnson, Rebecca A; Kierski, Katharine R; Jones, Brian G

    2017-05-01

    OBJECTIVE To quantify nausea and sedation scores, gastric emptying time, and gastrointestinal transit time after IV administration of a lidocaine hydrochloride bolus followed by a constant rate infusion (CRI) in clinically normal dogs. ANIMALS 6 Beagles. PROCEDURES In a crossover study, dogs were fed thirty 1.5-mm barium-impregnated spheres (BIPS) and received a saline (0.9% NaCl) solution bolus (0.05 mL/kg) IV (time 0) followed by a CRI at 10 mL/h, a lidocaine bolus (1 mg/kg) IV followed by a CRI at 25 μg/kg/min, or a lidocaine bolus (1 mg/kg) IV followed by a CRI at 50 μg/kg/min; CRIs were for 12 hours. Nausea and sedation scores were assessed and abdominal radiographs obtained immediately after feeding of BIPS and every hour for 12 hours and again 16 hours after CRI start. Percentage of BIPSs in the small and large intestines, gastric emptying time, and gastrointestinal transit time were assessed. RESULTS Gastric emptying time did not differ significantly among treatments. Significantly more BIPS were in the large intestine 4 to 7 hours after treatment start for the 50-μg/kg/min treatment than for the other 2 treatments. Six hours after treatment start, significantly more BIPS were in the large intestine for the 25-μg/kg/min treatment than for the saline solution treatment. Higher sedation and nausea scores were associated with the 50-μg/kg/min CRI. CONCLUSIONS AND CLINICAL RELEVANCE In clinically normal dogs, lidocaine CRI did not significantly affect gastric emptying. However, gastrointestinal transit time was mildly decreased and sedation and nausea scores increased in dogs administered a lidocaine CRI at clinically used doses.

  12. Estimating the plasma effect-site equilibrium rate constant (Ke₀) of propofol by fitting time of loss and recovery of consciousness.

    Science.gov (United States)

    Wu, Qi; Sun, Baozhu; Wang, Shuqin; Zhao, Lianying; Qi, Feng

    2013-01-01

    The present paper proposes a new approach for fitting the plasma effect-site equilibrium rate constant (Ke0) of propofol to satisfy the condition that the effect-site concentration (Ce) is equal at the time of loss of consciousness (LOC) and recovery of consciousness (ROC). Forty patients receiving intravenous anesthesia were divided into 4 groups and injected propofol 1.4, 1.6, 1.8, or 2 mg/kg at 1,200 mL/h. Durations from the start of injection to LOC and to ROC were recorded. LOC and ROC were defined as an observer's assessment of alertness and sedation scale change from 3 to 2 and from 2 to 3, respectively. Software utilizing bisection method iteration algorithms was built. Then, Ke0 satisfying the CeLOC=CeROC condition was estimated. The accuracy of the Ke0 estimated by our method was compared with the Diprifusor TCI Pump built-in Ke0 (0.26 min(-1)), and the Orchestra Workstation built-in Ke0 (1.21 min(-1)) in another group of 21 patients who were injected propofol 1.4 to 2 mg/kg. Our results show that the population Ke0 of propofol was 0.53 ± 0.18 min(-1). The regression equation for adjustment by dose (mg/kg) and age was Ke0=1.42-0.30 × dose-0.0074 × age. Only Ke0 adjusted by dose and age achieved the level of accuracy required for clinical applications. We conclude that the Ke0 estimated based on clinical signs and the two-point fitting method significantly improved the ability of CeLOC to predict CeROC. However, only the Ke0 adjusted by dose and age and not a fixed Ke0 value can meet clinical requirements of accuracy.

  13. Effects of maintenance of propofol-ketamine anesthesia with repeat bolus and constant rate infusion of propofol on physiological, biochemical, anesthetic and analgesic indices in dogs

    National Research Council Canada - National Science Library

    Njoku, Njoku

    2015-01-01

    The research work was aimed at investigating physiological, biochemical, analgesic and anesthetic indices of dogs anesthetized with propofol-ketamine and maintained with repeat bolus and constant infusions of propofol...

  14. Hypochlorous acid-mediated oxidation of lipid components and antioxidants present in low-density lipoproteins: absolute rate constants, product analysis, and computational modeling.

    Science.gov (United States)

    Pattison, David I; Hawkins, Clare L; Davies, Michael J

    2003-04-01

    Oxidation of low-density lipoproteins (LDL) is believed to contribute to the increased uptake of LDL by macrophages, which is an early event in atherosclerosis. Hypochlorous acid (HOCl) has been implicated as one of the major oxidants involved in these processes. In a previous study, the rates of reaction of HOCl with the reactive sites in proteins were investigated (Pattison, D. I., and Davies, M. J. (2001) Chem. Res. Toxicol. 14, 1453-1464). The work presented here expands on those studies to determine absolute second-order rate constants for the reactions of HOCl with various lipid components and antioxidants in aqueous solution (pH 7.4). The reactions of HOCl with phosphoryl-serine and phosphoryl-ethanolamine are rapid (k approximately 10(5) M(-)(1) s(-)(1)) and of comparable reactivity to many of the protein sites. The major products formed in these reactions are chloramines, which decay to give both nitrogen- and carbon-centered radicals. Subsequent reactions of these species may induce oxidation of the LDL lipid component. In contrast, phosphoryl-choline reacted much more slowly (k < 10(-)(2) M(-)(1) s(-)(1)). Reaction of HOCl with 3-pentenoic acid was used as a model of lipid double bonds and yielded k = 9 M(-)(1) s(-)(1). The reactions of the lipid-soluble antioxidants, alpha-tocopherol and ubiquinol-10, with HOCl were investigated with model compounds. For the reactions of HOCl with both Trolox and ubiquinol-0, k = 1.3 x 10(3) M(-)(1) s(-)(1); thus, these lipid soluble antioxidants are relatively ineffective as direct scavengers for HOCl as compared to water soluble antioxidants (e.g., ascorbate, k ca. 10(6) M(-)(1) s(-)(1)). The reaction of HOCl with hydroquinone (a simple model for ubiquinol-10) was also investigated both in aqueous solution (k = 45 M(-)(1) s(-)(1)) and in a less polar environment (k approximately 0.5 M(-)(1) s(-)(1) in THF). A computational model was developed using these kinetic parameters to predict which LDL targets are oxidized

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-05-01

    We have measured and assigned rate constants for energy transfer between chromophores in the light-harvesting protein C-phycocyanin (PC), in the monomeric and trimeric aggregation states, isolated from Synechococcus sp. PCC 7002. In order to compare the measured rate constants with those predicted by Fdrster`s theory of inductive resonance in the weak coupling limit, we have experimentally resolved several properties of the three chromophore types ({beta}{sub 155} {alpha}{sub 84}, {beta}{sub 84}) found in PC monomers, including absorption and fluorescence spectra, extinction coefficients, fluorescence quantum yields, and fluorescence lifetimes. The cpcB/C155S mutant, whose PC is missing the {beta}{sub 155} chromophore, was, useful in effecting the resolution of the chromophore properties and in assigning the experimentally observed rate constants for energy transfer to specific pathways.

  16. Rate constants for the gas-phase reactions of OH radicals with CH3CHF2 and CHCl2CF3 over the temperature range 295-388 K

    DEFF Research Database (Denmark)

    Nielsen, O.J.

    1991-01-01

    Rate constants for the reactions of OH radicals with CH3CHF2 and CHCl2CF3 have been determined over the temperature range 295-388 K and a total pressure of 1 atm. The OH rate data were obtained using the absolute rate technique of pulse radiolysis combined with kinetic spectroscopy. The data can...... and in the light of the important role CH3CHF2 and CHCl2CF3 play as alternatives to the fully halogenated chlorofluorocarbons....

  17. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  18. SU-E-P-55: The Reaserch of Cervical Cancer Delivered with Constant Dose Rate and Gantry Speed Arc Therapy(CDR-CAS-IMAT) On Conventional Linac

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, R; Bai, W; Chi, Z; Gao, C; Xiaomei, F [The Fourth Hospital of Hebei Medical University, Shijiazhuang, Hebei (China); Gao, Y [Hebei General Hospital, Shijiazhuang, Hebei (China)

    2015-06-15

    Purpose: Postoperative cervical cancer patients with large target volume and the target shape is concave, treatmented with static intensity-modulated radiotherapy (IMRT) is time consuming. The purpose of this study is to investigate using constant dose rate and gantry speed arc therapy(CDR-CAS-IMAT) on conventional linear accelrator, by comparing with the IMRT technology to evaluate the performance of CDR-CAS-IMAT on postoperative cervical cancer patients. Methods: 18 cervical cancer patients treated with IMRT on Varian 23IX were replanted using CDR-CAS-IMAT. The plans were generated on Oncentra v4.1 planning system, PTV was prescribed to 50.4 Gy in 28 fractions. Plans were evaluated based on the ability to meet the dose volume histogram. The homogeneity index (HI), conformity index (CI) of target volume, the dose of organs at risk, radiation delivery time and monitor units were also compared. SPSS 19.0 software paired T-test analysis was carried out on the two sets of data. Results: Compared with the IMRT plans PTV’s CI (t= 3.85, P =0.001), CTV’s CI, HI, D90, D95, D98, V95, V98, V100 (t=4.21, −3.18, 2.13, 4.65, 7.79, 2.29, 6.00, 2.13, p=0.001, 0.005, 0.049, 0.000, 0.000, 0.035, 0.000, 0.049), and cord D2 and rectum V40 (t=−2.65, −2.47, p= P =0.017, 0.025), and treatment time and MU (t=−36.0, −6.26, P =0.000, 0.000) were better than that of IMRT group. But the IMRT plans in terms of decreasing bladder V50, bowel V30 (t=2.14, 3.00, P =0.048, 0.008) and low dose irradiation volume were superior to that of CDR-CAS-IMAT plans. There were no significant differences in other statistical index. Conclusion: Cervical cancer patients with CDR-CAS-IMAT on Varian Clinical 23IX can get equivalent or superior dose distribution compared with the IMRT technology. IMAT have much less treatment time and MU can reduce the uncertainty factor and patient discomfort in treatment. This work was supported by the Medical Science Foundation of the health department of Hebei

  19. Preformulation Studies of Zidovudine Derivatives: Acid Dissociation Constants, Differential Scanning Calorimetry, Thermogravimetry, X-Ray Powder Diffractometry and Aqueous Stability Studies

    Science.gov (United States)

    Raviolo, Mónica A.; Briñón, Margarita C.

    2011-01-01

    As part as of the preformulation studies of new 5′-OH derivatives of zidovudine, compounds 2–6, their acid dissociation constants, Differential Scanning Calorimetry (DSC) and Thermogravimetry (TG) curves, X-Ray Powder diffractograms and aqueous stability are reported. A sensitive technique such as differential scanning potentiometry was used to determine the pKa constants of the above mentioned compounds. In addition, pKa values were calculated from theoretical methods, and no significant differences with those of experimental ones were observed. X-Ray Powder Diffractometry data demonstrated that compounds 2–4 were crystalline while 5 and 6 were amorphous. DSC analysis indicated that all of them presented an exothermic decomposition peak above 150 °C which is accompanied by a weight loss in the respective TG curves. The stability of these compounds in aqueous medium at different pH values was investigated, using a validated High Performance Liquid Chromatography (HPLC) method, which demonstrated to be rapid, selective, sensitive, accurate and stability-indicating. Good recovery, linearity and precision were also achieved. For all compounds the aqueous hydrolysis followed a pseudo-first-order kinetics, depending on pH and the union existing between AZT and the associate moiety. The hydrolysis was catalyzed by hydroxide ion in the 7.4–13.2 pH range, while all compounds exhibited pH-independent stability from acidic to neutral media (pHs 1.0–7.4). PMID:21886898

  20. Quasiclassical Trajectory Calculations of the Rate Constant of the OH + HBr → Br + H2O Reaction Using a Full-Dimensional Ab Initio Potential Energy Surface Over the Temperature Range 5 to 500 K.

    Science.gov (United States)

    de Oliveira-Filho, Antonio G S; Ornellas, Fernando R; Bowman, Joel M

    2014-02-20

    We report a permutationally invariant, ab initio potential energy surface (PES) for the OH + HBr → Br + H2O reaction. The PES is a fit to roughly 26 000 spin-free UCCSD(T)/cc-pVDZ-F12a energies and has no classical barrier to reaction. It is used in quasiclassical trajectory calculations with a focus on the thermal rate constant, k(T), over the temperature range 5 to 500 K. Comparisons with available experimental data over the temperature range 23 to 416 K are made using three approaches to treat the OH rotational and associated electronic partition function. All display an inverse temperature dependence of k(T) below roughly 160 K and a nearly constant temperature dependence above 160 K, in agreement with experiment. The calculated rate constant with no treatment of spin-orbit coupling is overall in the best agreement with experiment, being (probably fortuitously) within 20% of it.

  1. 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.

  2. Photochemical properties of trans-1-chloro-3,3,3-trifluoropropene (trans-CHCl═CHCF3): OH reaction rate constant, UV and IR absorption spectra, global warming potential, and ozone depletion potential.

    Science.gov (United States)

    Orkin, Vladimir L; Martynova, Larissa E; Kurylo, Michael J

    2014-07-17

    Measurements of the rate constant for the gas-phase reactions of OH radicals with trans-1-chloro-3,3,3-trifluoropropene (trans-CHCl═CHCF3) were performed using a flash photolysis resonance-fluorescence technique over the temperature range 220-370 K. The reaction rate constant exhibits a noticeable curvature of the temperature dependence in the Arrhenius plot, which can be represented by the following expression: kt-CFP (220-370 K) = 1.025 × 10(-13) × (T/298)(2.29) exp(+384/T) cm(3 )molecule(-1) s(-1). The room-temperature rate constant was determined to be kt-CFP (298 K) = (3.29 ± 0.10) × 10(-13) cm(3) molecule(-1) s(-1), where the uncertainty includes both two standard errors (statistical) and the estimated systematic error. For atmospheric modeling purposes, the rate constant below room temperature can be represented by the following expression: kt-CFP (220-298 K) = (7.20 ± 0.46) × 10(-13) exp[-(237 ± 16)/T] cm(3) molecule(-1) s(-1). There was no difference observed between the rate constants determined at 4 kPa (30 Torr) and 40 kPa (300 Torr) at both 298 and 370 K. The UV and IR absorption cross sections of this compound were measured at room temperature. The atmospheric lifetime, global warming potential, and ozone depletion potential of trans-CHCl═CHCF3 were estimated.

  3. A direct comparison of U.S. Environmental Protection Agency's method 304B and batch tests for determining activated-sludge biodegradation rate constants for volatile organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Cano, M.L.; Wilcox, M.E.; Compernolle, R. van

    1999-12-01

    Biodegradation rate constants for volatile organic compounds (VOCs) in activated-sludge systems are needed to quantify emissions. One current US environmental Protection Agency method for determining a biodegradation rate constant is Method 304B. In this approach, a specific activated-sludge unit is simulated by a continuous biological treatment system with a sealed headspace. Batch experiments, however, can be alternatives to Method 304B. Two of these batch methods are the batch test that uses oxygen addition (BOX) and the serum bottle test (SBT). In this study, Method 304B was directly compared to BOX and SBT experiments. A pilot-scale laboratory reactor was constructed to serve as the Method 304B unit. Biomass from the unit was also used to conduct BOX and modified SBT experiments (modification involved use of a sealed draft-tube reactor with a headspace recirculation pump instead of a serum bottle) for 1,2-dichloroethane, diisopropyl ether, methyl tertiary butyl ether, and toluene. Three experimental runs--each consisting of one Method 304B experiment, one BOX experiment, and one modified SBT experiment--were completed. The BOX and SBT data for each run were analyzed using a Monod model, and best-fit biodegradation kinetic parameters were determined for each experiment, including a first-order biodegradation rate constant (K{sub 1}). Experimental results suggest that for readily biodegradable VOCs the two batch techniques can provide improved means of determining biodegradation rate constants compared with Method 304B. In particular, these batch techniques avoid the Method 304B problem associated with steady-state effluent concentrations below analytical detection limits. However, experimental results also suggest that the two batch techniques should not be used to determine biodegradation rate constants for slowly degraded VOCs (i.e., K{sub 1} {lt} 0.1 L/g VSS-h).

  4. Rate coefficients for the reaction of methylglyoxal (CH3COCHO) with OH and NO3 and glyoxal (HCO)2 with NO3

    Science.gov (United States)

    Talukdar, R. K.; Zhu, L.; Feierabend, K. J.; Burkholder, J. B.

    2011-11-01

    Rate coefficients, k, for the gas-phase reaction of CH3COCHO (methylglyoxal) with the OH and NO3 radicals and (CHO)2 (glyoxal) with the NO3 radical are reported. Rate coefficients for the OH + CH3COCHO (k1) reaction were measured under pseudo-first-order conditions in OH as a function of temperature (211-373 K) and pressure (100-220 Torr, He and N2 bath gases) using pulsed laser photolysis to produce OH radicals and laser induced fluorescence to measure its temporal profile. k1 was found to be independent of the bath gas pressure with k1(295 K) = (1.29 ± 0.13) × 10-11 cm3 molecule-1 s-1 and a temperature dependence that is well represented by the Arrhenius expression k1(T) = (1.74 ± 0.20) × 10-12 exp[(590 ± 40)/T] cm3 molecule-1 s-1 where the uncertainties are 2σ and include estimated systematic errors. Rate coefficients for the NO3 + (CHO)2 (k3) and NO3 + CH3COCHO (k4) reactions were measured using a relative rate technique to be k3(296 K) = (4.0 ± 1.0) × 10-16 cm3 molecule-1 s-1 and k4(296 K) = (5.1 ± 2.1) × 10-16 cm3 molecule-1 s-1. k3(T) was also measured using an absolute rate coefficient method under pseudo-first-order conditions at 296 and 353 K to be (4.2 ± 0.8) × 10-16 and (7.9 ± 3.6) × 10-16 cm3 molecule-1 s-1, respectively, in agreement with the relative rate result obtained at room temperature. The atmospheric implications of the OH and NO3 reaction rate coefficients measured in this work are discussed.

  5. Rate coefficients for the reaction of methylglyoxal (CH3COCHO with OH and NO3 and glyoxal (HCO2 with NO3

    Directory of Open Access Journals (Sweden)

    J. B. Burkholder

    2011-11-01

    Full Text Available Rate coefficients, k, for the gas-phase reaction of CH3COCHO (methylglyoxal with the OH and NO3 radicals and (CHO2 (glyoxal with the NO3 radical are reported. Rate coefficients for the OH + CH3COCHO (k1 reaction were measured under pseudo-first-order conditions in OH as a function of temperature (211–373 K and pressure (100–220 Torr, He and N2 bath gases using pulsed laser photolysis to produce OH radicals and laser induced fluorescence to measure its temporal profile. k1 was found to be independent of the bath gas pressure with k1(295 K = (1.29 ± 0.13 × 10−11 cm3 molecule−1 s−1 and a temperature dependence that is well represented by the Arrhenius expression k1(T = (1.74 ± 0.20 × 10−12 exp[(590 ± 40/T] cm3 molecule−1 s−1 where the uncertainties are 2σ and include estimated systematic errors. Rate coefficients for the NO3 + (CHO2 (k3 and NO3 + CH3COCHO (k4 reactions were measured using a relative rate technique to be k3(296 K = (4.0 ± 1.0 × 10−16 cm3 molecule−1 s−1 and k4(296 K = (5.1 ± 2.1 × 10−16 cm3 molecule−1 s−1. k3(T was also measured using an absolute rate coefficient method under pseudo-first-order conditions at 296 and 353 K to be (4.2 ± 0.8 × 10−16 and (7.9 ± 3.6 × 10−16 cm3 molecule−1 s−1, respectively, in agreement with the relative rate result obtained at room temperature. The atmospheric implications of the OH and NO3 reaction rate coefficients measured in this work are discussed.

