Reaction rate of propene pyrolysis.

Science.gov (United States)

Han, Peipei; Su, Kehe; Liu, Yan; Wang, Yanli; Wang, Xin; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong

2011-10-01

The reaction rate of propene pyrolysis was investigated based on the elementary reactions proposed in Qu et al., J Comput Chem 2009, 31, 1421. The overall reaction rate was developed with the steady-state approximation and the rate constants of the elementary reactions were determined with the variational transition state theory. For the elementary reaction having transition state, the vibrational frequencies of the selected points along the minimum energy path were calculated with density functional theory at B3PW91/6-311G(d,p) level and the energies were improved with the accurate model chemistry method G3(MP2). For the elementary reaction without transition state, the frequencies were calculated with CASSCF/6-311G(d,p) and the energies were refined with the multireference configuration interaction method MRCISD/6-311G(d,p). The rate constants were evaluated within 200-2000 K and the fitted three-parameter expressions were obtained. The results are consistent with those in the literatures in most cases. For the overall rate, it was found that the logarithm of the rate and the reciprocal temperature have excellent linear relationship above 400 K, predicting that the rate follows a typical first-order law at high temperatures of 800-2000 K, which is also consistent with the experiments. The apparent activation energy in 800-2000 K is 317.3 kJ/mol from the potential energy surface of zero Kelvin. This value is comparable with the energy barriers, 365.4 and 403.7 kJ/mol, of the rate control steps. However, the apparent activation energy, 215.7 kJ/mol, developed with the Gibbs free energy surface at 1200 K is consistent with the most recent experimental result 201.9 ± 0.6 kJ/mol. Copyright © 2011 Wiley Periodicals, Inc.

Reaction rate of hydrolysis of iodine

International Nuclear Information System (INIS)

Miyake, Yoshikazu; Eguchi, Wataru; Adachi, Motonari

1979-01-01

Absorption rates of dilute iodine vapor contained in air by aqueous mixtures of sodium hydroxide and boric acid were measured using a laminar liquid jet column absorber at 298 K. Absorption rates in this system are controlled by a series of complex reactions taking place in the liquid phase. The reaction rate constant of iodine hydrolysis in the aqueous phase was determined from the absorption rates observed under the conditions that the base-catalytic hydrolysis reaction of iodine can be considered to be irreversible and that other reactions can be neglected. The absorption rates calculated theoretically with the rate constant value obtained above were in good accordance with the whole experimental data observed for a wide range of experimental conditions. (author)

Oxidative Dehydrogenation on Nanocarbon: Insights into the Reaction Mechanism and Kinetics via in Situ Experimental Methods.

Science.gov (United States)

Qi, Wei; Yan, Pengqiang; Su, Dang Sheng

2018-03-20

Sustainable and environmentally benign catalytic processes are vital for the future to supply the world population with clean energy and industrial products. The replacement of conventional metal or metal oxide catalysts with earth abundant and renewable nonmetallic materials has attracted considerable research interests in the field of catalysis and material science. The stable and efficient catalytic performance of nanocarbon materials was discovered at the end of last century, and these materials are considered as potential alternatives for conventional metal-based catalysts. With its rapid development in the past 20 years, the research field of carbon catalysis has been experiencing a smooth transition from the discovery of novel nanocarbon materials or related new reaction systems to the atomistic-level mechanistic understanding on the catalytic process and the subsequent rational design of the practical catalytic reaction systems. In this Account, we summarize the recent progress in the kinetic and mechanistic studies on nanocarbon catalyzed alkane oxidative dehydrogenation (ODH) reactions. The paper attempts to extract general concepts and basic regularities for carbon catalytic process directing us on the way for rational design of novel efficient metal-free catalysts. The nature of the active sites for ODH reactions has been revealed through microcalorimetric analysis, ambient pressure X-ray photoelectron spectroscopy (XPS) measurement, and in situ chemical titration strategies. The detailed kinetic analysis and in situ catalyst structure characterization suggests that carbon catalyzed ODH reactions involve the redox cycles of the ketonic carbonyl-hydroxyl pairs, and the key physicochemical parameters (activation energy, reaction order, and rate/equilibrium constants, etc.) of the carbon catalytic systems are proposed and compared with conventional transition metal oxide catalysts. The proposal of the intrinsic catalytic activity (TOF) provides the

Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide

International Nuclear Information System (INIS)

Jin, Jun-Cheng; Tong, Wen-Quan; Fu, Ai-Yun; Xie, Cheng-Gen; Chang, Wen-Gui; Wu, Ju; Xu, Guang-Nian; Zhang, Ya-Nan; Li, Jun; Li, Yong; Yang, Peng-Qi

2015-01-01

Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2 1 helical chains. While the Nd(III) ions are bridged through μ 2 -HIDC 2− and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2 1 helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2 1 helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature

Temperature effects on lithium-nitrogen reaction rates

International Nuclear Information System (INIS)

Ijams, W.J.; Kazimi, M.S.

1985-08-01

A series of experiments have been run with the aim of measuring the reaction rate of lithium and nitrogen over a wide spectrum of lithium pool temperatures. In these experiments, pure nitrogen was blown at a controlled flow rate over a preheated lithium pool. The pool had a surface area of approximately 4 cm 2 and a total volume of approximately 6 cm 3 . The system pressure varied from 0 to 4 psig. The reaction rate was very small - approximately 0.002 to 0.003 g Li min cm 2 for lithium temperatures below 500 0 C. Above 500 0 C the reaction rate began to increase sharply, and reached a maximum of approximately 0.80 g Li min cm 2 above 700 0 C. It dropped off beyond 1000 0 C and seemed to approach zero at 1150 0 C. The maximum reaction rate observed in these forced convection experiments was higher by 60% than those previously observed in experiments where the nitrogen flowed to the reaction site by means of natural convection. During a reaction, a hard nitride layer built up on the surface of the lithium pool - its effect on the reaction rate was observed. The effect of the nitrogen flow rate on the reaction rate was also observed

Measurement of inertial confinement fusion reaction rate

International Nuclear Information System (INIS)

Peng Xiaoshi; Wang Feng; Tang Daorun; Liu Shenye; Huang Tianxuan; Liu Yonggang; Xu Tao; Chen Ming; Mei Yu

2011-01-01

Fusion reaction rate is an important parameter for measuring compression during the implosion in inertial confinement fusion experiment. We have developed a system for fusion reaction history measurement with high temporal resolution. The system is composed of plastic scintillator and nose cone, optical system and streak camera. We have applied this system on the SG-III prototype for fusion reaction rate measuring. For the first time, fusion reaction rate history have been measured for deuterium-tritium filled targets with neutrons yields about 10 10 . We have analyzed possible influence factor during fusion reaction rate measuring. It indicates that the instrument measures fusion reaction bang time at temporal resolutions as low as 30 ps.(authors)

Fast and calibration free determination of first order reaction kinetics in API synthesis using in-situ ATR-FTIR.

Science.gov (United States)

Rehbein, Moritz C; Husmann, Sascha; Lechner, Christian; Kunick, Conrad; Scholl, Stephan

2018-05-01

In early stages of drug development only sparse amounts of the key substances are available, which is problematic for the determination of important process data like reaction kinetics. Therefore, it is important to perform experiments as economically as possible, especially in regards to limiting compounds. Here we demonstrate the use of a temperature step experiment enabling the determination of complete reaction kinetics in a single non-isothermal experiment. In contrast to the traditionally used HPLC, the method takes advantage of the high measuring rate and the low amount of labor involved in using in-situ ATR-FTIR to determine time-dependent concentration-equivalent data. Copyright © 2017 Elsevier B.V. All rights reserved.

In situ alkali-silica reaction observed by x-ray microscopy

International Nuclear Information System (INIS)

Kurtis, K.E.; Monteiro, P.J.M.; Brown, J.T.; Meyer-Ilse, W.