  6. Three applications of path integrals: equilibrium and kinetic isotope effects, and the temperature dependence of the rate constant of the [1,5] sigmatropic hydrogen shift in (Z)-1,3-pentadiene.

    Science.gov (United States)

    Zimmermann, Tomáš; Vaníček, Jiří

    2010-11-01

    Recent experiments have confirmed the importance of nuclear quantum effects even in large biomolecules at physiological temperature. Here we describe how the path integral formalism can be used to describe rigorously the nuclear quantum effects on equilibrium and kinetic properties of molecules. Specifically, we explain how path integrals can be employed to evaluate the equilibrium (EIE) and kinetic (KIE) isotope effects, and the temperature dependence of the rate constant. The methodology is applied to the [1,5] sigmatropic hydrogen shift in pentadiene. Both the KIE and the temperature dependence of the rate constant confirm the importance of tunneling and other nuclear quantum effects as well as of the anharmonicity of the potential energy surface. Moreover, previous results on the KIE were improved by using a combination of a high level electronic structure calculation within the harmonic approximation with a path integral anharmonicity correction using a lower level method.

  7. The reaction of fluorine atoms with methanol: yield of CH3O/CH2OH and rate constant of the reactions CH3O + CH3O and CH3O + HO2.

    Science.gov (United States)

    Assaf, Emmanuel; Schoemaecker, Coralie; Vereecken, Luc; Fittschen, Christa

    2017-11-15

    Xenondifluoride, XeF 2 , has been photolysed in the presence of methanol, CH 3 OH. Two reaction pathways are possible: F + CH 3 OH → CH 2 OH + HF and F + CH 3 OH → CH 3 O + HF. Both products, CH 2 OH and CH 3 O, will be converted to HO 2 in the presence of O 2 . The rate constants for the reaction of both radicals with O 2 differ by more than 3 orders of magnitude, which allows an unequivocal distinction between the two reactions when measuring HO 2 concentrations in the presence of different O 2 concentrations. The following yields have then been determined from time-resolved HO 2 profiles: ϕ CH 2 OH = (0.497 ± 0.013) and ϕ CH 3 O = (0.503 ± 0.013). Experiments under low O 2 concentrations lead to reaction mixtures containing nearly equal amounts of HO 2 (converted from the first reaction) and CH 3 O (from the second reaction). The subsequent HO 2 decays are very sensitive to the rate constants of the reaction between these two radicals and the following rate constants have been obtained: k(CH 3 O + CH 3 O) = (7.0 ± 1.4) × 10 -11 cm 3 s -1 and k(CH 3 O + HO 2 ) = (1.1 ± 0.2) × 10 -10 cm 3 s -1 . The latter reaction has also been theoretically investigated on the CCSD(T)//M06-2X/aug-cc-pVTZ level of theory and CH 3 OH + O 2 have been identified as the main products. Using μVTST, a virtually pressure independent rate constant of k(CH 3 O + HO 2 ) = 4.7 × 10 -11 cm 3 s -1 has been obtained, in good agreement with the experiment.

  8. Rate constant and mechanism of the reaction Cl + CFCl₂H → CFCl₂ + HCl over the temperature range 298-670 K in N₂ or N₂/O₂ diluent.

    Science.gov (United States)

    Kaiser, E W; Jawad, Khadija M

    2014-05-08

    The rate constant of the reaction Cl + CFCl2H (k1) has been measured relative to the established rate constant for the reaction Cl + CH4 (k2) at 760 Torr. The measurements were carried out in Pyrex reactors using a mixture of CFCl2H, CH4, and Cl2 in either N2 or N2/O2 diluent. Reactants and products were quantified by GC/FID analysis. Cl atoms were generated by irradiation of the mixture with 360 nm light to dissociate the Cl2 for temperatures up to ~550 K. At higher temperature, the Cl2 dissociated thermally, and no irradiation was used. Over the temperature range 298-670 K, k1 is consistently a factor of ~5 smaller than that of k2 with a nearly identical temperature dependence. The optimum non-Arrhenius rate constant is represented by the expression k1 = 1.14 × 10(-22) T(3.49) e(-241/T) cm(3) molecule(-1) s(-1) with an estimated uncertainty of ±15% including uncertainty in the reference reaction. CFCl3 formed from the reaction CFCl2 + Cl2 (k3) is the sole product in N2 diluent. In ~20% O2 at 298 K, the CFCl3 product is suppressed. The rate constant of reaction 3 was measured relative to that of reaction 4 [CFCl2 + O2 (k4)] giving the result k3/k4 = 0.0031 ± 0.0005 at 298 K. An earlier experiment by others observed C(O)FCl to be the major product of reaction channel 4 [formed via the sequence, CFCl2(O2) → CFCl2O → C(O)FCl + Cl]. Our current experiments verified that there is a Cl atom chain reaction in the presence of O2 as required by this mechanism.

  9. Electron attachment to halomethanes at high temperature: CH2Cl2, CF2Cl2, CH3Cl, and CF3Cl attachment rate constants up to 1100 K

    Science.gov (United States)

    Miller, Thomas M.; Friedman, Jeffrey F.; Schaffer, Linda C.; Viggiano, A. A.

    2009-08-01

    We have used a high-temperature flowing-afterglow Langmuir-probe apparatus to measure rate constants for electron attachment to halomethanes which attach electrons very inefficiently at room temperature, yielding Cl- ion product. We studied CH2Cl2 (495-973 K), CF2Cl2 (291-1105 K), and CF3Cl (524-1004 K) and include our recent measurement for CH3Cl (700-1100 K) in the discussion of the electron attachment results. The measured attachment rate constants show Arrhenius behavior in the temperature ranges examined, from which estimates of rate constants at 300 K may be made: CH2Cl2 (1.8×10-13 cm3 s-1), CH3Cl (1.1×10-17 cm3 s-1), and CF3Cl (4.2×10-14 cm3 s-1), all of which are difficult to measure directly. In the case of CF2Cl2, the room temperature rate constant was sufficiently large to be measured (1.6×10-9 cm3 s-1). The Arrhenius plots yield activation energies for the attachment reactions: 390±50 meV (CH2Cl2), 124±20 meV (CF2Cl2), 670±70 meV (CH3Cl), and 406±50 meV (CF3Cl). Comparisons are made with existing data where available. G3 calculations were carried out to obtain reaction energetics. They show that the parent anions of CH2Cl2 CF2Cl2, CH3Cl, and CF3Cl are stable, though CH3Cl- exists only as an electrostatically bound complex.

  10. 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.

  11. Rate constants of the equilibrium reactions SO⨪4 + HNO3 ⇄ HSO-4 + NO3 and SO⨪4 + NO-3 ⇄ SO2-4 + NO3

    DEFF Research Database (Denmark)

    Løgager, T.; Sehested, K.; Holcman, J.

    1993-01-01

    Rate constants of the following equilibrium reactions were determined by pulse radiolysis at high solute concentrations: SO4.- + HNO, half arrow right over half arrow left HSO4- + NO3. [k(f) = (2.7 +/- 0.5) x 10(6) M-1 s-1, k(r) = (5.6 +/- 1.0) x 10(3) M-1 s-1] and SO4.- + NO3- half arrow right...

  12. Oxygenation, local muscle oxygen consumption and joint specific power in cycling: the effect of cadence at a constant external work rate.

    Science.gov (United States)

    Skovereng, Knut; Ettema, Gertjan; van Beekvelt, Mireille C P

    2016-06-01

    The present study investigates the effect of cadence on joint specific power and oxygenation and local muscle oxygen consumption in the vastus lateralis and vastus medialis in addition to the relationship between joint specific power and local muscle oxygen consumption (mVO2). Seventeen recreationally active cyclists performed 6 stages of constant load cycling using cadences of 60, 70, 80, 90, 100 and 110 rpm. Joint specific power was calculated using inverse dynamics and mVO2 and oxygenation were measured using near-infrared spectroscopy. Increasing cadence led to increased knee joint power and decreased hip joint power while the ankle joint was unaffected. Increasing cadence also led to an increased deoxygenation in both the vastus lateralis and vastus medialis. Vastus lateralis mVO2 increased when cadence was increased. No effect of cadence was found for vastus medialis mVO2. This study demonstrates a different effect of cadence on the mVO2 of the vastus lateralis and vastus medialis. The combined mVO2 of the vastus lateralis and medialis showed a linear increase with increasing knee joint specific power, demonstrating that the muscles combined related to power generated over the joint.

  13. Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation.

    Science.gov (United States)

    Bao, Junwei Lucas; Zhang, Xin; Truhlar, Donald G

    2016-06-22

    Understanding the falloff in rate constants of gas-phase unimolecular reaction rate constants as the pressure is lowered is a fundamental problem in chemical kinetics, with practical importance for combustion, atmospheric chemistry, and essentially all gas-phase reaction mechanisms. In the present work, we use our recently developed system-specific quantum RRK theory, calibrated by canonical variational transition state theory with small-curvature tunneling, combined with the Lindemann-Hinshelwood mechanism, to model the dissociation reaction of fluoroform (CHF3), which provides a definitive test for falloff modeling. Our predicted pressure-dependent thermal rate constants are in excellent agreement with experimental values over a wide range of pressures and temperatures. The present validation of our methodology, which is able to include variational transition state effects, multidimensional tunneling based on the directly calculated potential energy surface along the tunneling path, and torsional and other vibrational anharmonicity, together with state-of-the-art reaction-path-based direct dynamics calculations, is important because the method is less empirical than models routinely used for generating full mechanisms, while also being simpler in key respects than full master equation treatments and the full reduced falloff curve and modified strong collision methods of Troe.

  14. Analysis of initial chlorophyll fluorescence induction kinetics in chloroplasts in terms of rate constants of donor side quenching release and electron trapping in photosystem II

    NARCIS (Netherlands)

    Vredenberg, W.J.

    2008-01-01

    The fluorescence induction F(t) of dark-adapted chloroplasts has been studied in multi-turnover 1 s light flashes (MTFs). A theoretical expression for the initial fluorescence rise is derived from a set of rate equations that describes the sequence of transfer steps associated with the reduction of

  15. Hydrolysis rate constants at 10–25 °C can be more than doubled by a short anaerobic pre-hydrolysis at 35 °C

    NARCIS (Netherlands)

    Zhang, L.; Gao, R.; Naka, A.; Hendrickx, T.L.G.; Rijnaarts, H.H.M.; Zeeman, G.

    2016-01-01

    Hydrolysis is the first step of the anaerobic digestion of complex wastewater and considered as the rate limiting step especially at low temperature. Low temperature (10–25 °C) hydrolysis was investigated with and without application of a short pre-hydrolysis at 35 °C. Batch experiments were

  16. DETERMINATION OF RATE CONSTANT AND STABILITY OF ADSORPTION IN COMPETITIVE ADSORPTION OF Cr(III AND Cd(II ON HUMIC ACID BY USING THE NEW MODEL OF KINETIC FORMULATION

    Directory of Open Access Journals (Sweden)

    Suyanta Suyanta

    2010-06-01

    Full Text Available Determination of rate and stability constants of adsorption in competitive adsorption of Cr(III and Cd(II on humic acid by using the new model of kinetic formulation has been done. The new model based on assumption that those adsorption was first order adsorption rearched equilibrium. Humic acid was isolated from Peat moss of Silaut- West Sumatra by modificated Schnitzer method. Humic acid characterization was conducted by using infrared spectrophotometer with KBR pellet method. The experiment of kinetic adsorption was conducted in batch system reactor using erlenmeyer at 25 ± 0.01 oC of water steam bath and in a series of sampling procedure. Initial concentration of both Cr(III and Cd(II was 4x10-4 M. Thirty milligrams of humic acid was added to 200 mL of metal solution, and then stirred continuously. At the fixed periode of time, 10 mL of sample was taken using a syringe, then filterd with 0.45 µm filter paper. Concentration of Cr(III and Cd(II in the filtrate was determinated by AAS, while that was adsorbed by humic acid was equal to difference between initial and equilibrium concentration. It was concluded that competitive adsorption of Cr(III and Cd(II on humic acid was first order adsorption rearched equilibrium as proposed in this research. Adsorption rate constant of Cr(III on humic acid  at competitive condition was greater than of Cd(II, but on the contrary for stability constant (K. Competition between Cr(III and Cd(II to interact with the active side of humic acid was dominated by Cr(III.   Keywords: rate constant, stability and competitive adsorption

  17. Flash photolytic generation and study of p-quinone methide in aqueous solution. An estimate of rate and equilibrium constants for heterolysis of the carbon-bromine bond in p-hydroxybenzyl bromide.

    Science.gov (United States)

    Chiang, Y; Kresge, A J; Zhu, Y

    2002-06-05

    Flash photolysis of p-hydroxybenzyl acetate in aqueous perchloric acid solution and formic acid, acetic acid, biphosphate ion, and tris(hydroxymethyl)methylammonium ion buffers produced p-quinone methide as a short-lived species that underwent hydration to p-hydroxybenzyl alcohol in hydronium ion catalyzed (k(H(+)) = 5.28 x 10(4) M(-1) s(-1)) and uncatalyzed (k(uc) = 3.33 s(-1)) processes. The inverse nature of the solvent isotope effect on the hydronium ion-catalyzed reaction, k(H(+))/k(D(+)) = 0.41, indicates that this process occurs by rapid and reversible protonation of the quinone methide on its carbonyl carbon atom, followed by rate-determining capture of the p-hydroxybenzyl carbocation so produced by water, while the magnitude of the rate constant on the uncatalyzed process indicates that this reaction occurs by simple nucleophilic addition of water to the methylene group of the quinone methide. p-Quinone methide also underwent hydronium ion-catalyzed and uncatalyzed nucleophilic addition reactions with chloride ion, bromide ion, thiocyanate ion, and thiourea. The solvent isotope effects on the hydronium ion-catalyzed processes again indicate that these reactions occurred by preequilibrium mechanisms involving a p-hydroxybenzyl carbocation intermediate, and assignment of a diffusion-controlled value to the rate constant for reaction of this cation with thiocyanate ion led to K(SH) = 110 M as the acidity constant of oxygen-protonated p-quinone methide. In a certain perchloric acid concentration range, the bromide ion reaction became biphasic, and least-squares analysis of the kinetic data using a double-exponential function provided k(Br(-)) = 3.8 x 10(8) M(-1) s(-1) as the rate constant for nucleophilic capture of the p-hydroxybenzyl carbocation by bromide ion, k(ionz) = 8.5 x 10(2) s(-1) for ionization of the carbon-bromine bond of p-hydroxybenzyl bromide, and K = 4.5 x 10(5) M(-1) as the equilibrium constant for the carbocation-bromide ion combination

  18. Cosmological constant, fine structure constant and beyond

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Hao; Zou, Xiao-Bo; Li, Hong-Yu; Xue, Dong-Ze [Beijing Institute of Technology, School of Physics, Beijing (China)

    2017-01-15

    In the present work, we consider the cosmological constant model Λ ∝ α{sup -6}, which is well motivated from three independent approaches. As is well known, the hint of varying fine structure constant α was found in 1998. If Λ ∝ α{sup -6} is right, it means that the cosmological constant Λ should also be varying. Here, we try to develop a suitable framework to model this varying cosmological constant Λ ∝ α{sup -6}, in which we view it from an interacting vacuum energy perspective. Then we consider the observational constraints on these models by using the 293 Δα/α data from the absorption systems in the spectra of distant quasars. We find that the model parameters can be tightly constrained to the very narrow ranges of O(10{sup -5}) typically. On the other hand, we can also view the varying cosmological constant model Λ ∝ α{sup -6} from another perspective, namely it can be equivalent to a model containing ''dark energy'' and ''warm dark matter'', but there is no interaction between them. We find that this is also fully consistent with the observational constraints on warm dark matter. (orig.)

  19. Ion exchange equilibrium constants

    CERN Document Server

    Marcus, Y

    2013-01-01

    Ion Exchange Equilibrium Constants focuses on the test-compilation of equilibrium constants for ion exchange reactions. The book first underscores the scope of the compilation, equilibrium constants, symbols used, and arrangement of the table. The manuscript then presents the table of equilibrium constants, including polystyrene sulfonate cation exchanger, polyacrylate cation exchanger, polymethacrylate cation exchanger, polysterene phosphate cation exchanger, and zirconium phosphate cation exchanger. The text highlights zirconium oxide anion exchanger, zeolite type 13Y cation exchanger, and

  20. Cheap but accurate calculation of chemical reaction rate constants from ab initio data, via system-specific, black-box force fields.

    Science.gov (United States)

    Steffen, Julien; Hartke, Bernd

    2017-10-28

    Building on the recently published quantum-mechanically derived force field (QMDFF) and its empirical valence bond extension, EVB-QMDFF, it is now possible to generate a reliable potential energy surface for any given elementary reaction step in an essentially black box manner. This requires a limited and pre-defined set of reference data near the reaction path and generates an accurate approximation of the reference potential energy surface, on and off the reaction path. This intermediate representation can be used to generate reaction rate data, with far better accuracy and reliability than with traditional approaches based on transition state theory (TST) or variational extensions thereof (VTST), even if those include sophisticated tunneling corrections. However, the additional expense at the reference level remains very modest. We demonstrate all this for three arbitrarily chosen example reactions.

  1. Cheap but accurate calculation of chemical reaction rate constants from ab initio data, via system-specific, black-box force fields

    Science.gov (United States)

    Steffen, Julien; Hartke, Bernd

    2017-10-01

    Building on the recently published quantum-mechanically derived force field (QMDFF) and its empirical valence bond extension, EVB-QMDFF, it is now possible to generate a reliable potential energy surface for any given elementary reaction step in an essentially black box manner. This requires a limited and pre-defined set of reference data near the reaction path and generates an accurate approximation of the reference potential energy surface, on and off the reaction path. This intermediate representation can be used to generate reaction rate data, with far better accuracy and reliability than with traditional approaches based on transition state theory (TST) or variational extensions thereof (VTST), even if those include sophisticated tunneling corrections. However, the additional expense at the reference level remains very modest. We demonstrate all this for three arbitrarily chosen example reactions.

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

    Science.gov (United States)

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

    2013-10-10

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

  3. Effects of uncertainty in SAPRC90 rate constants and selected product yields on reactivity adjustment factors for alternative fuel vehicle emissions. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Bergin, M.S.; Russell, A.G.; Yang, Y.J.; Milford, J.B.; Kirchner, F.; Stockwell, W.R.

    1996-07-01

    Tropospheric ozone is formed in the atmosphere by a series of reactions involving volatile organic compounds (VOCs) and nitrogen oxides (NO{sub x}). While NOx emissions are primarily composed of only two compounds, nitrogen oxide (NO) and nitrogen dioxide (NO{sub 2}), there are hundreds of different VOCs being emitted. In general, VOCs promote ozone formation, however, the rate and extent of ozone produced by the individual VOCs varies considerably. For example, it is widely acknowledged that formaldehyde (HCHO) is a very reactive VOC, and produces ozone rapidly and efficiently under most conditions. On the other hand, VOCs such as methane, ethane, propane, and methanol do not react as quickly, and are likely to form less urban ozone than a comparable mass of HCHO. The difference in ozone forming potential is one of the bases for the use of alternative fuels. The fuels considered in this study included compressed natural gas, LPG, mixtures of methanol and gasoline, ethanol and gasoline, and a reformulated gasoline.

  4. Acid Hydrolysis of Bromazepam Catalyzed by Micelles, Reverse Micelles, and Microemulsions

    OpenAIRE

    Ferdousi Begum; Mollah, M. Yousuf A.; M. Muhibur Rahman; Md. Abu Bin Hasan Susan

    2015-01-01

    Kinetics of the acid hydrolysis of bromazepam (Bz) has been investigated in micelles, reverse micelles, and microemulcions of cetyltrimethylammonium bromide (CTAB) by spectrophotometric method. The rate of the acid hydrolysis of Bz was found to be enhanced both below and above the critical micelle concentration (CMC) of CTAB in aqueous solution. The pseudo-first-order rate constant (k′) shows an initial decrease for both low and high H+ concentrations. With further increase in [CTAB], at low ...