1997-01-01

In concrete, alkali metal ions and hydroxyl ions contributed by the cement and reactive silicates present in aggregate can participate in a destructive alkali-silica reaction (ASR). This reaction of the alkalis with the silicates produces a gel that tends to imbibe water found in the concrete pores, leading to swelling of the gel and eventual cracking of the affected concrete member. Over 104 cases of alkali-aggregate reaction in dams and spillways have been reported around the world. At present, no method exists to arrest the expansive chemical reaction which generates significant distress in the affected structures. Most existing techniques available for the examination of concrete microstructure, including ASR products, demand that samples be dried and exposed to high pressure during the observation period. These sample preparation requirements present a major disadvantage for the study of alkali-silica reaction. Given the nature of the reaction and the affect of water on its products, it is likely that the removal of water will affect the morphology, creating artifacts in the sample. The purpose of this research is to observe and characterize the alkali-silica reaction, including each of the specific reactions identified previously, in situ without introducing sample artifacts. For observation of unconditioned samples, x-ray microscopy offers an opportunity for such an examination of the alkali-silica reaction. Currently, this investigation is focusing on the effect of calcium ions on the alkali-silica reaction

In situ alkali-silica reaction observed by x-ray microscopy

Energy Technology Data Exchange (ETDEWEB)

Kurtis, K.E.; Monteiro, P.J.M. [Univ. of California, Berkeley, CA (United States); Brown, J.T.; Meyer-Ilse, W. [Ernest Orlando Lawrence Berkeley National Lab., CA (United States)

1997-04-01

In concrete, alkali metal ions and hydroxyl ions contributed by the cement and reactive silicates present in aggregate can participate in a destructive alkali-silica reaction (ASR). This reaction of the alkalis with the silicates produces a gel that tends to imbibe water found in the concrete pores, leading to swelling of the gel and eventual cracking of the affected concrete member. Over 104 cases of alkali-aggregate reaction in dams and spillways have been reported around the world. At present, no method exists to arrest the expansive chemical reaction which generates significant distress in the affected structures. Most existing techniques available for the examination of concrete microstructure, including ASR products, demand that samples be dried and exposed to high pressure during the observation period. These sample preparation requirements present a major disadvantage for the study of alkali-silica reaction. Given the nature of the reaction and the affect of water on its products, it is likely that the removal of water will affect the morphology, creating artifacts in the sample. The purpose of this research is to observe and characterize the alkali-silica reaction, including each of the specific reactions identified previously, in situ without introducing sample artifacts. For observation of unconditioned samples, x-ray microscopy offers an opportunity for such an examination of the alkali-silica reaction. Currently, this investigation is focusing on the effect of calcium ions on the alkali-silica reaction.

The Oxford-Diamond In Situ Cell for studying chemical reactions using time-resolved X-ray diffraction

Science.gov (United States)

Moorhouse, Saul J.; Vranješ, Nenad; Jupe, Andrew; Drakopoulos, Michael; O'Hare, Dermot

2012-08-01

A versatile, infrared-heated, chemical reaction cell has been assembled and commissioned for the in situ study of a range of chemical syntheses using time-resolved energy-dispersive X-ray diffraction (EDXRD) on Beamline I12 at the Diamond Light Source. Specialized reactor configurations have been constructed to enable in situ EDXRD investigation of samples under non-ambient conditions. Chemical reactions can be studied using a range of sample vessels such as alumina crucibles, steel hydrothermal autoclaves, and glassy carbon tubes, at temperatures up to 1200 °C.

Representing Rate Equations for Enzyme-Catalyzed Reactions

Science.gov (United States)

Ault, Addison

2011-01-01

Rate equations for enzyme-catalyzed reactions are derived and presented in a way that makes it easier for the nonspecialist to see how the rate of an enzyme-catalyzed reaction depends upon kinetic constants and concentrations. This is done with distribution equations that show how the rate of the reaction depends upon the relative quantities of…

Cross-section and reaction rates for some reactions involved in explosive nucleosynthesis

International Nuclear Information System (INIS)

Cheng, C.W.

1979-03-01

Total proton-induced and alpha-induced reaction cross sections have been determined for the 24 Mg(α,n), 25 Mg(p,n), 26 Mg(p,n), 27 Al(p,n), 28 Si(α,n), 42 Ca(p,γ), 42 Ca(α,n) and 44 Ca(p,n) reactions from energies near threshold (except the exothermic (p,γ) reaction) to about 3 to 4 MeV above threshold. The product nuclei are all positron emitters with half-lives ranging from about 3 sec to about 4 hours. From the measured cross sections reaction rates have been calculated in the temperature range 1 9 9 =1, at which the discrepancy is large. Included also are analytic forms for (p,n), (α,n), and (p,γ) reactions which can be used to describe the reaction rate within the temperature range 1 9 <=6 and which agree with the experimental rates at the discrete temperatures where the reaction rates have been calculated

Rates of Thermonuclear Reactions in Dense Plasmas

International Nuclear Information System (INIS)

Tsytovich, V.N.; Bornatici, M.