  5. Calculating constants of the rates of the reactions of excitation, ionization, and atomic exchange: A model of a shock oscillator with a change of the Hamiltonian of the system

    Science.gov (United States)

    Tsyganov, D. L.

    2017-11-01

    A new model for calculating the rates of reactions of excitation, ionization, and atomic exchange is proposed. Diatomic molecule AB is an unstructured particle M upon the exchange of elastic-vibrational (VT) energy, i.e., a model of a shock forceful oscillator with a change in Hamiltonian (SFOH). The SFOH model is based on the quantum theory of strong perturbations. The SFOH model allows generalization in simulating the rates of the reactions of excitation, ionization, and atomic exchange in the vibrational-vibrational (VV) energy exchange of diatomic molecules, and the exchange of VV- and VT-energy of polyatomic molecules. The rate constants of the excitation of metastables A 3Σ u +, B 3Π g , W 3Δ u , B'3Σ u -, a'3Σ u -, and the ionization of a nitrogen molecules from ground state X2Σ g + upon a collision with a heavy structureless particle (a nitrogen molecule), are found as examples.

  6. Radium, Thorium and Radioactive Lead Isotopes in Groundwaters: Application to the in Situ Determination of Adsorption-Desorption Rate Constants and Retardation Factors

    Science.gov (United States)

    Krishnaswami, S.; Graustein, William C.; Turekian, Karl K.; Dowd, John F.

    1982-12-01

    Five groundwater samples taken from different Hydrogeologie settings in Connecticut were analyzed for major cation chemistry and the concentration of U and Th decay series nuclides 238U, 234Th, 226Ra, 222Rn, 210Pb, 210Po, 232Th, 228Ra, 228Th, and 224Ra. The concentration of 222Rn in the waters ranged between 103 and 104 dpm l-1 and was three to four orders of magnitude greater than that of the short-lived alpha daughters 224Ra, 228Ra, and 234Th, even though the rates of supply of these four nuclides to solution are expected to be similar. We infer that sorption removes radium and thorium from these groundwaters on a time scale of 3 minutes or less. The (224Ra/228Ra) and (234Th/228Th) activity ratios in these waters indicate that desorption of these nuclides occurs on a time scale of a week or less and that equilibrium between solution and surface phases is established. In situ retardation factors for radium, thorium, and lead may therefore be calculated directly from the isotopic data; values range from 4,500 to 200,000. Neither sorption time scales nor retardation factors are strongly dependent on the nuclide or on hydrogeology of the aquifer. Since our study includes nuclides with diverse chemical properties, we suggest that other uncomplexed heavy metals and transuranic elements will also behave in a manner similar to those measured here. The approach presented here should therefore find application in developing site-specific models of the transport of radioactive or stable elemental waste through water-saturated media.

  7. Cosmological Constant, Fine Structure Constant and Beyond

    CERN Document Server

    Wei, Hao; Li, Hong-Yu; Xue, Dong-Ze

    2016-01-01

    In this work, we consider the cosmological constant model $\\Lambda\\propto\\alpha^{-6}$, which is well motivated from three independent approaches. As is well known, the evidence of varying fine structure constant $\\alpha$ was found in 1998. If $\\Lambda\\propto\\alpha^{-6}$ is right, it means that the cosmological constant $\\Lambda$ should be also varying. In this work, we try to develop a suitable framework to model this varying cosmological constant $\\Lambda\\propto\\alpha^{-6}$, in which we view it from an interacting vacuum energy perspective. We propose two types of models to describe the evolutions of $\\Lambda$ and $\\alpha$. Then, we consider the observational constraints on these models, by using the 293 $\\Delta\\alpha/\\alpha$ data from the absorption systems in the spectra of distant quasars, and the data of type Ia supernovae (SNIa), cosmic microwave background (CMB), baryon acoustic oscillation (BAO). We find that the model parameters can be tightly constrained to the narrow ranges of ${\\cal O}(10^{-5})$ t...

  8. Determinação da constante cinética de cristalização não-isotérmica de polipropilenos modificados com ácido acrílico e anidrido maleico Determination of the non-isothermal crystallization rate constant of grafted maleic anhydride and grafted acrylic acid polypropylenes

    Directory of Open Access Journals (Sweden)

    Benjamim de M. Carvalho

    2006-12-01

    Full Text Available O propósito do presente trabalho foi testar a validade do Método da Curva Mestre para a determinação da constante de cristalização não-isotérmica de polipropilenos modificados com anidrido maleico e ácido acrílico. Experimentos de cristalização não-isotérmica foram realizados a diversas taxas de resfriamento por meio de Calorimetria Exploratória Diferencial (DSC. Para serem usadas no Método da Curva Mestre, as curvas originais obtidas em DSC foram corrigidas em termos da defasagem de temperatura entre a amostra polimérica e o forno do equipamento. A equação de Nakamura e a constante de cristalização determinada foram utilizadas para simular as curvas de cristalinidade relativa em função da temperatura para as diversas taxas de resfriamento. As curvas simuladas apresentaram boa concordância com as curvas experimentais para ambas as amostras de polipropileno modificado, mostrando que o Método da Curva Mestre pode ser empregado com sucesso para este polímero.The purpose of the present work was to evaluate the Master Curve Approach in the determination of the non-isothermal crystallization constant, for samples of two modified polypropylenes (grafted maleic anhydride and grafted acrylic acid polypropylenes. Non-isothermal crystallization experiments were carried out in a differential scanning calorimeter, DSC, at several cooling rates. The original DSC curves were corrected for the temperature lag between the sample and the DSC furnace. The Nakamura equation and the non-isothermal crystallization constant obtained by the Master Curve Approach were employed to simulate the curves of relative crystallinity as a function of temperature, for the different cooling rates. The generated curves presented good agreement with the experimental data for both samples of grafted polypropylene, showing that the Master Curve Approach can be successfully employed for these polymers.

  9. Constant Proportion Debt Obligations (CPDOs)

    DEFF Research Database (Denmark)

    Cont, Rama; Jessen, Cathrine

    2012-01-01

    Constant Proportion Debt Obligations (CPDOs) are structured credit derivatives that generate high coupon payments by dynamically leveraging a position in an underlying portfolio of investment-grade index default swaps. CPDO coupons and principal notes received high initial credit ratings from...

  10. Rate constants for the gas-phase reactions of (Z)-CF3CHdbnd CHF and (E)-CF3CHdbnd CHF with OH radicals at 253-328 K

    Science.gov (United States)

    Zhang, Ni; Chen, Liang; Mizukado, Junji; Quan, Hengdao; Suda, Hiroyuki

    2015-02-01

    Rate constants for the reactions of (Z)-CF3CHdbnd CHF (k1) and (E)-CF3CHdbnd CHF (k2) with OH radicals assessed by a relative rate method were: (0.911 ± 0.234) × 10-12 exp[(114 ± 70)/T], (1.05 ± 0.02) × 10-12 exp[-(118 ± 10)/T] at 253-328 K; and (1.37 ± 0.04) × 10-12, (0.699 ± 0.043) × 10-12 at 298 K cm3 molecule-1 s-1. The atmospheric lifetimes were determined as ∼8.4 and 17 days, respectively. GWPs for the 100 year time horizon were estimated to be 3 and 7, respectively.

  11. Estimation of hydrolysis rate constants for carbamates

    Science.gov (United States)

    Cheminformatics based tools, such as the Chemical Transformation Simulator under development in EPA’s Office of Research and Development, are being increasingly used to evaluate chemicals for their potential to degrade in the environment or be transformed through metabolism...

  12. A simple UV-ozone surface treatment to enhance photocatalytic performance of TiO 2 loaded polymer nanofiber membranes

    KAUST Repository

    Dilpazir, S.

    2016-01-29

    Homogeneously dispersed titanium dioxide loaded polyacrylonitrile nanofiber membranes with increased active mass loading, Ti3+ surface defects and hydrophilicity were fabricated by combining electrospinning and UV-ozone surface treatment. The photocatalytic activity improved by a factor of ∼2 and the kinetics of photodegradation switched from pseudo-first order to pseudo-second order with increasing TiO2 content with a maximum rate constant of 20.7 h-1. © The Royal Society of Chemistry 2016.

  13. Belousov-Zhabotinsky oscillatory reaction. Kinetics of malonic acid decomposition

    Directory of Open Access Journals (Sweden)

    LJILJANA KOLAR-ANIC

    2000-10-01

    Full Text Available The kinetics of the Belousov-Zhabotinsky (BZ oscillatory reaction was analyzed. With this aim, the time evolution of a reaction mixture composed of malonic acid, bromate, sulfuric acid and cerium(III was studied at 298 K. Pseudo-first order kinetics with respect to malonic acid as the species undergoing decomposition with a corresponding rate constant, k = 7.5×10-3 min-1, was found.

  14. ESR melting under constant voltage conditions

    Energy Technology Data Exchange (ETDEWEB)

    Schlienger, M.E.

    1997-02-01

    Typical industrial ESR melting practice includes operation at a constant current. This constant current operation is achieved through the use of a power supply whose output provides this constant current characteristic. Analysis of this melting mode indicates that the ESR process under conditions of constant current is inherently unstable. Analysis also indicates that ESR melting under the condition of a constant applied voltage yields a process which is inherently stable. This paper reviews the process stability arguments for both constant current and constant voltage operation. Explanations are given as to why there is a difference between the two modes of operation. Finally, constant voltage process considerations such as melt rate control, response to electrode anomalies and impact on solidification will be discussed.

  15. On Aryabhata's Planetary Constants

    OpenAIRE

    Kak, Subhash

    2001-01-01

    This paper examines the theory of a Babylonian origin of Aryabhata's planetary constants. It shows that Aryabhata's basic constant is closer to the Indian counterpart than to the Babylonian one. Sketching connections between Aryabhata's framework and earlier Indic astronomical ideas on yugas and cyclic calendar systems, it is argued that Aryabhata's system is an outgrowth of an earlier Indic tradition.

  16. Generalized Pickands constants

    NARCIS (Netherlands)

    K.G. Debicki

    2001-01-01

    textabstractPickands constants play an important role in the exact asymptotic of extreme values for Gaussian stochastic processes. By the {it generalized Pickands constant ${cal H_{eta$ we mean the limit begin{eqnarray* {cal H_{eta= lim_{T to inftyfrac{ {cal H_{eta(T){T, end{eqnarray* where ${cal

  17. Systematics of constant roll inflation

    Science.gov (United States)

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

    2018-02-01

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

  18. An investigation of the heart rate, heart rate variability, cardiac ions, troponin-I and CK-MB in men exposed to 1.5 T constant magnetic fields.

    Science.gov (United States)

    Sert, Cemil; Aktı, Zeynep; Sırmatel, Ocal; Yılmaz, Remzi

    2010-09-01

    The aim of this study was to investigate heart rate (HR), heart rate variability (HRV) and other cardiac parameters in individuals who were exposed to a high static magnetic field. 30 healthy male volunteers aged between 20-30 years were included. The searching was divided into three phases: pre-magnetic field, during the magnetic field and post-magnetic field. Every phase lasted 30 minutes. Pulse, systolic and diastolic blood pressure, respiration rate and elektrocardiography (ECG), recorded for 30 minutes, in all of the individuals were measured during three phases. The men were exposed to a 1.5 T static magnetic field. The levels of Na(+), K(+), Ca(2+), Cl(-), CK-MB, troponin-I and HR and HRV parameters were investigated. There was an increase in the respiration rate, and no change in the systolic and diastolic blood pressure and pulse in the individuals exposed to the magnetic field. There was also an enhancement in the values of ions, CK-MB and troponin-I after exposure to the magnetic field. Heart rate parameters (minimum HR-I, maximum HR-I, average HR-I) were decreased and rMSSD, pNN50, power, VLF, HF, LF values increased during the magnetic field.

  19. The Henry's constant of monochloramine.

    Science.gov (United States)

    Garcia, Miguel A; Anderson, Michael A

    2018-02-01

    Monochloramine is a secondary disinfectant used in drinking water and is also formed in chlorinated wastewater. While known to hydrolyze over time and react with dissolved organic matter, its partitioning between the aqueous and gas phase has not been extensively studied. Preliminary experiments demonstrated that monochloramine concentrations in solutions open to the atmosphere or actively aerated decreased more rapidly than in sealed solutions, indicating significant losses to the atmosphere. For example, a monochloramine solution open to the atmosphere yielded a loss rate constant of 0.08 d-1, a value twice that for sealed samples without headspace (0.04 d-1) where loss occurs exclusively as a result of hydrolysis. A solution aerated at 10 mL s-1 had a loss rate constant nearly 10× greater than that for hydrolysis alone (0.35 d-1). To better understand partitioning of monochloramine to the gas phase and potential for volatilization, the dimensionless Henry's law constants of monochloramine (KH) were determined using an equilibrium headspace technique at five different temperatures (11, 16, 21, 27, and 32 °C). The resulting values ranged from 8 × 10-3 to 4 × 10-2, indicating a semi-volatile compound, and were found to be consistent with quantitative structure activity relationship predictions. At 20 °C, monochloramine exhibits a dimensionless Henry's constant of about 1.7 × 10-2 which is 35 times greater than ammonia but comparable to the Henry's constant of inorganic semi-volatile compounds such sulfur dioxide. The Henry's constant values for monochloramine suggests that volatilization could be a relevant loss process in open systems such as rivers receiving chlorinated wastewater effluent, swimming pools and cooling towers. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Ferric ion-specific sequestering agents. 7. Synthesis, iron-exchange kinetics, and stability constants of N-substituted, sulfonated catechoylamide analogs of enterobactin

    Energy Technology Data Exchange (ETDEWEB)

    Pecoraro, Vincent L. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Weit, Frederick L. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Raymond, Kenneth N. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

    1981-08-01

    For treatment of chronic iron overload (as occurs in Cooley's anemia), ferric ion sequestering agents with specific properties are necessary. Two analogues of enterobactin [a microbial chelating agent with the greatest stability constant known for an Fe(III) complex] are reported which exhibit: i) hydrolytic stability; ii) water solubility; iii) N-substitution to block peptidase hydrolysis. The first compound, N,N',N"- trimethyl-N,N',N"-tris(2,3-dihydroxysulfobenzoyl)1,3,5-triaminomethyl- benzene, [Me3MECAMS, 6] was prepared from the amide of trimesloyl chloride (1) and MeNH2. The resulting amide was reduced to the triamine (3) and converted in three steps to the final product 6 in 6% overall yield. The proton-dependent formation constant (log K*) for the reaction: Fe3+ + H3L6- = FeL6- + 3H+ is 4.87, which gives an equilibrium concentration of [Fe3+] at pH 7.4 of 2 x 10-27 M for 10-5 M L (6) and 10-6 M total Fe3+. The estimated formation constant (log β110) is 40. At low pH the FeL6- complex undergoes a series of three, one-proton reactions which probably gives a tris-salicylate complex formed by the carbonyl and ortho-catechol oxygen of the 2,3-dihydroxybenzoyl units (the same reaction that occurs with ferric enterobactin). After six hours in the presence of 6 mM ascorbate, Me3MECAMS (6.0 mM) removed 3.7% of the ferric ion initially sequestered by the iron storage protein, ferritin. The human iron transport protein transferrin gives up iron to Me3MECAMS with a pseudo first-order rate constant of 1.9 x 10-3min-1 (ligand concentration 2 X 10-4 M). This rate is comparable to that of enterobactin and other catechoyl amide sequestering agents, and greatly exceeds that of desferrioxamine B (Desferal®), the current drug of choice in treating iron

  1. 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

  2. The H + HeH(+) → He + H2(+) reaction from the ultra-cold regime to the three-body breakup: exact quantum mechanical integral cross sections and rate constants.

    Science.gov (United States)

    De Fazio, Dario

    2014-06-21

    In this work, we present a quantum mechanical scattering study of the title reaction from 1 mK to 2000 K. Total integral cross sections and thermal rate constants are compared with previous theoretical and experimental data and with simpler theoretical models to understand the range of validity of the approximations used in the previous studies. The obtained quantum reactive observables have been found to be nearly insensitive to the roto-vibrational energy of the reactants at high temperatures. More sensitive to the reactant's roto-vibrational energy are the data in the cold and ultra-cold regimes. The implications of the new data presented here in the early universe scenario are also discussed and analyzed.

  3. Transition state theory thermal rate constants and RRKM-based branching ratios for the N((2)D) + CH(4) reaction based on multi-state and multi-reference ab initio calculations of interest for the Titan's chemistry.

    Science.gov (United States)

    Ouk, Chanda-Malis; Zvereva-Loëte, Natalia; Scribano, Yohann; Bussery-Honvault, Béatrice

    2012-10-30

    Multireference single and double configuration interaction (MRCI) calculations including Davidson (+Q) or Pople (+P) corrections have been conducted in this work for the reactants, products, and extrema of the doublet ground state potential energy surface involved in the N((2)D) + CH(4) reaction. Such highly correlated ab initio calculations are then compared with previous PMP4, CCSD(T), W1, and DFT/B3LYP studies. Large relative differences are observed in particular for the transition state in the entrance channel resolving the disagreement between previous ab initio calculations. We confirm the existence of a small but positive potential barrier (3.86 ± 0.84 kJ mol(-1) (MR-AQCC) and 3.89 kJ mol(-1) (MRCI+P)) in the entrance channel of the title reaction. The correlation is seen to change significantly the energetic position of the two minima and five saddle points of this system together with the dissociation channels but not their relative order. The influence of the electronic correlation into the energetic of the system is clearly demonstrated by the thermal rate constant evaluation and it temperature dependance by means of the transition state theory. Indeed, only MRCI values are able to reproduce the experimental rate constant of the title reaction and its behavior with temperature. Similarly, product branching ratios, evaluated by means of unimolecular RRKM theory, confirm the NH production of Umemoto et al., whereas previous works based on less accurate ab initio calculations failed. We confirm the previous findings that the N((2)D) + CH(4) reaction proceeds via an insertion-dissociation mechanism and that the dominant product channels are CH(2)NH + H and CH(3) + NH. Copyright © 2012 Wiley Periodicals, Inc.

  4. Deconstructing the Cosmological Constant

    CERN Document Server

    Jejjala, V; Minic, D; Jejjala, Vishnu; Leigh, Robert G.; Minic, Djordje

    2003-01-01

    Deconstruction provides a novel way of dealing with the notoriously difficult ultraviolet problems of four-dimensional gravity. This approach also naturally leads to a new perspective on the holographic principle, tying it to the fundamental requirements of unitarity and diffeomorphism invariance, as well as to a new viewpoint on the cosmological constant problem. The numerical smallness of the cosmological constant is implied by a unique combination of holography and supersymmetry, opening a new window into the fundamental physics of the vacuum.

  5. Path integral calculation of thermal rate constants within the quantum instanton approximation: application to the H + CH4 --> H2 + CH3 hydrogen abstraction reaction in full Cartesian space.

    Science.gov (United States)

    Zhao, Yi; Yamamoto, Takeshi; Miller, William H

    2004-02-15

    The quantum instanton approximation for thermal rate constants of chemical reactions [Miller, Zhao, Ceotto, and Yang, J. Chem. Phys. 119, 1329 (2003)], which is modeled after the earlier semiclassical instanton approach, is applied to the hydrogen abstraction reaction from methane by a hydrogen atom, H + CH4 --> H2 + CH3, using a modified and recalibrated version of the Jordan-Gilbert potential surface. The quantum instanton rate is evaluated using path integral Monte Carlo approaches based on the recently proposed implementation schemes [Yamamoto and Miller, J. Chem. Phys. 120, 3086 (2004)]. The calculations were carried out using the Cartesian coordinates of all the atoms (thus involving 18 degrees of freedom), thereby taking explicit account of rotational effects of the whole system and also allowing the equivalent treatment of the four methane hydrogens. To achieve such a treatment, we present extended forms of the path integral estimators for relevant quantities that may be used for general N-atom systems with any generalized reaction coordinates. The quantum instanton rates thus obtained for the temperature range T = 200-2000 K show good agreement with available experimental data, which gives support to the accuracy of the underlying potential surface used. Copyright 2004 American Institute of Physics

  6. Rapid burst kinetics in the hydrolysis of 4-nitrophenyl acetate by penicillin G acylase from Kluyvera citrophila. Effects of mutation F360V on rate constants for acylation and de-acylation.

    Science.gov (United States)

    Roa, A; Goble, M L; García, J L; Acebal, C; Virden, R

    1996-06-01

    The kinetics of release of 4-nitrophenol were followed by stopped-flow spectrophotometry with two 4-nitrophenyl ester substrates of penicillin G acylase from Kluyvera citrophila. With the ester of acetic acid, but not of propionic acid, there was a pre-steady-state exponential phase, the kinetics of which were inhibited by phenylacetic acid (a product of hydrolysis of specific substrates) to the extent predicted from Ki values. This was interpreted as deriving from rapid formation (73 mM-1.s-1) and slow hydrolysis (0.76 s-1) of an acetyl derivative of the side chain of the catalytic-centre residue Ser-290. With the mutant F360V, which differs from the wild-type enzyme in its ability to hydrolyse adipyl-L-leucine and has a kcat for 4-nitrophenyl acetate one-twentieth that of the wild-type enzyme, the corresponding values for the rates of formation and hydrolysis of the acetyl-enzyme were 11.1 mM-1.s-1 and 0.051 s-1 respectively. The ratio of these rate constants was three times that for the wild-type enzyme, suggesting that the mutant is less impaired in the rate of formation of an acetyl-enzyme than in its subsequent hydrolysis.

  7. Nonlinear regression analysis of kinetics of the photocatalytic decolorization of an azo dye in aqueous TiO2 slurry.

    Science.gov (United States)

    Behnajady, Mohammad A; Modirshahla, Nasser

    2006-11-01

    The kinetics of decolorization of an anionic monoazo dye of acid class named C.I. Acid Red 27 (AR27) was investigated in the UV/TiO2 process with nonlinear regression analysis. The experimental results indicated that the kinetics of decolorization of AR27 in this process fit well by pseudo-first order kinetics. With nonlinear regression analysis a model was developed for pseudo-first order rate constant (k(ap,UV/TiO2)) as a function of operational parameters such as TiO2 dosage, initial concentration of AR27, concentration of O2 and UV-light intensity (I0) as following: k(ap,UV/TiO2) = 0.0025 [TiO2](0.65) [AR27]0(-0.96) [O2](0.16)I0. This rate expression can be used for predicting k(ap,UV/TiO2) at different conditions.

  8. Beyond the Hubble Constant

    Science.gov (United States)

    1995-08-01

    about the distances to galaxies and thereby about the expansion rate of the Universe. A simple way to determine the distance to a remote galaxy is by measuring its redshift, calculate its velocity from the redshift and divide this by the Hubble constant, H0. For instance, the measured redshift of the parent galaxy of SN 1995K (0.478) yields a velocity of 116,000 km/sec, somewhat more than one-third of the speed of light (300,000 km/sec). From the universal expansion rate, described by the Hubble constant (H0 = 20 km/sec per million lightyears as found by some studies), this velocity would indicate a distance to the supernova and its parent galaxy of about 5,800 million lightyears. The explosion of the supernova would thus have taken place 5,800 million years ago, i.e. about 1,000 million years before the solar system was formed. However, such a simple calculation works only for relatively ``nearby'' objects, perhaps out to some hundred million lightyears. When we look much further into space, we also look far back in time and it is not excluded that the universal expansion rate, i.e. the Hubble constant, may have been different at earlier epochs. This means that unless we know the change of the Hubble constant with time, we cannot determine reliable distances of distant galaxies from their measured redshifts and velocities. At the same time, knowledge about such change or lack of the same will provide unique information about the time elapsed since the Universe began to expand (the ``Big Bang''), that is, the age of the Universe and also its ultimate fate. The Deceleration Parameter q0 Cosmologists are therefore eager to determine not only the current expansion rate (i.e., the Hubble constant, H0) but also its possible change with time (known as the deceleration parameter, q0). Although a highly accurate value of H0 has still not become available, increasing attention is now given to the observational determination of the second parameter, cf. also the Appendix at the

  9. Elastic constants of calcite

    Science.gov (United States)

    Peselnick, L.; Robie, R.A.

    1962-01-01

    The recent measurements of the elastic constants of calcite by Reddy and Subrahmanyam (1960) disagree with the values obtained independently by Voigt (1910) and Bhimasenachar (1945). The present authors, using an ultrasonic pulse technique at 3 Mc and 25??C, determined the elastic constants of calcite using the exact equations governing the wave velocities in the single crystal. The results are C11=13.7, C33=8.11, C44=3.50, C12=4.82, C13=5.68, and C14=-2.00, in units of 1011 dyncm2. Independent checks of several of the elastic constants were made employing other directions and polarizations of the wave velocities. With the exception of C13, these values substantially agree with the data of Voigt and Bhimasenachar. ?? 1962 The American Institute of Physics.

  10. Algorithm for structure constants

    CERN Document Server

    Paiva, F M

    2011-01-01

    In a $n$-dimensional Lie algebra, random numerical values are assigned by computer to $n(n-1)$ especially selected structure constants. An algorithm is then created, which calculates without ambiguity the remaining constants, obeying the Jacobi conditions. Differently from others, this algorithm is suitable even for poor personal computer. ------------- En $n$-dimensia algebro de Lie, hazardaj numeraj valoroj estas asignitaj per komputilo al $n(n-1)$ speciale elektitaj konstantoj de strukturo. Tiam algoritmo estas kreita, kalkulante senambigue la ceterajn konstantojn, obeante kondicxojn de Jacobi. Malsimile al aliaj algoritmoj, tiu cxi tauxgas ecx por malpotenca komputilo.

  11. Radiographic constant exposure technique

    DEFF Research Database (Denmark)

    Domanus, Joseph Czeslaw

    1985-01-01

    The constant exposure technique has been applied to assess various industrial radiographic systems. Different X-ray films and radiographic papers of two producers were compared. Special attention was given to fast film and paper used with fluorometallic screens. Radiographic image quality was tes...... was tested by the use of ISO wire IQI's and ASTM penetrameters used on Al and Fe test plates. Relative speed and reduction of kilovoltage obtained with the constant exposure technique were calculated. The advantages of fast radiographic systems are pointed out...

  12. Kinetic Study of Free Radicals Scavenging by Saffron Petal Extracts

    Directory of Open Access Journals (Sweden)

    T. Ardalan

    2013-01-01

    Full Text Available Saffron petal is the main by-product of saffron processing which is produced in large amounts, annually. The objectives of this study were to study the antioxidant activity and free radical-scavenging effects of saffron petal extracts. The ability of saffron petal to act as an antioxidant using the 2, 2-diphenyl-1-picrylhydrazyl (DPPH free-radical method was investigated by applying the Uv–Vis spectrometry. The Uv–Vis spectra of reaction mixtures in acetonitrile revealed that saffron petal has a considerable effect on scavenging free radical. Kinetic studies were conducted by measuring the disappearance of DPPH in acetonitrile over the wavelength range of 515-522 nm under pseudo-first-order conditions at 37oC. Furthermore, the pseudo first order rate constants were determined

  13. The Fine Structure Constant

    Indian Academy of Sciences (India)

    IAS Admin

    electromagnetic force between subatomic charged parti- cles, and essentially determines how an atom holds to- gether its electrons. It is however not obvious why this constant has this ..... about α in 1948: “The theoretical interpretation of its numerical value is one of the most important unsolved problems of atomic physics.”

  14. Gravitational constant calculation methodologies

    OpenAIRE

    Shakhparonov, V. M.; Karagioz, O. V.; Izmailov, V. P.

    2011-01-01

    We consider the gravitational constant calculation methodologies for a rectangular block of the torsion balance body presented in the papers Phys. Rev. Lett. 102, 240801 (2009) and Phys.Rev. D. 82, 022001 (2010). We have established the influence of non-equilibrium gas flows on the obtained values of G.

  15. Reduction in the rates of protein and amino acid catabolism to slow down the accumulation of endogenous ammonia: a strategy potentially adopted by mudskippers (Periophthalmodon schlosseri snd Boleophthalmus boddaerti) during aerial exposure in constant darkness.

    Science.gov (United States)

    Lim, C B; Chew, S F; Anderson, P M; Ip, Y K

    2001-05-01

    This study was designed to elucidate the strategies adopted by mudskippers to handle endogenous ammonia during aerial exposure in constant darkness. Under these conditions, specimens exhibited minimal locomotory activity, and the ammonia and urea excretion rates in both Periophthalmodon schlosseri and Boleophthalmus boddaerti decreased significantly. As a consequence, ammonia accumulation occurred in the tissues of both species of mudskipper. A significant increase in urea levels was found in the liver of P. schlosseri after 24h of aerial exposure, but no similar increase was seen in the tissues of B. boddaerti. It is unlikely that these two species of mudskipper detoxified ammonia to urea during aerial exposure since B. boddaerti does not possess a complete ornithine-urea cycle (OUC) and, although all the OUC enzymes were present in P. schlosseri, the activity of carbamoyl phosphate synthetase present in the liver mitochondria was too low to render the OUC functional for ammonia detoxification. Peritoneal injection of 15NH4Cl into P. schlosseri showed that this mudskipper was capable of incorporating some of the labelled ammonia into urea in its liver. However, aerial exposure did not affect this capability and did not induce detoxification of the accumulated ammonia to urea. Mudskippers exposed to terrestrial conditions and constant darkness did, however, show significant decreases in the total free amino acid content in the liver and blood, in the case of P. schlosseri and in the muscle of B. boddaerti. No changes in the alanine or glutamine content of the muscle were found in either species. Analyses of the balance between the reduction in nitrogenous excretion and the increase in nitrogenous accumulation further revealed that these two species of mudskipper were capable of reducing their protein and amino acid catabolic rates. Such adaptations constitute the most efficient way to avoid the build-up of internal ammonia, and would render unnecessary the

  16. The characterization of the adsorption of cadmium from aqueous solution using natural fibers treated with nanoparticles

    Science.gov (United States)

    Rediske, Nicole M.

    The objective of this research was to characterize natural carbon fibers from coconut husks, both bare and impregnated with metallic nanoparticles, in removing cadmium from aqueous media. The adsorbent load, kinetics, isotherm parameters, removal efficiencies, desorption capacity and possible contaminant removal mechanisms were evaluated. It was found that the fibers treated with metallic nanoparticles performed better than the bare fibers in removing cadmium from water. The ideal conditions were found to be neutral pH with low initial cadmium concentrations. Through the kinetic analyses, the adsorption process was first thought to be pseudo first order with two separate adsorption mechanisms apparent. Upon further analysis, it was seen that the first mechanism does not follow the pseudo first order kinetics model. An increase in calcium and magnesium concentrations was observed as the cadmium concentrations decreases. This increase corresponds with first mechanism. This suggests the cadmium removal in the first mechanism is due to ion exchange. The second mechanism's rate constant was consistently lower than the first mechanisms rate constant by an order of magnitude. This led to the hypothesis that the second mechanism is controlled by van de Waals forces, specifically ion-induced dipole interactions, and physical adsorption. It was also found that the cadmium does not effectively desorb from the wasted fibers in DI water. Keywords: Adsorption; kinetics; pseudo first order; cadmium; metallic nanoparticles; natural fibers; removal efficiencies; ion exchange.

  17. Perturbing effects of chiral stationary phase on enantiomerization second-order rate constants determined by enantioselective dynamic high-performance liquid chromatography: a practical tool to quantify the accessible acid and basic catalytic sites bonded on chromatographic supports.

    Science.gov (United States)

    Cirilli, Roberto; Costi, Roberta; Di Santo, Roberto; La Torre, Francesco; Pierini, Marco; Siani, Gabriella

    2009-05-01

    Second-order rate constants of the diethylamine-promoted enantiomerization of 2-[2-(1-methyl-1H-pyrrol-2-yl)-2-oxo-1-phenylethyl]-isoindole-1,3-dione, a chiral alpha-substituted ketone endowed with high anti-MAO activity type-A, were measured by dynamic high-performance liquid chromatography (DHPLC), stopped-flow high-performance liquid chromatography (sf-HPLC), and a classical method based on enantioselective HPLC as the monitoring tool. The chiral column used in all determinations was the commercial Chiralpak AD. By comparison of the obtained data, perturbing effects of the stationary phase on the DHPLC and sf-HPLC determinations were highlighted and distinguished in indirect (SP(IPC)) and direct (SP(DPC)) type. It was evidenced that SP(DPC) noise effects may be completely erased by simple mathematical treatment of data obtained at different concentrations of the basic catalyst. Perturbations of type SP(IPC) may instead only be partially kept down by modulating the concentration of the basic catalyst. An estimation of the density distribution of catalytic sites covalently bonded to the stationary phase (SP) of the Chiralpak AD was performed exploiting the quantified SP(DPC) effects. Such an approach might be of general application, supplying a useful way to characterize the attitude of SPs to speed acid- or base-catalyzed equilibria possibly active during chromatographic separations.

  18. High-level direct-dynamics variational transition state theory calculations including multidimensional tunneling of the thermal rate constants, branching ratios, and kinetic isotope effects of the hydrogen abstraction reactions from methanol by atomic hydrogen.

    Science.gov (United States)

    Meana-Pañeda, Rubén; Truhlar, Donald G; Fernández-Ramos, Antonio

    2011-03-07

    We report a detailed theoretical study of the hydrogen abstraction reaction from methanol by atomic hydrogen. The study includes the analysis of thermal rate constants, branching ratios, and kinetic isotope effects. Specifically, we have performed high-level computations at the MC3BB level together with direct dynamics calculations by canonical variational transition state theory (CVT) with the microcanonically optimized multidimensional tunneling (μOMT) transmission coefficient (CVT/μOMT) to study both the CH(3)OH+H→CH(2)OH+H(2) (R1) reaction and the CH(3)OH+H→CH(3)O+H(2) (R2) reaction. The CVT/μOMT calculations show that reaction R1 dominates in the whole range 298≤T (K)≤2500 and that anharmonic effects on the torsional mode about the C-O bond are important, mainly at high temperatures. The activation energy for the total reaction sum of R1 and R2 reactions changes substantially with temperature and, therefore, the use of straight-line Arrhenius plots is not valid. We recommend the use of new expressions for the total R1 + R2 reaction and for the R1 and R2 individual reactions. © 2011 American Institute of Physics.

  19. Hydrolysis rate constants at 10-25 °C can be more than doubled by a short anaerobic pre-hydrolysis at 35 °C.

    Science.gov (United States)

    Zhang, L; Gao, R; Naka, A; Hendrickx, T L G; Rijnaarts, H H M; Zeeman, G

    2016-11-01

    Hydrolysis is the first step of the anaerobic digestion of complex wastewater and considered as the rate limiting step especially at low temperature. Low temperature (10-25 °C) hydrolysis was investigated with and without application of a short pre-hydrolysis at 35 °C. Batch experiments were executed using cellulose and tributyrin as model substrates for carbohydrates and lipids. The results showed that the low temperature anaerobic hydrolysis rate constants increased by a factor of 1.5-10, when the short anaerobic pre-hydrolysis at 35 °C was applied. After the pre-hydrolysis phase at 35 °C and decreasing the temperature, no lag phase was observed in any case. Without the pre-hydrolysis, the lag phase for cellulose hydrolysis at 35-10 °C was 4-30 days. Tributyrin hydrolysis showed no lag phase at any temperature. The hydrolysis efficiency of cellulose increased from 40 to 62%, and from 9.6 to 40% after 9.1 days at 15 and 10 °C, respectively, when the pre-hydrolysis at 35 °C was applied. The hydrolysis efficiency of tributyrin at low temperatures with the pre-hydrolysis at 35 °C was similar to those without the pre-hydrolysis. The hydrolytic activity of the supernatant collected from the digestate after batch digestion of cellulose and tributyrin at 35 °C was higher than that of the supernatants collected from the low temperature (≤25 °C) digestates. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Rate Constant for the Reaction CH3 + CH3 Yields C2H6 at T = 155 K and Model Calculation of the CH3 Abundance in the Atmospheres of Saturn and Neptune

    Science.gov (United States)

    Cody, Regina J.; Romani, Paul N.; Nesbitt, Fred L.; Iannone, Mark A.; Tardy, Dwight C.; Stief, Louis J.

    2003-01-01

    The column abundances of CH3 observed by the Infrared Space Observatory (ISO) satellite on Saturn and Neptune were lower than predicted by atmospheric photochemical models, especially for Saturn. It has been suggested that the models underestimated the loss of CH3 due to poor knowledge of the rate constant k of the CH3 + CH3 self-reaction at the low temperatures and pressures of these atmospheres. Motivated by this suggestion, we undertook a combined experimental and photochemical modeling study of the CH3 + CH3 reaction and its role in determining planetary CH3 abundances. In a discharge flow-mass spectrometer system, k was measured at T = 155 K and three pressures of He. The results in units of cu cm/molecule/s are k(0.6 Torr) = 6.82 x 10(exp -11), k(1.0 Torr) = 6.98 x 10(exp -11), and k(1.5 Torr) = 6.91 x 10(exp -11). Analytical expressions for k were derived that (1) are consistent with the present laboratory data at T = 155 K, our previous data at T = 202 K and 298 K, and those of other studies in He at T = 296-298 K and (2) have some theoretical basis to provide justification for extrapolation. The derived analytical expressions were then used in atmospheric photochemical models for both Saturn and Neptune. These model results reduced the disparity with observations of Saturn, but not with observations of Neptune. However, the disparity for Neptune is much smaller. The solution to the remaining excess CH3 prediction in the models relative to the ISO observations lies, to a large extent, elsewhere in the CH3 photochemistry or transport, not in the CH3 + CH3 rate.

  1. The Hubble Constant.

    Science.gov (United States)

    Jackson, Neal

    2015-01-01

    I review the current state of determinations of the Hubble constant, which gives the length scale of the Universe by relating the expansion velocity of objects to their distance. There are two broad categories of measurements. The first uses individual astrophysical objects which have some property that allows their intrinsic luminosity or size to be determined, or allows the determination of their distance by geometric means. The second category comprises the use of all-sky cosmic microwave background, or correlations between large samples of galaxies, to determine information about the geometry of the Universe and hence the Hubble constant, typically in a combination with other cosmological parameters. Many, but not all, object-based measurements give H0 values of around 72-74 km s(-1) Mpc(-1), with typical errors of 2-3 km s(-1) Mpc(-1). This is in mild discrepancy with CMB-based measurements, in particular those from the Planck satellite, which give values of 67-68 km s(-1) Mpc(-1) and typical errors of 1-2 km s(-1) Mpc(-1). The size of the remaining systematics indicate that accuracy rather than precision is the remaining problem in a good determination of the Hubble constant. Whether a discrepancy exists, and whether new physics is needed to resolve it, depends on details of the systematics of the object-based methods, and also on the assumptions about other cosmological parameters and which datasets are combined in the case of the all-sky methods.