2000-01-01

The problem of plasma screening of thermonuclear reactions has attracted considerable scientific interest ever since Salpeter's seminal paper, but it is still faced with controversial statements and without any definite conclusion. It is of relevant importance to thermonuclear reactions in dense astrophysical plasmas, for which charge screening can substantially affect the reaction rates. Whereas Salpeter and a number of subsequent investigations have dealt with static screening, Carraro, Schafer, and Koonin have drawn attention to the fact that plasma screening of thermonuclear reactions is an essentially dynamic effect. In addressing the issue of collective plasma effects on the thermonuclear reaction rates, the first critical overview of most of the work carried out so far is presented and the validity of the test particle approach is assessed. In contrast to previous investigations, we base our description on the kinetic equation for nonequilibrium plasmas, which accounts for the effects on the rates of thermonuclear reactions of both plasma fluctuations and screening and allows one to analyze explicitly the effects of the fluctuations on the reaction rates. Such a kinetic formulation is more general than both Salpeter's approach and the recently developed statistical approaches and makes it possible to obtain a more comprehensive understanding of the problem. A noticeable result of the fluctuation approach is that the static screening, which affects both the interaction and the self-energy of the reacting nuclei, does not affect the reaction rates, in contrast with the results obtained so far. Instead, a reduction of the thermonuclear reaction rates is obtained as a result of the effect of plasma fluctuations related to the free self-energy of the reacting nuclei. A simple physical explanation of the slowing down of the reaction rates is given, and the relation to the dynamically screened test particle approach is discussed. Corrections to the reaction rates

Phosphorus-31 NMR magnetization transfer measurements of metabolic reaction rates in the rat heart and kidney in vivo

International Nuclear Information System (INIS)

Koretsky, A.P.

1984-01-01

31 P NMR is a unique tool to study bioenergetics in living cells. The application of magnetization transfer techniques to the measurement of steady-state enzyme reaction rates provides a new approach to understanding the regulation of high energy phosphate metabolism. This dissertation is concerned with the measurement of the rates of ATP synthesis in the rat kidney and of the creatine kinase catalyzed reaction in the rat heart in situ. The theoretical considerations of applying magnetization transfer techniques to intact organs are discussed with emphasis on the problems associated with multiple exchange reactions and compartmentation of reactants. Experimental measurements of the ATP synthesis rate were compared to whole kidney oxygen consumption and Na + reabsorption rates to derive ATP/O values. The problems associated with ATP synthesis rate measurements in kidney, e.g. the heterogeneity of the inorganic phosphate resonance, are discussed and experiments to overcome these problems proposed. In heart, the forward rate through creatine kinase was measured to be larger than the reverse rate. To account for the difference in forward and reverse rates a model is proposed based on the compartmentation of a small pool of ATP

In situ feeding rates of plantonic copepods: A comparison of four methods

DEFF Research Database (Denmark)

Kiørboe, Thomas; Møhlenberg, Flemming; Riisgård, Hans Ulrik

1985-01-01

into estimates of in situ algal grazing rates by means of independently estimated gut turnover times, and were compared with chlorophyll and particle-volume grazing rates of animals sampled simultaneously and incubated in water from the collection depth. In addition, egg-production rates of adult females were...... problems of the different methods are discussed, and it is concluded that they all approach representative (although minimum) estimates of in situ feeding rates....

Typewriting rate as a function of reaction time.

Science.gov (United States)

Hayes, V; Wilson, G D; Schafer, R L

1977-12-01

This study was designed to determine the relationship between reaction time and typewriting rate. Subjects were 24 typists ranging in age from 19 to 39 yr. Reaction times (.001 sec) to a light were recorded for each finger and to each alphabetic character and three punctuation marks. Analysis of variance yielded significant differences in reaction time among subjects and fingers. Correlation between typewriting rate and average reaction time to the alphabetic characters and three punctuation marks was --.75. Correlation between typewriting rate and the difference between the reaction time of the hands was --.42. Factors influencing typewriting rate may include reaction time of the fingers, difference between the reaction time of the hands, and reaction time to individual keys on the typewriter. Implications exist for instructional methodology and further research.