  2. The Hubble Constant

    Directory of Open Access Journals (Sweden)

    Neal Jackson

    2015-09-01

    Full Text Available I review the current state of determinations of the Hubble constant, which gives the length scale of the Universe by relating the expansion velocity of objects to their distance. There are two broad categories of measurements. The first uses individual astrophysical objects which have some property that allows their intrinsic luminosity or size to be determined, or allows the determination of their distance by geometric means. The second category comprises the use of all-sky cosmic microwave background, or correlations between large samples of galaxies, to determine information about the geometry of the Universe and hence the Hubble constant, typically in a combination with other cosmological parameters. Many, but not all, object-based measurements give H_0 values of around 72–74 km s^–1 Mpc^–1, with typical errors of 2–3 km s^–1 Mpc^–1. This is in mild discrepancy with CMB-based measurements, in particular those from the Planck satellite, which give values of 67–68 km s^–1 Mpc^–1 and typical errors of 1–2 km s^–1 Mpc^–1. The size of the remaining systematics indicate that accuracy rather than precision is the remaining problem in a good determination of the Hubble constant. Whether a discrepancy exists, and whether new physics is needed to resolve it, depends on details of the systematics of the object-based methods, and also on the assumptions about other cosmological parameters and which datasets are combined in the case of the all-sky methods.

  3. Spaces of constant curvature

    CERN Document Server

    Wolf, Joseph A

    2010-01-01

    This book is the sixth edition of the classic Spaces of Constant Curvature, first published in 1967, with the previous (fifth) edition published in 1984. It illustrates the high degree of interplay between group theory and geometry. The reader will benefit from the very concise treatments of riemannian and pseudo-riemannian manifolds and their curvatures, of the representation theory of finite groups, and of indications of recent progress in discrete subgroups of Lie groups. Part I is a brief introduction to differentiable manifolds, covering spaces, and riemannian and pseudo-riemannian geomet

  4. Enhanced peptide nucleic acid binding to supercoiled DNA: possible implications for DNA "breathing" dynamics

    DEFF Research Database (Denmark)

    Bentin, T; Nielsen, Peter E.

    1996-01-01

    to that of relaxed DNA. The pseudo-first-order rate constant [k psi (sigma)] obeys an exponential function, k psi (sigma) = k psi (lin)e-sigma delta, where delta is a constant of 105 and k psi lin is the rate of PNA binding to linear DNA (sigma = 0). The activation energy [Ea(sigma)] was determined as approximately...... efficient with supercoiled than with linear DNA. In the presence of 140 mM KCI, the PNA binding rate was reduced but, notably, highly dependent on template topology. Negative supercoiling (mean superhelix density, sigma approximately -0.051) increased the rate of binding by 2 orders of magnitude compared...

  5. Quantum Theory without Planck's Constant

    OpenAIRE

    Ralston, John P.

    2012-01-01

    Planck's constant was introduced as a fundamental scale in the early history of quantum mechanics. We find a modern approach where Planck's constant is absent: it is unobservable except as a constant of human convention. Despite long reference to experiment, review shows that Planck's constant cannot be obtained from the data of Ryberg, Davisson and Germer, Compton, or that used by Planck himself. In the new approach Planck's constant is tied to macroscopic conventions of Newtonian origin, wh...

  6. Adsorption of food dyes acid blue 9 and food yellow 3 onto chitosan: stirring rate effect in kinetics and mechanism.

    Science.gov (United States)

    Dotto, G L; Pinto, L A A

    2011-03-15

    Adsorption of food dyes acid blue 9 and food yellow 3 onto chitosan was studied. Stirring rate influence on kinetics and mechanism was verified. Infra-red analysis was carried out before and after adsorption in order to verify the adsorption nature. Adsorption experiments were carried out in batch systems with different stirring rates (15-400 rpm). Kinetic behavior was analyzed through the pseudo-first-order, pseudo-second-order and Elovich models. Adsorption mechanism was verified according to the film diffusion model and HSDM model. Pseudo-second-order and Elovich models were satisfactory in order to represent experimental data in all stirring rates. For both dyes, adsorption occurred by film and intraparticle diffusion, and the stirring rate increase caused a decrease in film diffusion resistance. Therefore, the film diffusivity increased the adsorption capacity and, consequently, intraparticle diffusivity increased. In all stirring rates, the rate-limiting step was film diffusion. Adsorption of acid blue 9 and food yellow 3 onto chitosan occurred by chemiosorption. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. When constants are important

    Energy Technology Data Exchange (ETDEWEB)

    Beiu, V.

    1997-04-01

    In this paper the authors discuss several complexity aspects pertaining to neural networks, commonly known as the curse of dimensionality. The focus will be on: (1) size complexity and depth-size tradeoffs; (2) complexity of learning; and (3) precision and limited interconnectivity. Results have been obtained for each of these problems when dealt with separately, but few things are known as to the links among them. They start by presenting known results and try to establish connections between them. These show that they are facing very difficult problems--exponential growth in either space (i.e. precision and size) and/or time (i.e., learning and depth)--when resorting to neural networks for solving general problems. The paper will present a solution for lowering some constants, by playing on the depth-size tradeoff.

  8. The Hubble Constant

    Directory of Open Access Journals (Sweden)

    Jackson Neal

    2007-09-01

    Full Text Available I review the current state of determinations of the Hubble constant, which gives the length scale of the Universe by relating the expansion velocity of objects to their distance. In the last 20 years, much progress has been made and estimates now range between 60 and 75 km s^-1 Mpc^-1, with most now between 70 and 75 km s^-1 Mpc^-1, a huge improvement over the factor-of-2 uncertainty which used to prevail. Further improvements which gave a generally agreed margin of error of a few percent rather than the current 10% would be vital input to much other interesting cosmology. There are several programmes which are likely to lead us to this point in the next 10 years.

  9. Philicities, Fugalities, and Equilibrium Constants.

    Science.gov (United States)

    Mayr, Herbert; Ofial, Armin R

    2016-05-17

    The mechanistic model of Organic Chemistry is based on relationships between rate and equilibrium constants. Thus, strong bases are generally considered to be good nucleophiles and poor nucleofuges. Exceptions to this rule have long been known, and the ability of iodide ions to catalyze nucleophilic substitutions, because they are good nucleophiles as well as good nucleofuges, is just a prominent example for exceptions from the general rule. In a reaction series, the Leffler-Hammond parameter α = δΔG(⧧)/δΔG° describes the fraction of the change in the Gibbs energy of reaction, which is reflected in the change of the Gibbs energy of activation. It has long been considered as a measure for the position of the transition state; thus, an α value close to 0 was associated with an early transition state, while an α value close to 1 was considered to be indicative of a late transition state. Bordwell's observation in 1969 that substituent variation in phenylnitromethanes has a larger effect on the rates of deprotonation than on the corresponding equilibrium constants (nitroalkane anomaly) triggered the breakdown of this interpretation. In the past, most systematic investigations of the relationships between rates and equilibria of organic reactions have dealt with proton transfer reactions, because only for few other reaction series complementary kinetic and thermodynamic data have been available. In this Account we report on a more general investigation of the relationships between Lewis basicities, nucleophilicities, and nucleofugalities as well as between Lewis acidities, electrophilicities, and electrofugalities. Definitions of these terms are summarized, and it is suggested to replace the hybrid terms "kinetic basicity" and "kinetic acidity" by "protophilicity" and "protofugality", respectively; in this way, the terms "acidity" and "basicity" are exclusively assigned to thermodynamic properties, while "philicity" and "fugality" refer to kinetics

  10. Evaluation of the kinetic oxidation of aqueous volatile organic compounds by permanganate.

    Science.gov (United States)

    Mahmoodlu, Mojtaba G; Hassanizadeh, S Majid; Hartog, Niels

    2014-07-01

    The use of permanganate solutions for in-situ chemical oxidation (ISCO) is a well-established groundwater remediation technology, particularly for targeting chlorinated ethenes. The kinetics of oxidation reactions is an important ISCO remediation design aspect that affects the efficiency and oxidant persistence. The overall rate of the ISCO reaction between oxidant and contaminant is typically described using a second-order kinetic model while the second-order rate constant is determined experimentally by means of a pseudo first order approach. However, earlier studies of chlorinated hydrocarbons have yielded a wide range of values for the second-order rate constants. Also, there is limited insight in the kinetics of permanganate reactions with fuel-derived groundwater contaminants such as toluene and ethanol. In this study, batch experiments were carried out to investigate and compare the oxidation kinetics of aqueous trichloroethylene (TCE), ethanol, and toluene in an aqueous potassium permanganate solution. The overall second-order rate constants were determined directly by fitting a second-order model to the data, instead of typically using the pseudo-first-order approach. The second-order reaction rate constants (M(-1) s(-1)) for TCE, toluene, and ethanol were 8.0×10(-1), 2.5×10(-4), and 6.5×10(-4), respectively. Results showed that the inappropriate use of the pseudo-first-order approach in several previous studies produced biased estimates of the second-order rate constants. In our study, this error was expressed as a function of the extent (P/N) in which the reactant concentrations deviated from the stoichiometric ratio of each oxidation reaction. The error associated with the inappropriate use of the pseudo-first-order approach is negatively correlated with the P/N ratio and reached up to 25% of the estimated second-order rate constant in some previous studies of TCE oxidation. Based on our results, a similar relation is valid for the other volatile

  11. Tebuconazole photocatalytic degradation kinetics

    OpenAIRE

    Prestes, Thiago de Hermann; Gibbon, Danielle de Oliveira; Lansarin, Marla Azário; Moro, Celso Camilo

    2010-01-01

    The tebuconazole photocatalytic degradation kinetics was studied in a batch reactor using TiO2 (P25-Degussa) as catalyst and a high pressure mercury lamp. The photolysis, adsorption and irradiation effects in the reaction rate were evaluated. Afterward, the suspension catalyst concentration and initial pH to the maximum reaction rate was determined. It was observed that the reaction rate can be approached by a pseudo-first order, with a maximum kinetics constant at 260 mg L-1catalyst concentr...

  12. Degradação fotocatalítica do fungicida tebuconazole em solução aquosa Tebuconazole photocatalytic degradation kinetics

    Directory of Open Access Journals (Sweden)

    Thiago de Hermann Prestes

    2010-01-01

    Full Text Available The tebuconazole photocatalytic degradation kinetics was studied in a batch reactor using TiO2 (P25-Degussa as catalyst and a high pressure mercury lamp. The photolysis, adsorption and irradiation effects in the reaction rate were evaluated. Afterward, the suspension catalyst concentration and initial pH to the maximum reaction rate was determined. It was observed that the reaction rate can be approached by a pseudo-first order, with a maximum kinetics constant at 260 mg L-1catalyst concentration and pH 7.7.

  13. 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...

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

    Directory of Open Access Journals (Sweden)

    Ignacio Vélez–Pareja

    2008-04-01

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

  15. Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform

    OpenAIRE

    Imit, Mokhtar; Yamamoto, Takakazu; Imin, Patigul

    2005-01-01

    Photochemical reactions of poly(3-butoxythiophene-2,5-diyl) with chloroform under irradiation with light were studied. The reactions were separately carried out under air, oxygen, and nitrogen. The obtained results showed that this reaction belongs to the pseudo-first-order reaction with a rate constant k obs of 1.4×10−5 s−1 at room temperature. The presence or absence of air, oxygen, and nitrogen did not have obvious effects on the reaction rate under irradiation with light.

  16. Radiation-induced degradation of methyl orange in aqueous solutions.

    Science.gov (United States)

    Chen, You-Peng; Liu, Shao-Yang; Yu, Han-Qing; Yin, Hao; Li, Qian-Rong

    2008-06-01

    Degradation of methyl orange under gamma-irradiation was investigated. The reactions followed pseudo first-order kinetics. Apparent degradation rate constant, estimated through linear regression analysis, increased with an increase of dose rate and a decrease of initial methyl orange concentration. Degradation of methyl orange was significantly accelerated under oxidative condition, but was slightly enhanced under reductive condition. However, the result of decoloration was better under reductive condition than oxidative one. An analysis on the intermediates using Fourier transform infrared and gas chromatography/mass spectrometry demonstrates that the radiolytic degradation of methyl orange was processed with different C-N cleavages under oxidative and reductive conditions.

  17. Chemistry and kinetics of I2 loss in urine distillate and humidity condensate

    Science.gov (United States)

    Atwater, James E.; Wheeler, Richard R., Jr.; Olivadoti, J. T.; Sauer, Richard L.

    1992-01-01

    Time-resolved molecular absorption spectrophotometry of iodinated ersatz humidity condensates and iodinated ersatz urine distillates across the UV and visible spectral regions are used to investigate the chemistry and kinetics of I2 loss in urine distillate and humidity condensate. Single contaminant systems at equivalent concentrations are also employed to study rates of iodine. Pseudo-first order rate constants are identified for ersatz contaminant model mixtures and for individual reactive constituents. The second order bimolecular reaction of elemental iodine with formic acid, producing carbon dioxide and iodine anion, is identified as the primary mechanism underlying the decay of residual I2 in ersatz humidity concentrate.

  18. Varying Constants, Gravitation and Cosmology.

    Science.gov (United States)

    Uzan, Jean-Philippe

    2011-01-01

    Fundamental constants are a cornerstone of our physical laws. Any constant varying in space and/or time would reflect the existence of an almost massless field that couples to matter. This will induce a violation of the universality of free fall. Thus, it is of utmost importance for our understanding of gravity and of the domain of validity of general relativity to test for their constancy. We detail the relations between the constants, the tests of the local position invariance and of the universality of free fall. We then review the main experimental and observational constraints that have been obtained from atomic clocks, the Oklo phenomenon, solar system observations, meteorite dating, quasar absorption spectra, stellar physics, pulsar timing, the cosmic microwave background and big bang nucleosynthesis. At each step we describe the basics of each system, its dependence with respect to the constants, the known systematic effects and the most recent constraints that have been obtained. We then describe the main theoretical frameworks in which the low-energy constants may actually be varying and we focus on the unification mechanisms and the relations between the variation of different constants. To finish, we discuss the more speculative possibility of understanding their numerical values and the apparent fine-tuning that they confront us with.

  19. Varying Constants, Gravitation and Cosmology

    Directory of Open Access Journals (Sweden)

    Jean-Philippe Uzan

    2011-03-01

    Full Text Available Fundamental constants are a cornerstone of our physical laws. Any constant varying in space and/or time would reflect the existence of an almost massless field that couples to matter. This will induce a violation of the universality of free fall. Thus, it is of utmost importance for our understanding of gravity and of the domain of validity of general relativity to test for their constancy. We detail the relations between the constants, the tests of the local position invariance and of the universality of free fall. We then review the main experimental and observational constraints that have been obtained from atomic clocks, the Oklo phenomenon, solar system observations, meteorite dating, quasar absorption spectra, stellar physics, pulsar timing, the cosmic microwave background and big bang nucleosynthesis. At each step we describe the basics of each system, its dependence with respect to the constants, the known systematic effects and the most recent constraints that have been obtained. We then describe the main theoretical frameworks in which the low-energy constants may actually be varying and we focus on the unification mechanisms and the relations between the variation of different constants. To finish, we discuss the more speculative possibility of understanding their numerical values and the apparent fine-tuning that they confront us with.

  20. Efficient Determination of Reverberation Chamber Time Constant

    OpenAIRE

    Zhang, Xiaotian; Robinson, Martin P.; Flintoft, Ian D.; Dawson, John F.

    2017-01-01

    Determination of the rate of energy loss in a reverberation chamber is fundamental to many different measurements such as absorption cross-section, antenna efficiency, radiated power, and shielding effectiveness. Determination of the energy decay time-constant in the time domain by linear fitting the power delay profile, rather than using the frequency domain quality-factor, has the advantage of being independent of the radiation efficiency of antennas used in the measurement. However, determ...

  1. Learning Read-constant Polynomials of Constant Degree modulo Composites

    DEFF Research Database (Denmark)

    Chattopadhyay, Arkadev; Gavaldá, Richard; Hansen, Kristoffer Arnsfelt

    2011-01-01

    Boolean functions that have constant degree polynomial representation over a fixed finite ring form a natural and strict subclass of the complexity class \\textACC0ACC0. They are also precisely the functions computable efficiently by programs over fixed and finite nilpotent groups. This class...... is not known to be learnable in any reasonable learning model. In this paper, we provide a deterministic polynomial time algorithm for learning Boolean functions represented by polynomials of constant degree over arbitrary finite rings from membership queries, with the additional constraint that each variable...... in the target polynomial appears in a constant number of monomials. Our algorithm extends to superconstant but low degree polynomials and still runs in quasipolynomial time....

  2. Effective cosmological constant induced by stochastic fluctuations of Newton's constant

    Directory of Open Access Journals (Sweden)

    Marco de Cesare

    2016-09-01

    Full Text Available We consider implications of the microscopic dynamics of spacetime for the evolution of cosmological models. We argue that quantum geometry effects may lead to stochastic fluctuations of the gravitational constant, which is thus considered as a macroscopic effective dynamical quantity. Consistency with Riemannian geometry entails the presence of a time-dependent dark energy term in the modified field equations, which can be expressed in terms of the dynamical gravitational constant. We suggest that the late-time accelerated expansion of the Universe may be ascribed to quantum fluctuations in the geometry of spacetime rather than the vacuum energy from the matter sector.

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

    Energy Technology Data Exchange (ETDEWEB)

    Nez, F

    2005-06-15

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

  4. Mirror QCD and Cosmological Constant

    Directory of Open Access Journals (Sweden)

    Roman Pasechnik

    2017-05-01

    Full Text Available An analog of Quantum Chromo Dynamics (QCD sector known as mirror QCD (mQCD can affect the cosmological evolution due to a non-trivial contribution to the Cosmological Constant analogous to that induced by the ground state in non-perturbative QCD. In this work, we explore a plausible hypothesis for trace anomalies cancellation between the usual QCD and mQCD. Such an anomaly cancellation between the two gauge theories, if it exists in Nature, would lead to a suppression or even elimination of their contributions to the Cosmological Constant. The trace anomaly compensation condition and the form of the non-perturbative mQCD coupling constant in the infrared limit have been proposed by analysing a partial non-perturbative solution of the Einstein–Yang-Mills equations of motion.

  5. Kinetic characteristics of gas-liquid ozone reactions

    Science.gov (United States)

    Levanov, A. V.; Isaikina, O. Ya.; Lunin, V. V.

    2017-10-01

    An experimental chemical method for determining the kinetic characteristics (volumetric mass transfer coefficient and rate constant of a second-order reaction) of gas-liquid ozone reactions in a bubble column reactor is described. The calculation formulas are substantiated, and the ranges of values of the experimental factors that determine the method's limits of applicability are found. The conditions under which the boundary-value problem of a gas-liquid ozone reaction of the second order can be reduced to a problem of a pseudo-first order reaction allowing an analytical solution are revealed.

  6. Quality by Design (QbD approach to develop HPLC method for eberconazole nitrate: Application oxidative and photolytic degradation kinetics

    Directory of Open Access Journals (Sweden)

    M. Vamsi Krishna

    2016-09-01

    Full Text Available Stability of eberconazole nitrate (EBZ was investigated using a stability indicating HPLC method. Quality by Design (QbD approach was used to facilitate method development. EBZ was exposed to different stress conditions, including hydrolytic (acid, base, neutral, oxidative, thermal and photolytic. Relevant degradation was found to take place in all the conditions. The degradation of EBZ followed (pseudo first-order kinetics under experimental conditions. The kinetic parameters (rate constant, t1/2, and t90 of the degradation of EBZ were calculated.

  7. GRAPHICAL DETERMINATION OF DISSOCIATION CONSTANT ...

    African Journals Online (AJOL)

    DR. AMINU

    ABSTRACT. The dissociation constant (pKa) of non – polar amino acids including (alanine, glycine, valine phenylalanine and tryptophan) were determined by potentiometric titration technique. The pKa values obtained by extrapolation for alanine, glycine, and valine were 10.29, 9.87 and 9.91 respectively. The implications ...