Rate Coefficients for the OH + (CHO)2 (Glyoxal) Reaction Between 240 and 400 K

Science.gov (United States)

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

2006-12-01

Glyoxal (CHO)2, the simplest dialdehyde, is an end product formed in the atmospheric oxidation of biogenic hydrocarbons, for example, isoprene. As such, glyoxal plays a role in regional air quality and ozone production in certain locations. Glyoxal is lost in the atmosphere via UV photolysis and reaction with OH. However, the currently available rate coefficient data for the OH + glyoxal reaction is limited to a single room- temperature measurement made using the relative rate method. A determination of the rate coefficient temperature dependence is therefore needed for a more complete interpretation of the atmospheric processing of glyoxal. This study reports the rate coefficient for the OH + (CHO)2 reaction measured under pseudo- first-order conditions in OH ([(CHO)2] > 1000 [OH]0). OH radicals were produced using 248 nm pulsed laser photolysis of H2O2 or HNO3 and detected by pulsed laser induced fluorescence. The concentration of glyoxal in the reactor was determined using three independent techniques; gas flow rates as well as in situ UV and IR absorption. The total pressure in the reactor was varied from 40 to 300 Torr (He), and the rate coefficient was found to be independent of pressure over the temperature range studied. The rate coefficient exhibits a negative temperature dependence between 240 and 400 K consistent with the dependence previously observed for many other aldehydes. Our room-temperature rate coefficient is smaller than the relative rate value that is currently recommended for use in atmospheric model calculations. Our measured rate coefficients are discussed with respect to those for other aldehydes. The atmospheric implications of our work will also be discussed.

In-situ nanoelectrospray for high-throughput screening of enzymes and real-time monitoring of reactions.

Science.gov (United States)

Yang, Yuhan; Han, Feifei; Ouyang, Jin; Zhao, Yunling; Han, Juan; Na, Na

2016-01-01

The in-situ and high-throughput evaluation of enzymes and real-time monitoring of enzyme catalyzed reactions in liquid phase is quite significant in the catalysis industry. In-situ nanoelectrospray, the direct sampling and ionization method for mass spectrometry, has been applied for high-throughput evaluation of enzymes, as well as the on-line monitoring of reactions. Simply inserting a capillary into a liquid system with high-voltage applied, analytes in liquid reaction system can be directly ionized at the capillary tip with small volume consumption. With no sample pre-treatment or injection procedure, different analytes such as saccharides, amino acids, alkaloids, peptides and proteins can be rapidly and directly extracted from liquid phase and ionized at the capillary tip. Taking irreversible transesterification reaction of vinyl acetate and ethanol as an example, this technique has been used for the high-throughput evaluation of enzymes, fast optimizations, as well as real-time monitoring of reaction catalyzed by different enzymes. In addition, it is even softer than traditional electrospray ionization. The present method can also be used for the monitoring of other homogenous and heterogeneous reactions in liquid phases, which will show potentials in the catalysis industry. Copyright © 2015 Elsevier B.V. All rights reserved.

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Luan; Tao, Franklin, E-mail: franklin.tao.2011@gmail.com [Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 (United States); Department of Chemical and Petroleum Engineering, University of Kansas, Lawrence, Kansas 66045 (United States)

2016-06-15

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

Development of a reaction cell for in-situ/operando studies of surface of a catalyst under a reaction condition and during catalysis

International Nuclear Information System (INIS)

Nguyen, Luan; Tao, Franklin

2016-01-01

Tracking surface chemistry of a catalyst during catalysis is significant for fundamental understanding of catalytic performance of the catalyst since it allows for establishing an intrinsic correlation between surface chemistry of a catalyst at its working status and its corresponding catalytic performance. Ambient pressure X-ray photoelectron spectroscopy can be used for in-situ studies of surfaces of different materials or devices in a gas. To simulate the gaseous environment of a catalyst in a fixed-bed a flowing gaseous environment of reactants around the catalyst is necessary. Here, we report the development of a new flowing reaction cell for simulating in-situ study of a catalyst surface under a reaction condition in gas of one reactant or during catalysis in a mixture of reactants of a catalytic reaction. The homemade reaction cell is installed in a high vacuum (HV) or ultrahigh vacuum (UHV) environment of a chamber. The flowing gas in the reaction cell is separated from the HV or UHV environment through well sealings at three interfaces between the reaction cell and X-ray window, sample door and aperture of front cone of an energy analyzer. Catalyst in the cell is heated through infrared laser beam introduced through a fiber optics interfaced with the reaction cell through a homemade feedthrough. The highly localized heating on the sample holder and Au-passivated internal surface of the reaction cell effectively minimizes any unwanted reactions potentially catalyzed by the reaction cell. The incorporated laser heating allows a fast heating and a high thermal stability of the sample at a high temperature. With this cell, a catalyst at 800 °C in a flowing gas can be tracked readily.