  8. GRAPHICAL DETERMINATION OF DISSOCIATION CONSTANT ...

    African Journals Online (AJOL)

    DR. AMINU

    3: Plot of pH versus Log [HA]/[A-] for pKa of Valine. CONCLUSION. The acid dissociation constant of non polar amino acids determined graphically for the first time from the available literature were found to be similar with corresponding calculated values reported in the literature. Therefore the graphical approach is ...

  9. Wormholes and the cosmological constant

    Science.gov (United States)

    Klebanov, Igor; Susskind, Leonard; Banks, Tom

    1989-05-01

    We review Coleman's wormhole mechanism for the vanishing of the cosmological constant. We show that in a minisuperspace model wormhole-connected universes dominate the path integral. We also provide evidence that the euclidean path integral over geometries with spherical topology is unstable with respect to formation of infinitely many wormhole-connected 4-spheres. Consistency is restored by summing over all topologies, which leads to Coleman's result. Coleman's argument for determination of other parameters is reviewed and applied to the mass of the pion. A discouraging result is found that the pion mass is driven to zero. We also consider qualitatively the implications of the wormhole theory for cosmology. We argue that a small number of universes containing matter and energy may exist in contact with infinitely many cold and empty universe. Contact with the cold universe insures that the cosmological constant in the warm ones in zero.

  10. Wormholes and the cosmological constant

    Energy Technology Data Exchange (ETDEWEB)

    Klebanov, I.; Susskind, L.; Banks, T.

    1989-05-08

    We review Coleman's wormhole mechanism for the vanishing of the cosmological constant. We show that in a minisuperspace model wormhole-connected universes dominate the path integral. We also provide evidence that the euclidean path integral over geometries with spherical topology is unstable with respect to formation of infinitely many wormhole-connected 4-spheres. Consistency is restored by summing over all topologies, which leads to Coleman's result. Coleman's argument for determination of other parameters is reviewed and applied to the mass of the pion. A discouraging result is found that the pion mass is driven to zero. We also consider qualitatively the implications of the wormhole theory for cosmology. We argue that a small number of universes containing matter and energy may exist in contact with infinitely many cold and empty universes. Contact with the cold universes insures that the cosmological constant in the warm ones is zero.

  11. A new cosmological constant model

    CERN Document Server

    López, J L; Lopez, J; Nanopoulos, D

    1996-01-01

    We propose a new cosmological model with a time-dependent cosmological constant (\\Lambda\\propto 1/t^2), which starting at the Planck time as \\Lambda_{Pl}\\sim M^2_{Pl}, evolves to the present-day allowed value of \\Lambda_0\\sim10^{-120}M^2_{Pl}. This scenario is supported by non-critical string theory considerations. We compute the age of the Universe and the time-dependence of the scale factor in this model, and find general agreement with recent determinations of the Hubble parameter for substantial values of \\Omega_{\\rm \\Lambda}. This effectively low-density open Universe model differs from the traditional cosmological constant model, and has observable implications for particle physics and cosmology.

  12. Cosmological Constant and Local Gravity

    CERN Document Server

    Bernabeu, Jose; Mavromatos, Nick E

    2010-01-01

    We discuss the linearization of Einstein equations in the presence of a cosmological constant, by expanding the solution for the metric around a flat Minkowski space-time. We demonstrate that one can find consistent solutions to the linearized set of equations for the metric perturbations, in the Lorentz gauge, which are not spherically symmetric, but they rather exhibit a cylindrical symmetry. We find that the components of the gravitational field satisfying the appropriate Poisson equations have the property of ensuring that a scalar potential can be constructed, in which both contributions, from ordinary matter and $\\Lambda > 0$, are attractive. In addition, there is a novel tensor potential, induced by the pressure density, in which the effect of the cosmological constant is repulsive. We also linearize the Schwarzschild-de Sitter exact solution of Einstein's equations (due to a generalization of Birkhoff's theorem) in the domain between the two horizons. We manage to transform it first to a gauge in whic...

  13. Strain sweeps from Oldroyd 8-constant framework

    Science.gov (United States)

    Saengow, Chaimongkol; Giacomin, Alan Jeffrey

    2017-05-01

    Large-amplitude oscillatory shear flow is a popular experiment for studying the nonlinear physics of complex fluids. Specifically, the strain sweep is used routinely to identify when a complex fluid begins to exhibit nonlinear behavior. In this paper, we give the exact shear stress expression for the Oldroyd 8-constant framework evaluated for large-amplitude oscillatory shear flow (LAOS). We choose the Oldroyd 8-constant framework for its rich diversity of popular special cases (we list 14 of these cases). From our shear stress expression, we get exact expressions for the real and imaginary parts of the complex viscosity as functions of both the test frequency, and the shear rate amplitude. We then demonstrate the use of our results for our favorite special case of the Oldroyd 8-constant framework, the corotational Jeffreys model. In our Worked Example, we use this case to explore the influence of η∞ on the strain sweep response. We find that increasing η∞ raises the real part of the complex viscosity, and decreases its imaginary part.

  14. Searching for Kaprekar's constants: algorithms and results

    OpenAIRE

    Walden, Byron L.

    2005-01-01

    We examine some new results on Kaprekar's constants, specifically establishing the unique 7-digit (in base 4) and 9-digit (in base 5) Kaprekar's constants and showing that there are no 15-, 21-, 27-, or 33-digit Kaprekar's constants.

  15. Page 1 Dissociation rate constants of some ETA complexes 289 ...

    Indian Academy of Sciences (India)

    Chem. Commun, 243057. Koryta J1967 Advances in electrochemistry and electrochemical engineering eds P Delahay and CW. Tobias (New York: InterScience) Vol. 6 p. 289. Pryszczewska M, Ralea Rand Koryta J1959 Coll. Czech, Chem. Commun. 243796. Radhakrishnan T P and Sundaram A K 1972 Proc. Indian Acad.

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

    African Journals Online (AJOL)

    aliyu.jibril

    2017-05-22

    May 22, 2017 ... animals is challenging due to lack of verbal communication. Hence ... action and minimal side effects (Perez et al., 2014). However, tramadol has a ... had access to clean drinking water ad libitum. .... Aggressive. Response to.

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

    African Journals Online (AJOL)

    The cardinal temperatures (base, Tb, optimum, To and ceiling, Tc) for the NEM cultivar were Tb: 7, To: 30 and Tc: 48.2 oC. The corresponding values for the QPM cultivar were Tb: 7.6, To: 27.5 and Tc: 43.4 oC. The base and optimal temperatures were not significantly different but the ceiling temperature for the QPM was ...

  18. a comparative study of the drying rate constant, drying efficiency ...

    African Journals Online (AJOL)

    J., 2011. A comparative study of direct and indirect solar drying of mango. Global Journal of Pure and. Applied Sciences. 17, (3): 273- 294. Doymaz, I., 2004a. Drying kinetics of white mulberry. Journal of Food Engineering (74): 341-346. Doymaz, I., 2004b. Pretreatment effect on sun drying of mulberry fruit (Morusalba L).

  19. DETERMINATION OF THE CONSTANT-RATE MASS-TRANSFER ...

    African Journals Online (AJOL)

    Journal of Modeling, Design and Management of Engineering Systems. Journal Home · ABOUT THIS JOURNAL · Advanced Search · Current Issue · Archives · Journal Home > Vol 2, No 1 (2003) >. Log in or Register to get access to full text downloads.

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

    Indian Academy of Sciences (India)

    Author Affiliations. J DEY1 P PHANI KUMAR2. Faculty, Department of Aerospace Engineering, Jain University, Bangalore 562112, India; Department of Aerospace Engineering, Indian Institute of Science, Bangalore 560012, India ...

  1. ESTER HYDROLYSIS RATE CONSTANT PREDICTION FROM INFRARED INTERFEROGRAMS

    Science.gov (United States)

    A method for predicting reactivity parameters of organic chemicals from spectroscopic data is being developed to assist in assessing the environmental fate of pollutants. he prototype system, which employs multiple linear regression analysis using selected points from the Fourier...

  2. Constant False Alarm Rate (CFAR) Autotrend Evaluation Report

    Science.gov (United States)

    2011-12-01

    represent a level of uncertainty in the performance analysis. The performance analysis produced the following Key Performance Indicators ( KPIs ) as...Identity KPI Key Performance Indicator MooN M-out-of-N MSPU Modernized Signal Processor Unit NFF No Fault Found PAT Parameter Allocation Table PD

  3. Exact constants in approximation theory

    CERN Document Server

    Korneichuk, N

    1991-01-01

    This book is intended as a self-contained introduction for non-specialists, or as a reference work for experts, to the particular area of approximation theory that is concerned with exact constants. The results apply mainly to extremal problems in approximation theory, which in turn are closely related to numerical analysis and optimization. The book encompasses a wide range of questions and problems: best approximation by polynomials and splines; linear approximation methods, such as spline-approximation; optimal reconstruction of functions and linear functionals. Many of the results are base

  4. Cryptography in constant parallel time

    CERN Document Server

    Applebaum, Benny

    2013-01-01

    Locally computable (NC0) functions are 'simple' functions for which every bit of the output can be computed by reading a small number of bits of their input. The study of locally computable cryptography attempts to construct cryptographic functions that achieve this strong notion of simplicity and simultaneously provide a high level of security. Such constructions are highly parallelizable and they can be realized by Boolean circuits of constant depth.This book establishes, for the first time, the possibility of local implementations for many basic cryptographic primitives such as one-way func

  5. Formas estructurales de fuerza constante

    Directory of Open Access Journals (Sweden)

    Zalewski, Waclaw

    1963-05-01

    Full Text Available The author seeks to prove the need to obtain the most essential form in the various types of structures by applying a number of rational principles, of which the constant stress principle is one of the most decisive. The structural form should be a logical consequence of all its functional circumstances, and this requires a clear understanding of the general behaviour of each part of the structure, and also of the main stresses which operate on it, considered as a unitary whole. To complete his theoretical argument, the author gives some examples, in the design of which the criterion of constant stress has been adopted. The author considers the various aspects which are involved in obtaining a structural design that satisfies given functional and aesthetic requirements. In doing so he refers to his personal experience within Poland, and infers technical principles of general validity which should determine the rational design of the form, as an integrated aspect of the structural pattern. The projects which illustrate this paper are Polish designs of undoubted constructive significance, in which the principle of constant stress has been applied. Finally the author condenses his whole theory in a simple and straightforward practical formula, which should be followed if a truly rational form is to be achieved: the constancy of stress in the various structural elements.El autor se esfuerza en mostrar la necesidad de llegar a la forma real en las distintas estructuras siguiendo una serie de principios racionales, entre los que domina el criterio de la fuerza constante. La forma ha de ser una consecuencia lógica en todos sus aspectos, y esto exige un claro conocimiento del comportamiento general de cada una de las partes de la estructura, y de los esfuerzos generales que dominan en la misma al considerarla como un todo. Para completar la exposición de orden teórico, el autor presenta algunos ejemplos en cuyo proyecto se ha seguido el criterio de

  6. Graphs with constant μ and μ

    NARCIS (Netherlands)

    van Dam, E.R.; Haemers, W.H.

    1995-01-01

    A graph G has constant u = u(G) if any two vertices that are not adjacent have u common neighbours. G has constant u and u if G has constant u = u(G), and its complement G has constant u = u(G). If such a graph is regular, then it is strongly regular, otherwise precisely two vertex degrees occur. We

  7. Stability constant estimator user`s guide

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B.P.; Castleton, K.J.; Rustad, J.R.

    1996-12-01

    The purpose of the Stability Constant Estimator (SCE) program is to estimate aqueous stability constants for 1:1 complexes of metal ions with ligands by using trends in existing stability constant data. Such estimates are useful to fill gaps in existing thermodynamic databases and to corroborate the accuracy of reported stability constant values.

  8. Effects of constant voltage and constant current stress in PCBM:P3HT solar cells

    DEFF Research Database (Denmark)

    Cester, Andrea; Rizzo, Aldo; Bazzega, A.

    2015-01-01

    The aimof this work is the investigation of forward and reverse bias stress effects, cell self-heating and annealing in roll coated organic solar cells with PCBM:P3HT active layer. In reverse bias stress cells show a constant degradation over time. In forward current stress cells alternate...... mechanisms: the decrease of the net generation rate (due to formation of exciton quenching centres or the reduction of exciton separation rate); the formation of small leaky paths between anode and cathode, which reduces the total current extracted from the cell. The stress-induced damage can be recovered...

  9. The Unimolecular Reactions of CF3CHF2Studied by Chemical Activation: Assignment of Rate Constants and Threshold Energies to the 1,2-H Atom Transfer, 1,1-HF and 1,2-HF Elimination Reactions, and the Dependence of Threshold Energies on the Number of F-Atom Substituents in the Fluoroethane Molecules.

    Science.gov (United States)

    Smith, Caleb A; Gillespie, Blanton R; Heard, George L; Setser, D W; Holmes, Bert E

    2017-11-22

    The recombination of CF 3 and CHF 2 radicals in a room-temperature bath gas was used to prepare vibrationally excited CF 3 CHF 2 * molecules with 101 kcal mol -1 of vibrational energy. The subsequent 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions were observed as a function of bath gas pressure by following the CHF 3 , CF 3 (F)C: and C 2 F 4 product concentrations by gas chromatography using a mass spectrometer as the detector. The singlet CF 3 (F)C: concentration was measured by trapping the carbene with trans-2-butene. The experimental rate constants are 3.6 × 10 4 , 4.7 × 10 4 , and 1.1 × 10 4 s -1 for the 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions, respectively. These experimental rate constants were matched to statistical RRKM calculated rate constants to assign threshold energies (E 0 ) of 88 ± 2, 88 ± 2, and 87 ± 2 kcal mol -1 to the three reactions. Pentafluoroethane is the only fluoroethane that has a competitive H atom transfer decomposition reaction, and it is the only example with 1,1-HF elimination being more important than 1,2-HF elimination. The trend of increasing threshold energies for both 1,1-HF and 1,2-HF processes with the number of F atoms in the fluoroethane molecule is summarized and investigated with electronic-structure calculations. Examination of the intrinsic reaction coordinate associated with the 1,1-HF elimination reaction found an adduct between CF 3 (F)C: and HF in the exit channel with a dissociation energy of ∼5 kcal mol -1 . Hydrogen-bonded complexes between HF and the H atom migration transition state of CH 3 (F)C: and the F atom migration transition state of CF 3 (F)C: also were found by the calculations. The role that these carbene-HF complexes could play in 1,1-HF elimination reactions is discussed.

  10. Constant training in direct ophthalmoscopy

    Directory of Open Access Journals (Sweden)

    Younan HC

    2017-08-01

    Full Text Available Helen-Cara Younan, Rishi Iyer, Janaki Natasha DesaiFaculty of Medicine, Imperial College London, London, UKWe read with great interest the review by Ricci and Ferraz on the advances in training and practice in ophthalmoscopy simulation.1As final year medical students, we have recently experienced direct ophthalmoscopy teaching and agree with the authors that “simulation is a helpful tool in ophthalmoscopy training”.1 Indeed, in our experience, simulation is useful in teaching a wide variety of clinical skills including venepuncture, intravenous cannulation, and catheterization. We were taught all of these clinical skills in our first clinical year of study through use of simulation models. With regards to our direct ophthalmoscopy teaching, we were first taught to recognize the normal retina and different retinal pathologies using images, before practicing our technique and recognition of those images in a model similar to the THELMA (The Human Eye Learning Model Assistant described by the authors.1However, we feel that the use of simulation models alone is not enough to provide confidence and competency in direct ophthalmoscopy among medical students. The authors conclude that “constant training is a well-known strategy for skill enhancement”,1 and we have found that a lack of constant training in direct ophthalmoscopy is evident. After learning venepuncture, cannulation, and catheterization on the simulation models, we were able to observe doctors performing these skills before performing them on patients either in the wards or in theatre. These are skills that we are constantly trained in across a wide variety of medical and surgical attachments. However, opportunities to observe and practice ophthalmoscopy during our attachments are more limited, and thus we are not continuing to use the skills we learn.Authors' replyLucas Holderegger Ricci,1 Caroline Amaral Ferraz21Department of Ophthalmology, School of Medicine, Laureate

  11. The fundamental constants a mystery of physics

    CERN Document Server

    Fritzsch, Harald

    2009-01-01

    The speed of light, the fine structure constant, and Newton's constant of gravity — these are just three among the many physical constants that define our picture of the world. Where do they come from? Are they constant in time and across space? In this book, physicist and author Harald Fritzsch invites the reader to explore the mystery of the fundamental constants of physics in the company of Isaac Newton, Albert Einstein, and a modern-day physicist

  12. Omnidirectional antenna having constant phase

    Energy Technology Data Exchange (ETDEWEB)

    Sena, Matthew

    2017-04-04

    Various technologies presented herein relate to constructing and/or operating an antenna having an omnidirectional electrical field of constant phase. The antenna comprises an upper plate made up of multiple conductive rings, a lower ground-plane plate, a plurality of grounding posts, a conical feed, and a radio frequency (RF) feed connector. The upper plate has a multi-ring configuration comprising a large outer ring and several smaller rings of equal size located within the outer ring. The large outer ring and the four smaller rings have the same cross-section. The grounding posts ground the upper plate to the lower plate while maintaining a required spacing/parallelism therebetween.

  13. Henry's law constants of polyols

    Science.gov (United States)

    Compernolle, S.; Müller, J.-F.

    2014-12-01

    Henry's law constants (HLC) are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. While deriving HLC and depending on the case, also infinite dilution activity coefficients (IDACs), solid state vapour pressures or activity coefficient ratios are obtained as intermediate results. An error analysis on the intermediate quantities and the obtained HLC is included. For most compounds, these are the first values reported, while others compare favourably with literature data in most cases. Using these values and those from a previous work (Compernolle and Müller, 2014), an assessment is made on the partitioning of polyols, diacids and hydroxy acids to droplet and aqueous aerosol.

  14. Henry's law constants of polyols

    Directory of Open Access Journals (Sweden)

    S. Compernolle

    2014-12-01

    Full Text Available Henry's law constants (HLC are derived for several polyols bearing between 2 and 6 hydroxyl groups, based on literature data for water activity, vapour pressure and/or solubility. While deriving HLC and depending on the case, also infinite dilution activity coefficients (IDACs, solid state vapour pressures or activity coefficient ratios are obtained as intermediate results. An error analysis on the intermediate quantities and the obtained HLC is included. For most compounds, these are the first values reported, while others compare favourably with literature data in most cases. Using these values and those from a previous work (Compernolle and Müller, 2014, an assessment is made on the partitioning of polyols, diacids and hydroxy acids to droplet and aqueous aerosol.

  15. Local Pain Dynamics during Constant Exhaustive Exercise.

    Directory of Open Access Journals (Sweden)

    Agne Slapsinskaite

    Full Text Available The purpose of this study was to delineate the topological dynamics of pain and discomfort during constant exercise performed until volitional exhaustion. Eleven physical education students were tested while cycling and running at a "hard" intensity level (e.g., corresponding to Borg's RPE (6-20 = 15. During the tests, participants reported their discomfort and pain on a body map every 15s. "Time on task" for each participant was divided into five equal non-overlapping temporal windows within which their ratings were considered for analysis. The analyses revealed that the number of body locations with perceived pain and discomfort increased throughout the five temporal windows until reaching the mean (± SE values of 4.2 ± 0.7 and 4.1 ± 0.6 in cycling and running, respectively. The dominant locations included the quadriceps and hamstrings during cycling and quadriceps and chest during running. In conclusion, pain seemed to spread throughout the body during constant cycling and running performed up to volitional exhaustion with differences between cycling and running in the upper body but not in the lower body dynamics.