Effect of excited states on thermonuclear reaction rates

International Nuclear Information System (INIS)

Sargood, D.G.

1983-01-01

Values of the ratio of the thermonuclear reaction rate of a reaction, with target nuclei in a thermal distribution of energy states, to the reaction rate with all target nuclei in their ground states are tabulated for neutron, proton and α-particle induced reactions on the naturally occurring nuclei from 20 Ne to 70 Zn, at temperatures of 1, 2, 3.5 and 5x10 9 K. The ratios are determined from reaction rates based on statistical model cross sections

Ex-situ and in-situ mineral carbonation as a means to sequester carbon dioxide

Energy Technology Data Exchange (ETDEWEB)

Gerdemann, Stephen J.; Dahlin, David C.; O' Connor, William K.; Penner, Larry R.; Rush, G.E.

2004-01-01

The U. S. Department of Energy's Albany Research Center is investigating mineral carbonation as a method of sequestering CO2 from coal-fired-power plants. Magnesium-silicate minerals such as serpentine [Mg3Si2O5(OH)4] and olivine (Mg2SiO4) react with CO2 to produce magnesite (MgCO3), and the calcium-silicate mineral, wollastonite (CaSiO3), reacts to form calcite (CaCO3). It is possible to carry out these reactions either ex situ (above ground in a traditional chemical processing plant) or in situ (storage underground and subsequent reaction with the host rock to trap CO2 as carbonate minerals). For ex situ mineral carbonation to be economically attractive, the reaction must proceed quickly to near completion. The reaction rate is accelerated by raising the activity of CO2 in solution, heat (but not too much), reducing the particle size, high-intensity grinding to disrupt the crystal structure, and, in the case of serpentine, heat-treatment to remove the chemically bound water. All of these carry energy/economic penalties. An economic study illustrates the impact of mineral availability and process parameters on the cost of ex situ carbon sequestration. In situ carbonation offers economic advantages over ex situ processes, because no chemical plant is required. Knowledge gained from the ex situ work was applied to long-term experiments designed to simulate in situ CO2 storage conditions. The Columbia River Basalt Group (CRBG), a multi-layered basaltic lava formation, has potentially favorable mineralogy (up to 25% combined concentration of Ca, Fe2+, and Mg cations) for storage of CO2. However, more information about the interaction of CO2 with aquifers and the host rock is needed. Core samples from the CRBG, as well as samples of olivine, serpentine, and sandstone, were reacted in an autoclave for up to 2000 hours at elevated temperatures and pressures. Changes in core porosity, secondary mineralizations, and both solution and solid chemistry were measured.

Non-equilibrium reaction rates in chemical kinetic equations

Science.gov (United States)

Gorbachev, Yuriy

2018-05-01

Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

Grain rotation and lattice deformation during photoinduced chemical reactions revealed by in situ X-ray nanodiffraction.

Science.gov (United States)

Huang, Zhifeng; Bartels, Matthias; Xu, Rui; Osterhoff, Markus; Kalbfleisch, Sebastian; Sprung, Michael; Suzuki, Akihiro; Takahashi, Yukio; Blanton, Thomas N; Salditt, Tim; Miao, Jianwei

2015-07-01

In situ X-ray diffraction (XRD) and transmission electron microscopy (TEM) have been used to investigate many physical science phenomena, ranging from phase transitions, chemical reactions and crystal growth to grain boundary dynamics. A major limitation of in situ XRD and TEM is a compromise that has to be made between spatial and temporal resolution. Here, we report the development of in situ X-ray nanodiffraction to measure high-resolution diffraction patterns from single grains with up to 5 ms temporal resolution. We observed, for the first time, grain rotation and lattice deformation in chemical reactions induced by X-ray photons: Br(-) + hv → Br + e(-) and e(-) + Ag(+) → Ag(0). The grain rotation and lattice deformation associated with the chemical reactions were quantified to be as fast as 3.25 rad s(-1) and as large as 0.5 Å, respectively. The ability to measure high-resolution diffraction patterns from individual grains with a temporal resolution of several milliseconds is expected to find broad applications in materials science, physics, chemistry and nanoscience.