  16. The Oxidation of 2-(2-Methoxyethoxyethanol and 2-(2-Ethoxyethoxyethanol by Ditelluratocuprate(III: A Kinetic and Mechanistic Study

    Directory of Open Access Journals (Sweden)

    Jin-huan Shan

    2013-01-01

    Full Text Available The oxidation of 2-(2-methoxyethoxyethanol (MEE and 2-(2-ethoxyethoxyethanol (EEE by ditelluratocuprate(III (DTC had been studied spectrophotometrically in alkaline medium. The reaction between and showed first-order dependence in DTC and fractional order in MEE and EEE. The rate constant of the pseudo-first-order reaction decreased with an increase of [TeO4  2−], whereas adding [OH−] enhanced the constant. In addition, the reaction had a negative salt effect. The rate of EEE was higher than that of MEE. A suitable assumption involving preequilibriums before the rate-controlling step and a free radical mechanism was proposed, based on the kinetic data. Activation parameters and the rate constant of the rate-determining step were calculated.

  17. Constant mortality and fertility over age in Hydra

    DEFF Research Database (Denmark)

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

    2015-01-01

    , or remain constant with age, but the data are scanty and problematic. Here, we present compelling evidence for constant age-specific death and reproduction rates in Hydra, a basal metazoan, in a set of experiments comprising more than 3.9 million days of observations of individual Hydra. Our data show...... that 2,256 Hydra from two closely related species in two laboratories in 12 cohorts, with cohort age ranging from 0 to more than 41 y, have extremely low, constant rates of mortality. Fertility rates for Hydra did not systematically decline with advancing age. This falsifies the universality...... of the theories of the evolution of aging that posit that all species deteriorate with age after maturity. The nonsenescent life history of Hydra implies levels of maintenance and repair that are sufficient to prevent the accumulation of damage for at least decades after maturity, far longer than the short life...

  18. Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms.

    Science.gov (United States)

    Díaz-de-Mera, Yolanda; Aranda, Alfonso; Bravo, Iván; Rodríguez, Diana; Rodríguez, Ana; Moreno, Elena

    2008-10-01

    The adverse environmental impacts of chlorinated hydrocarbons on the Earth's ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C-F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF(3)CF(2)CF(2)OCH(3)) (1) and its isomer CF(3)CF(2)CF(2)CH(2)OH (2). Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube-mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266-333 and 298-353 K for reactions of HFE-7000 and CF(3)CF(2)CF(2)CH(2)OH, respectively. The measured room temperature rate constants were k(Cl+CF(3)CF(2)CF(2)OCH(3)) = (1.24 +/- 0.28) x 10(-13) cm(3) molecule(-1) s(-1)and k(Cl+CF(3)CF(2)CF(2)CH(2)OH) = (8.35 +/- 1.63) x 10(-13) cm(3) molecule(-1) s(-1) (errors are 2sigma + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k (1)(266-333 K) = (6.1 +/- 3.8) x 10(-13)exp[-(445 +/- 186)/T] cm(3) molecule(-1) s(-1) and k (2)(298-353 K) = (1.9 +/- 0.7) x 10(-12)exp[-(244 +/- 125)/T] cm(3) molecule(-1) s(-1) (errors

  19. The fundamental constants and quantum electrodynamics

    CERN Document Server

    Taylor, Barry N; Langenberg, D N

    1969-01-01

    Introduction ; review of experimental data ; least-squares adjustment to obtain values of the constants without QED theory ; implications for quantum electrodynamics ; final recommended set of fundamental constants ; summary and conclusions.

  20. Capacitive Cells for Dielectric Constant Measurement

    Science.gov (United States)

    Aguilar, Horacio Munguía; Maldonado, Rigoberto Franco

    2015-01-01

    A simple capacitive cell for dielectric constant measurement in liquids is presented. As an illustrative application, the cell is used for measuring the degradation of overheated edible oil through the evaluation of their dielectric constant.

  1. Critical survey of stability constants of EDTA complexes critical evaluation of equilibrium constants in solution stability constants of metal complexes

    CERN Document Server

    Anderegg, G

    2013-01-01

    Critical Survey of Stability Constants of EDTA Complexes focuses on the computations, values, and characteristics of stability constants. The book emphasizes that for a critical discussion of experimentally determined stability constants, it is important to consider the precision of the values that manifests the self-consistency of the constant, taking into consideration the random errors. The publication reviews the stability constants of metal complexes. The numerical calculations affirm the reactions and transformations of metal ions when exposed to varying conditions. The text also present

  2. Surprises in numerical expressions of physical constants

    OpenAIRE

    Amir, Ariel; Lemeshko, Mikhail; Tokieda, Tadashi

    2016-01-01

    In science, as in life, `surprises' can be adequately appreciated only in the presence of a null model, what we expect a priori. In physics, theories sometimes express the values of dimensionless physical constants as combinations of mathematical constants like pi or e. The inverse problem also arises, whereby the measured value of a physical constant admits a `surprisingly' simple approximation in terms of well-known mathematical constants. Can we estimate the probability for this to be a me...

  3. Searching for Kaprekar's constants: algorithms and results

    Directory of Open Access Journals (Sweden)

    Byron L. Walden

    2005-01-01

    Full Text Available We examine some new results on Kaprekar's constants, specifically establishing the unique 7-digit (in base 4 and 9-digit (in base 5 Kaprekar's constants and showing that there are no 15-, 21-, 27-, or 33-digit Kaprekar's constants.

  4. Untangling Fixed Effects and Constant Regressors

    NARCIS (Netherlands)

    Klaassen, F.; Teulings, R.

    2015-01-01

    Fixed effects (FE) in panel data models overlap each other and prohibit the identification of the impact of "constant" regressors. Think of regressors that are constant across countries in a country-time panel with time FE. The traditional approach is to drop some FE and constant regressors by

  5. VLT and E-ELT spectrographs & fundamental-constants

    Science.gov (United States)

    Molaro, Paolo

    2010-11-01

    The fundamental dimensionless physical constants cannot be predicted by theory but can only be measured experimentally. And so it is of their possible variation where there are several theoretical predictions but unfortunately with little theoretical guidance on the expected rate of change. The role of fundamental constants in the representation of nature as well as the implications of their variability for the Equivalence Principle and cosmology have been highlighted in many contributions at this conference (cfr K. Olive and J.P Uzan, these proceedings). Measuring the variability of the fine structure constant α or the electron-to-proton ratio μ by means of absorption lines implies the measurement of a tiny variation of the position of one or a few lines with regard to other lines which are taken as reference. For the fine structure constant the relation between its change and the doppler velocity shift is:

  6. Reaction of a hydrated electron with gentamycin and collagen—A pulse radiolysis study

    Science.gov (United States)

    Pietrucha, K.; Góra, L.; Doillon, C. J.

    1996-01-01

    The reactions of a hydrated electron (e aq-) with aminoglycoside anbiotic gentamycin and collagen in aqueous medium at different pH have been investigated employing a pulse radiolysis technique. The pseudo-first order equation of reaction kinetics was used to give an accurate description of the decay of e aq- in gentamycin solutions. The rate constant of the e aq- decay in collagen solution was high and reached 3.2 × 10 10 M -1 s -1. The rate constants for the reaction of the e aq- with gentamycin were found to be influenced by pH, decreasing with the deprotonation of the -NH 3 groups, while for pH > pK a which for gentamycin is equal to 7.8, the rate constant was unchanged. These observations suggest that when the amino groups are protonated, reductive deamination occurs, but for unprotonated non-reactive amino groups, a radical anion is formed on the glycoside moiety.

  7. Peptide production and decay rates affect the quantitative accuracy of protein cleavage isotope dilution mass spectrometry (PC-IDMS).

    Science.gov (United States)

    Shuford, Christopher M; Sederoff, Ronald R; Chiang, Vincent L; Muddiman, David C

    2012-09-01

    No consensus has been reached on the proper time to add stable-isotope labeled (SIL) peptides in protein cleavage isotope dilution mass spectrometry workflows. While quantifying 24 monolignol pathway enzymes in the xylem tissue of Populus trichocarpa, we compared the protein concentrations obtained when adding the SIL standard peptides concurrently with the enzyme or after quenching of the digestion (i.e. postdigestion) and observed discrepancies for nearly all tryptic peptides investigated. In some cases, greater than 30-fold differences were observed. To explain these differences and potentially correct for them, we developed a mathematical model based on pseudo-first-order kinetics to account for the dynamic production and decay (e.g. degradation and precipitation) of the native peptide targets in conjunction with the decay of the SIL peptide standards. A time course study of the digests confirmed the results predicted by the proposed model and revealed that the discrepancy between concurrent and postdigestion introduction of the SIL standards was related to differential decay experienced by the SIL peptide and the native peptide in each method. Given these results, we propose concurrent introduction of the SIL peptide is most appropriate, though not free from bias. Mathematical modeling of this method reveals that overestimation of protein quantities would still result when rapid peptide decay occurs and that this bias would be further exaggerated by slow proteolysis. We derive a simple equation to estimate the bias for each peptide based on the relative rates of production and decay. According to this equation, nearly half of the peptides evaluated here were estimated to have quantitative errors greater than 10% and in a few cases over 100%. We conclude that the instability of peptides can often significantly bias the protein quantities measured in protein cleavage isotope dilution mass spectrometry-based assays and suggest peptide stability be made a priority

  8. Investigation of dissolution mechanisms of six Turkish coals in tetralin with microwave energy

    Energy Technology Data Exchange (ETDEWEB)

    Simsek, E.H.; Karaduman, A.; Olcay, A. [Ankara University, Ankara (Turkey). Chemical Engineering Department

    2001-12-05

    Rates of formation of oil, asphaltenes, and preasphaltenes during liquefaction of six Turkish coals in tetralin with microwave heating have been experimentally determined. Five reaction mechanisms have been proposed and tested to estimate the rates of formation of products. Proposed mechanisms are based on assumption that the reactions are irreversible and pseudo-first order with respect to the reacting species. Pseudo-first order rate constants for each of the indicated mechanistic steps have been calculated by multivariable non-linear regression analysis. The best fit between experimental data and models suggested was obtained from model 3 (this model suggests that oils, asphaltenes and preasphaltenes formed directly from coal) with Tuncbilek and Zonguldak, from model 4 (this model assumes oils to be produced directly from preasphaltenes in addition to being formed from coal according to model 3) with Mugla-Yatagan and Soma-Merkez, and from model 5 (this model describes conversion of coal tolsvent fraction products incorporating both series and parallel reactions) with Bolu-Goeynuek and Beypazari coals. The results indicated that the reaction mechanism of coal liquefaction depends on the coal type. 31 refs., 6 figs., 3 tabs.

  9. Analytical solutions for the recovery tests after constant-discharge ...

    African Journals Online (AJOL)

    A new analytical solution for residual drawdown during the recovery period after a constant rate pumping test is described. A comparison between the proposed solution, existing solutions and experimental data from field observation are presented. The proposed analytical solution is in perfect agreement with the ...

  10. Kinetics and Mechanism of Oxidation of Triethylene Glycol and Tetraethylene Glycol by Ditelluratoargentate (III in Alkaline Medium

    Directory of Open Access Journals (Sweden)

    Jinhuan Shan

    2013-01-01

    Full Text Available The kinetics of oxidation of triethylene glycol and tetraethylene glycol by ditelluratoargentate (III (DTA in alkaline liquids has been studied spectrophotometrically in the temperature range of 293.2 K–313.2 K. The reaction rate showed first-order dependence in DTA and fractional order with respect to triethylene glycol or tetraethylene glycol. It was found that the pseudo-first-order rate constant (kobs increased with an increase in concentration of OH− and a decrease in concentration of H4TeO6 2−. There was a negative salt effect and no free radicals were detected. A plausible mechanism involving a two-electron transfer was proposed, and the rate equations derived from the mechanism explained all the experimental results and observations. The activation parameters along with the rate constants of the rate-determining step were calculated.

  11. Axiomatic approach to the cosmological constant

    Science.gov (United States)

    Beck, Christian

    2009-09-01

    A theory of the cosmological constant Λ is currently out of reach. Still, one can start from a set of axioms that describe the most desirable properties a cosmological constant should have. This can be seen in certain analogy to the Khinchin axioms in information theory, which fix the most desirable properties an information measure should have and that ultimately lead to the Shannon entropy as the fundamental information measure on which statistical mechanics is based. Here we formulate a set of axioms for the cosmological constant in close analogy to the Khinchin axioms, formally replacing the dependence of the information measure on probabilities of events by a dependence of the cosmological constant on the fundamental constants of nature. Evaluating this set of axioms one finally arrives at a formula for the cosmological constant given by Λ=1ħG(, where G is the gravitational constant, me the electron mass, and α the low-energy limit of the fine structure constant. This formula is in perfect agreement with current WMAP data. Our approach gives physical meaning to the Eddington-Dirac large-number hypothesis and suggests that the observed value of the cosmological constant is not at all unnatural.

  12. A natural cosmological constant from chameleons

    Energy Technology Data Exchange (ETDEWEB)

    Nastase, Horatiu, E-mail: nastase@ift.unesp.br [Instituto de Física Teórica, UNESP-Universidade Estadual Paulista, R. Dr. Bento T. Ferraz 271, Bl. II, Sao Paulo 01140-070, SP (Brazil); Weltman, Amanda, E-mail: amanda.weltman@uct.ac.za [Astrophysics, Cosmology & Gravity Center, Department of Mathematics and Applied Mathematics, University of Cape Town, Private Bag, Rondebosch 7700 (South Africa)

    2015-07-30

    We present a simple model where the effective cosmological constant appears from chameleon scalar fields. For a Kachru–Kallosh–Linde–Trivedi (KKLT)-inspired form of the potential and a particular chameleon coupling to the local density, patches of approximately constant scalar field potential cluster around regions of matter with density above a certain value, generating the effect of a cosmological constant on large scales. This construction addresses both the cosmological constant problem (why Λ is so small, yet nonzero) and the coincidence problem (why Λ is comparable to the matter density now)

  13. A natural cosmological constant from chameleons

    Directory of Open Access Journals (Sweden)

    Horatiu Nastase

    2015-07-01

    Full Text Available We present a simple model where the effective cosmological constant appears from chameleon scalar fields. For a Kachru–Kallosh–Linde–Trivedi (KKLT-inspired form of the potential and a particular chameleon coupling to the local density, patches of approximately constant scalar field potential cluster around regions of matter with density above a certain value, generating the effect of a cosmological constant on large scales. This construction addresses both the cosmological constant problem (why Λ is so small, yet nonzero and the coincidence problem (why Λ is comparable to the matter density now.

  14. Cooperation between bound waters and hydroxyls in controlling isotope-exchange rates

    Science.gov (United States)

    Panasci, Adele F.; McAlpin, J. Gregory; Ohlin, C. André; Christensen, Shauna; Fettinger, James C.; Britt, R. David; Rustad, James R.; Casey, William H.

    2012-02-01

    Mineral oxides differ from aqueous ions in that the bound water molecules are usually attached to different metal centers, or vicinal, and thus separated from one another. In contrast, for most monomeric ions used to establish kinetic reactivity trends, such as octahedral aquo ions (e.g., Al(H 2O) 63+), the bound waters are closely packed, or geminal. Because of this structural difference, the existing literature about ligand substitution in monomer ions may be a poor guide to the reactions of geochemical interest. To understand how coordination of the reactive functional groups might affect the rates of simple water-exchange reactions, we synthesized two structurally similar Rh(III) complexes, [Rh(phen) 2(H 2O) 2] 3+ [ 1] and [Rh(phen) 2(H 2O)Cl] 2+ [ 2] where (phen) = 1,10-phenanthroline. Complex [ 1] has two adjacent, geminal, bound waters in the inner-coordination sphere and [ 2] has a single bound water adjacent to a bound chloride ion. We employed Rh(III) as a trivalent metal rather than a more geochemically relevant metal like Fe(III) or Al(III) to slow the rate of reaction, which makes possible measurement of the rates of isotopic substitution by simple mass spectrometry. We prepared isotopically pure versions of the molecules, dissolved them into isotopically dissimilar water, and measured the rates of exchange from the extents of 18O and 16O exchange at the bound waters. The pH dependency of rates differ enormously between the two complexes. Pseudo-first-order rate coefficients at 298 K for water exchanges from the fully protonated molecules are close: k0298 = 5 × 10 -8(±0.5 × 10 -8) s -1 for [ 1] and k0298 = 2.5 × 10 -9(±1 × 10 -9) for [ 2]. Enthalpy and entropy activation parameters (Δ H‡ and Δ S‡) were measured to be 119(±3) kJ mol -1, and 14(±1) J mol -1 K -1, respectively for [ 1]. The corresponding parameters for the mono-aquo complex, [ 2], are 132(±3) kJ mol -1 and 41.5(±2) J mol -1 K -1. Rates increase by many orders of magnitude

  15. Manganese-oxidizing and -reducing microorganisms isolated from biofilms in chlorinated drinking water systems.

    Science.gov (United States)

    Cerrato, José M; Falkinham, Joseph O; Dietrich, Andrea M; Knocke, William R; McKinney, Chad W; Pruden, Amy

    2010-07-01

    The interaction of chemical, physical and biological factors that affect the fate, transport and redox cycling of manganese in engineered drinking water systems is not clearly understood. This research investigated the presence of Mn-oxidizing and -reducing bacteria in conventional water treatment plants exposed to different levels of chlorine. Mn(II)-oxidizing and Mn(IV)-reducing bacteria, principally Bacillus spp., were isolated from biofilm samples recovered from four separate drinking water systems. Rates of Mn-oxidation and -reduction for selected individual isolates were represented by pseudo-first-order kinetics. Pseudo-first-order rate constants were obtained for Mn-oxidation (range: 0.106-0.659 days(-1)), aerobic Mn-reduction (range: 0.036-0.152 days(-1)), and anaerobic Mn-reduction (range: 0.024-0.052 days(-1)). The results indicate that microbial-catalyzed Mn-oxidation and -reduction (aerobic and anaerobic) can take place simultaneously in aqueous environments exposed to considerable oxygen and chlorine levels and thus affect Mn-release and -deposition in drinking water systems. This has important implications for Mn-management strategies, which typically assume Mn-reduction is not possible in the presence of chlorine and oxidizing conditions. Copyright 2010 Elsevier Ltd. All rights reserved.

  16. Investigation of Ag-TiO2 nanostructures photocatalytic properties prepared by modified dip coating method

    Science.gov (United States)

    AlArfaj, Esam

    2016-05-01

    In this article, titanium dioxide and silver nanostructures were deposited on glass substrates using modified sol-gel methods and dip-coating technique. The films were characterised chemically and physically using different techniques (TLC, UV-Vis and XRD) and tested for environmental applications regarding degradation of aromatic hydrocarbons. The photocatalytic activity of the TiO2 nanostructures is tested with different small concentrations of phenol in water and reaction mechanisms discussed. Considerable enhancement is observed in the photodegradation activity of Ag-modified (3 wt.%) TiO2 compared to unmodified TiO2 nanostructures for phenol concentrations within the pseudo-first-order Langmuir-Hinshelwood (LH) model for reaction kinetics. The pseudo-first-order global degradation rate constant increased from absorption to the visible region by its surface plasmon resonances and to suppress the anatase-rutile phase transformation. Moreover, TiO2 grain size prepared was found to be 10 nm which maximises the active surface area. For phenol initial concentrations as low as 0.0002 M, saturation trend in the degradation process occurred at 0.00014 M and the reaction rate can be fitted with half-order LH kinetics.

  17. Influence of operational parameters and kinetics analysis on the photocatalytic reduction of Cr(VI) by immobilized ZnO.

    Science.gov (United States)

    Behnajady, Mohammad A; Mansoriieh, Nafiseh; Modirshahla, Nasser; Shokri, Mohammad

    2012-01-01

    In the present work the performance of immobilized ZnO on a glass plate with the heat attachment method has been described for photoreduction of Cr(VI) to the less harmful Cr(III) at different operational parameters. The photoreduction of Cr(VI) on the surface of the immobilized ZnO catalyst was studied as a function of the pH of solution, initial Cr(VI) concentration and ultraviolet (UV) light intensity. Results indicated that the reduction rate decreases with increasing initial concentration of Cr(VI) and initial pH of solution, whereas it increases with increasing UV light intensity. The photoreduction rate of Cr(VI) on the surface of the immobilized ZnO in the presence of O2 as mobile gas is more than Ar and N2. The reduction process of Cr(VI) by immobilized ZnO also could be done under visible light irradiation. Pseudo first-order kinetics were observed for the photoreduction of Cr(VI) at different operational conditions. With non-linear regression analysis a mathematical kinetics model was developed for the pseudo first-order constant (k(ap)) as a function of operational parameters.

  18. Continuous preparation of nanoscale zero-valent iron using impinging stream-rotating packed bed reactor and their application in reduction of nitrobenzene

    Science.gov (United States)

    Jiao, Weizhou; Qin, Yuejiao; Luo, Shuai; Feng, Zhirong; Liu, Youzhi

    2017-02-01

    Nanoscale zero-valent iron (nZVI) was continuously prepared by high-gravity reaction precipitation through a novel impinging stream-rotating packed bed (IS-RPB). Reactant solutions of FeSO4 and NaBH4 were conducted into the IS-RPB with flow rates of 60 L/h and rotating speed of 1000 r/min for the preparation of nZVI. As-prepared nZVI obtained by IS-RPB were quasi-spherical morphology and almost uniformly distributed with a particle size of 10-20 nm. The reactivity of nZVI was estimated by the degradation of 100 ml nitrobenzene (NB) with initial concentration of 250 mg/L. The optimum dosage of nZVI obtained by IS-RPB was 4.0 g/L as the NB could be completely removed within 10 min, which reduced 20% compared with nZVI obtained by stirred tank reactor (STR). The reduction of NB and production of aniline (AN) followed pseudo-first-order kinetics, and the pseudo-first-order rate constants were 0.0147 and 0.0034 s-1, respectively. Furthermore, the as-prepared nZVI using IS-RPB reactor in this work can be used within a relatively wide range pH of 1-9.

  19. Programmable Shape Recovery Process of Water-Responsive Shape-Memory Poly(vinyl alcohol) by Wettability Contrast Strategy.

    Science.gov (United States)

    Fang, Zhiqiang; Kuang, Yudi; Zhou, Panpan; Ming, Siyi; Zhu, Penghui; Liu, Yu; Ning, Honglong; Chen, Gang

    2017-02-15

    Water-responsive shape-memory polymers (SMPs) are desirable for biomedical applications, but their limited shape recovery process is problematic. Herein, we demonstrate a shape-memory poly(vinyl alcohol) (SM-PVA) with programmable multistep shape recovery processes in water via a wettability contrast strategy. A hexamethyldisilazane (HMDS)-treated SiO2 nanoparticle layer with varying loading weights was rationally deposited onto the surface of SM-PVA, aiming to create surface-wettability contrast. The varying wettability led to different water adsorption behaviors of SM-PVA that could be well-described by the pseudo-first-order kinetic model. The results calculated from the kinetic model showed that both the pseudo-first order-adsorption rate constant and the saturated water absorption of SM-PVA demonstrated a declining trend as the loading weight of SiO2 increased, which laid the foundation for the local regulation of the water-responsive rate of SM-PVA. Finally, two proof-of-concept drug-delivery devices with diverse three-dimensional structures and actuations are presented based on the water-responsive SM-PVA with preprogrammed multistep shape recovery processes. We believe the programmable shape-memory behavior of water-responsive SM-PVA could highly extend its use in drug delivery, tissue engineering scaffolds, and smart implantable devices, etc.

  20. Five-Loop Running of the QCD Coupling Constant.

    Science.gov (United States)

    Baikov, P A; Chetyrkin, K G; Kühn, J H

    2017-02-24

    We analytically compute the five-loop term in the beta function which governs the running of α_{s}-the quark-gluon coupling constant in QCD. The new term leads to a reduction of the theory uncertainty in α_{s} taken at the Z-boson scale as extracted from the τ-lepton decays as well as to new, improved by one more order of perturbation theory, predictions for the effective coupling constants of the standard model Higgs boson to gluons and for its total decay rate to the quark-antiquark pairs.

  1. Constant Width Planar Computation Characterizes ACC0

    DEFF Research Database (Denmark)

    Hansen, K.A.

    2004-01-01

    We obtain a characterization of ACC 0 in terms of a natural class of constant width circuits, namely in terms of constant width polynomial size planar circuits. This is shown via a characterization of the class of acyclic digraphs which can be embedded on a cylinder surface in such a way that all...

  2. Stability constants for silicate adsorbed to ferrihydrite

    DEFF Research Database (Denmark)

    Hansen, Hans Christian Bruun; Wetche, T.P.; Raulund-Rasmussen, Karsten

    1994-01-01

    Intrinsic surface acidity constants (K(a1)intr, K(a2)intr) and surface complexation constant for adsorption of orthosilicate onto synthetic ferrihydrite (K(Si) for the complex = FeOSi(OH)3) have been determined from acid/base titrations in 0.001-0.1 m NaClO4 electrolytes and silicate adsorption e...

  3. The case for the cosmological constant

    Indian Academy of Sciences (India)

    I present a short overview of current observational results and theoretical models for a cosmological constant. The main motivation for invoking a small cosmological constant (or -term) at the present epoch has to do with observations of high redshift Type Ia supernovae which suggest an accelerating universe.

  4. The case for the cosmological constant

    Indian Academy of Sciences (India)

    Abstract. I present a short overview of current observational results and theoretical models for a cosmological constant. The main motivation for invoking a small cosmological constant (orA-term) at the present epoch has to do with observations of high redshift Type Ia supernovae which suggest an accelerating universe.

  5. 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.

  6. Some zero-sum constants with weights

    Indian Academy of Sciences (India)

    Home; Journals; Proceedings – Mathematical Sciences; Volume 118; Issue 2. Some Zero-Sum Constants with Weights. S D Adhikari ... Motivated by some recent developments around the notion of Davenport constant with weights, we study them in some basic cases. We also define a new combinatorial invariant related to ...

  7. Fullerene derivatives with increased dielectric constants

    NARCIS (Netherlands)

    Jahani, Fatemeh; Torabi, Solmaz; Chiechi, Ryan C; Koster, L Jan Anton; Hummelen, Jan C

    2014-01-01

    The invention of new organic materials with high dielectric constants is of extreme importance for the development of organic-based devices such as organic solar cells. We report on a synthetic way to increase the dielectric constant of fullerene derivatives. It is demonstrated that introducing

  8. Electromechanical systems generating constant frequency alternating current

    Directory of Open Access Journals (Sweden)

    Т.А. Мазур

    2008-01-01

    Full Text Available  In the article we consider the usage of electromechanical drivers of constant speed rotation, which is based on many stepped electrodynamic reduction unit, in onboard main systems of electric supply of alternative current with constant frequency.

  9. Shapley value for constant-sum games

    NARCIS (Netherlands)

    Khmelnitskaya, Anna Borisovna

    2003-01-01

    It is proved that Young’s [4] axiomatization for the Shapley value by marginalism, efficiency, and symmetry is still valid for the Shapley value defined on the class of nonnegative constant-sum games with nonzero worth of grand coalition and on the entire class of constant-sum games as well.

  10. Graviton fluctuations erase the cosmological constant

    Science.gov (United States)

    Wetterich, C.

    2017-10-01

    Graviton fluctuations induce strong non-perturbative infrared renormalization effects for the cosmological constant. The functional renormalization flow drives a positive cosmological constant towards zero, solving the cosmological constant problem without the need to tune parameters. We propose a simple computation of the graviton contribution to the flow of the effective potential for scalar fields. Within variable gravity, with effective Planck mass proportional to the scalar field, we find that the potential increases asymptotically at most quadratically with the scalar field. The solutions of the derived cosmological equations lead to an asymptotically vanishing cosmological ;constant; in the infinite future, providing for dynamical dark energy in the present cosmological epoch. Beyond a solution of the cosmological constant problem, our simplified computation also entails a sizeable positive graviton-induced anomalous dimension for the quartic Higgs coupling in the ultraviolet regime, substantiating the successful prediction of the Higgs boson mass within the asymptotic safety scenario for quantum gravity.

  11. Automated real time constant-specificity surveillance for disease outbreaks

    Directory of Open Access Journals (Sweden)

    Brownstein John S

    2007-06-01

    Full Text Available Abstract Background For real time surveillance, detection of abnormal disease patterns is based on a difference between patterns observed, and those predicted by models of historical data. The usefulness of outbreak detection strategies depends on their specificity; the false alarm rate affects the interpretation of alarms. Results We evaluate the specificity of five traditional models: autoregressive, Serfling, trimmed seasonal, wavelet-based, and generalized linear. We apply each to 12 years of emergency department visits for respiratory infection syndromes at a pediatric hospital, finding that the specificity of the five models was almost always a non-constant function of the day of the week, month, and year of the study (p Conclusion Modeling the variance of visit patterns enables real-time detection with known, constant specificity at all times. With constant specificity, public health practitioners can better interpret the alarms and better evaluate the cost-effectiveness of surveillance systems.

  12. Path-dependent variational effects and multidimensional tunneling in multi-path variational transition state theory: rate constants calculated for the reactions of HO2 with tert-butanol by including all 46 paths for abstraction at C and all six paths for abstraction at O.

    Science.gov (United States)

    Bao, Junwei Lucas; Sripa, Pattrawan; Truhlar, Donald G

    2016-01-14

    Multi-path variational transition state theory (MP-VTST) provides a conformationally complete framework for calculating gas-phase rate constants. For reactions in which the transition state has distinguishable torsional minima (which include most reactions), there are multiple possible reaction paths. In principle MP-VTST includes the contributions from all the reaction paths, and it should explicitly treat the variational and tunneling effects of each path, but in practice one may need to truncate the number of paths included in MP-VTST calculations in order to achieve a balance between computational cost and accuracy. In this work, we present calculations including all paths for two prototype combustion reactions, namely the two hydrogen abstraction reactions from tert-butanol by HO2 radical. For both reactions we included all the reaction paths. Since abstraction at C has 46 paths, it provided a good opportunity to carry out a case study in which we investigated the errors introduced by truncating the number of paths. For the reaction studied, we found that the variational and multidimensional tunneling transmission coefficients are very different for different reaction paths, which provides new evidence that MP-VTST is necessary for treating path-dependent variational effects and multidimensional tunneling. We found that tunneling transmission coefficients can be much larger for higher-energy paths than for lower-energy ones. Interestingly, the simple hypothesis that higher barriers are narrower does not explain this finding in the present case; we found instead that the effect is due to higher-energy barriers having the possibility of tunneling at energies farther below the barrier top. We also show that a previously applied criterion for judging convergence with respect to the number of paths may not be reliable at low temperature.

  13. Encapsulation of iron nanoparticles in alginate biopolymer for trichloroethylene remediation

    Science.gov (United States)

    Bezbaruah, Achintya N.; Shanbhogue, Sai Sharanya; Simsek, Senay; Khan, Eakalak

    2011-12-01

    Nanoscale zero-valent iron (NZVI) particles (10-90 nm) were encapsulated in biodegradable calcium-alginate capsules for the first time for application in environmental remediation. Encapsulation is expected to offers distinct advances over entrapment. Trichloroethylene (TCE) degradation was 89-91% in 2 h, and the reaction followed pseudo first order kinetics for encapsulated NZVI systems with an observed reaction rate constant ( k obs) of 1.92-3.23 × 10-2 min-1 and a surface normalized reaction rate constant ( k sa) of 1.02-1.72 × 10-3 L m-2 min-1. TCE degradation reaction rates for encapsulated and bare NZVI were similar indicating no adverse affects of encapsulation on degradation kinetics. The shelf-life of encapsulated NZVI was found to be four months with little decrease in TCE removal efficiency.

  14. Chemistry of N,N'-dimethylformamidine. II. Hydrolysis: kinetically controlled formation of cis-N-methylformamide

    Energy Technology Data Exchange (ETDEWEB)

    Halliday, J.D.; Symons, E.A.

    1978-06-01

    The hydrolysis of N,N'-dimethylformamidine (DMFA) has been investigated in acid and alkaline aqueous media by /sup 1/H nmr; only a narrow basic pH range could be extensively studied kinetically. The pseudo-first-order k/sub obs/, rose steadily from pH 11.5 to 13.0 (reaction approximately first order in OH/sup -/), then became independent of pH above 13.5 (9.3 x 10/sup -4/ s/sup -1/ at 10/sup 0/C). In contrast to many amidines, DMFA is quite stable in acid solution (estimated value of the pseudo-first-order hydrolysis rate constant is 1.4 x 10/sup -11/ s/sup -1/ at 10/sup 0/C, pH 0.05, from measurements at 100 and 140/sup 0/C). This stability is ascribed to the difficulty of eliminating the fairly stron base methylamine from the tetrahedral intermediate in acid solution. N-Methylformamide (NMF), one of the products, is formed initially as the cis isomer. A somewhat slower conversion then occurs to the thermodynamically more stable trans isomer. This unusual result is explained in terms of Deslongchamps and co-workers' theory of stereo-electronic control for the orbital-assisted breakdown of tetrahedral intermediates. 4 figures, 1 table.

  15. Nanocasted synthesis of magnetic mesoporous iron cerium bimetal oxides (MMIC) as an efficient heterogeneous Fenton-like catalyst for oxidation of arsenite.

    Science.gov (United States)

    Wen, Zhipan; Zhang, Yalei; Dai, Chaomeng; Sun, Zhen

    2015-04-28

    Magnetic mesoporous iron cerium bimetal oxides (MMIC) with large surface area and pore volume was synthesized via the hard template approach. This obtained MMIC was easily separated from aqueous solution with an external magnetic field and was proposed as a heterogeneous Fenton-like catalyst for oxidation of As(III). The MMIC presented excellent catalytic activity for the oxidation of As(III), achieving almost complete oxidation of 1000ppb As(III) after 60min and complete removal of arsenic species after 180min with reaction conditions of 0.4g/L catalyst, pH of 3.0 and 0.4mM H2O2. Kinetics analysis showed that arsenic removal followed the pseudo-first order, and the pseudo-first-order rate constants increased from 0.0014min(-1) to 0.0548min(-1) as the H2O2 concentration increased from 0.04mM to 0.4mM. On the basis of the effects of XPS analysis and reactive oxidizing species, As(III) in aqueous solution was mainly oxidized by OH radicals, including the surface-bound OHads generated on the MMIC surface which were involved in Fe(2+) and Ce(3+), and free OHfree generation by soluble iron ions which were released from the MMIC into the bulk solution, and the generated As(V) was finally removed by MMIC through adsorption. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Kinetics and isotherm studies of Cd(II) adsorption from aqueous solution utilizing seeds of bottlebrush plant ( Callistemon chisholmii)

    Science.gov (United States)

    Rao, Rifaqat Ali Khan; Kashifuddin, Mohammad

    2014-12-01

    Seeds of bottlebrush, a novel plant material, were found to exhibit excellent adsorption capacity over a wide range of Cd(II) concentration. It was characterized by Fourier transform infrared spectroscopy and Scanning Electron Microscopy to support the adsorption of Cd(II) ions. Effect of various parameters like pH, contact time, initial concentration and different electrolytes was investigated using batch process to optimize conditions for maximum adsorption. The adsorbent data were analyzed using Langmuir, Freundlich, Temkin and Dubinin-Redushkeuich isotherm equations at 30°, 40° and 50 °C. Thermodynamic parameters such as standard enthalpy change (Δ H°), free energy change (Δ G°) and entropy change (Δ S°) were also evaluated and the results indicated that adsorption of Cd(II) are spontaneous and endothermic. Various kinetics models including the Pseudo-first-order kinetics, Pseudo-second-order kinetics and Intraparticle diffusion models have been applied to the experimental data to predict the adsorption kinetics. Kinetic study was carried out by varying initial concentration of Cd(II) at constant temperature and it was found that pseudo-second-order rate equation was better obeyed than pseudo-first-order equation supporting that chemisorption process was involved.

  17. Constants and Pseudo-Constants of Coupled Beam Motion in the PEP-II Rings

    Energy Technology Data Exchange (ETDEWEB)

    Decker, F.J.; Colocho, W.S.; Wang, M.H.; Yan, Y.T.; Yocky, G.; /SLAC

    2011-11-01

    Constants of beam motion help as cross checks to analyze beam diagnostics and the modeling procedure. Pseudo-constants, like the betatron mismatch parameter or the coupling parameter det C, are constant till certain elements in the beam line change them. This can be used to visually find the non-desired changes, pinpointing errors compared with the model.

  18. Interacting universes and the cosmological constant

    Energy Technology Data Exchange (ETDEWEB)

    Alonso-Serrano, A. [Centro de Física “Miguel Catalán”, Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 121, 28006 Madrid (Spain); Estación Ecológica de Biocosmología, Pedro de Alvarado 14, 06411 Medellín (Spain); Bastos, C. [Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Avenida Rovisco Pais 1, 1049-001 Lisboa (Portugal); Bertolami, O. [Instituto de Plasmas e Fusão Nuclear, Instituto Superior Técnico, Avenida Rovisco Pais 1, 1049-001 Lisboa (Portugal); Departamento de Física e Astronomia, Faculdade de Ciências da Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto (Portugal); Robles-Pérez, S., E-mail: salvarp@imaff.cfmac.csic.es [Centro de Física “Miguel Catalán”, Instituto de Física Fundamental, Consejo Superior de Investigaciones Científicas, Serrano 121, 28006 Madrid (Spain); Estación Ecológica de Biocosmología, Pedro de Alvarado 14, 06411 Medellín (Spain); Física Teórica, Universidad del País Vasco, Apartado 644, 48080 Bilbao (Spain)

    2013-02-12

    In this Letter it is studied the effects that an interaction scheme among universes can have in the values of their cosmological constants. In the case of two interacting universes, the value of the cosmological constant of one of the universes becomes very close to zero at the expense of an increasing value of the cosmological constant of the partner universe. In the more general case of a chain of N interacting universes with periodic boundary conditions, the spectrum of the Hamiltonian splits into a large number of levels, each of them associated with a particular value of the cosmological constant, that can be occupied by single universes revealing a collective behavior that plainly shows that the multiverse is much more than the mere sum of its parts.

  19. Graviton fluctuations erase the cosmological constant

    Directory of Open Access Journals (Sweden)

    C. Wetterich

    2017-10-01

    Full Text Available Graviton fluctuations induce strong non-perturbative infrared renormalization effects for the cosmological constant. The functional renormalization flow drives a positive cosmological constant towards zero, solving the cosmological constant problem without the need to tune parameters. We propose a simple computation of the graviton contribution to the flow of the effective potential for scalar fields. Within variable gravity, with effective Planck mass proportional to the scalar field, we find that the potential increases asymptotically at most quadratically with the scalar field. The solutions of the derived cosmological equations lead to an asymptotically vanishing cosmological “constant” in the infinite future, providing for dynamical dark energy in the present cosmological epoch. Beyond a solution of the cosmological constant problem, our simplified computation also entails a sizeable positive graviton-induced anomalous dimension for the quartic Higgs coupling in the ultraviolet regime, substantiating the successful prediction of the Higgs boson mass within the asymptotic safety scenario for quantum gravity.

  20. The time constant of the somatogravic illusion

    NARCIS (Netherlands)

    Correia Grácio, B.J.; Winkel, K.N. de; Groen, E.L.; Wentink, M.; Bos, J.E.

    2013-01-01

    Met desdemona hebben we gevonden dat de tijd constante van de somatografische illusie rond twee seconden is. Dit resultaat verschilt van wat was gevonden in ander onderzoek dat gebruikt maakt van een gewone centrifuge