Effect of nuclear reaction rates on primordial abundances

International Nuclear Information System (INIS)

Mishra, Abhishek; Basu, D.N.

2011-01-01

The theoretical predictions of the primordial abundances of elements in the big-bang nucleosynthesis (BBN) are dominated by uncertainties in the input nuclear reaction rates. The effect of modifying these reaction rates on light element abundance yields in BBN by replacing the thirty-five reaction rates out of the existing eighty-eight has been investigated. Also the study have been taken of these yields as functions of evolution time or temperature. Here it has been found that using these new reaction rates results in only a little increase in helium mass fraction over that obtained previously in BBN calculations. This allows insights into the role of the nuclear reaction rates in the setting of the neutron-to-proton ratio during the BBN epoch. We observe that most of these nuclear reactions have minimal effect on the standard BBN abundance yields of 6 Li and 7 Li

Pulsed laser-assisted focused electron-beam-induced etching of titanium with XeF2: enhanced reaction rate and precursor transport.

Science.gov (United States)

Noh, J H; Fowlkes, J D; Timilsina, R; Stanford, M G; Lewis, B B; Rack, P D

2015-02-25

In order to enhance the etch rate of electron-beam-induced etching, we introduce a laser-assisted focused electron-beam-induced etching (LA-FEBIE) process which is a versatile, direct write nanofabrication method that allows nanoscale patterning and editing. The results demonstrate that the titanium electron stimulated etch rate via the XeF2 precursor can be enhanced up to a factor of 6 times with an intermittent pulsed laser assist. The evolution of the etching process is correlated to in situ stage current measurements and scanning electron micrographs as a function of time. The increased etch rate is attributed to photothermally enhanced Ti-F reaction and TiF4 desorption and in some regimes enhanced XeF2 surface diffusion to the reaction zone.

Thermonuclear reaction rates in a deuterium-tritium plasma

International Nuclear Information System (INIS)

Beckman, L.

1978-12-01

In a deuterium-tritium plasma six thermonuclear reactions take place between the deuterons, tritons and the 3 He-particles formed in about half of the d-d-reactions. The rate constants for these six reactions have been calculated from the latest evaluations of the reaction cross sections which were available. In some cases, notably the reactions t+t, t+ 3 He and 3 He+ 3 He, the number of published cross section measurements is small, and the uncertainty in the calculated rate constants consequently large. Analytical expressions for the rate constants as functions of the plasma temperature have been set up. (author)

Improved predictions of nuclear reaction rates with the TALYS reaction code for astrophysical applications

International Nuclear Information System (INIS)

Goriely, S.; Hilaire, S.; Koning, A.J

2008-01-01

Context. Nuclear reaction rates of astrophysical applications are traditionally determined on the basis of Hauser-Feshbach reaction codes. These codes adopt a number of approximations that have never been tested, such as a simplified width fluctuation correction, the neglect of delayed or multiple-particle emission during the electromagnetic decay cascade, or the absence of the pre-equilibrium contribution at increasing incident energies. Aims. The reaction code TALYS has been recently updated to estimate the Maxwellian-averaged reaction rates that are of astrophysical relevance. These new developments enable the reaction rates to be calculated with increased accuracy and reliability and the approximations of previous codes to be investigated. Methods. The TALYS predictions for the thermonuclear rates of relevance to astrophysics are detailed and compared with those derived by widely-used codes for the same nuclear ingredients. Results. It is shown that TALYS predictions may differ significantly from those of previous codes, in particular for nuclei for which no or little nuclear data is available. The pre-equilibrium process is shown to influence the astrophysics rates of exotic neutron-rich nuclei significantly. For the first time, the Maxwellian- averaged (n, 2n) reaction rate is calculated for all nuclei and its competition with the radiative capture rate is discussed. Conclusions. The TALYS code provides a new tool to estimate all nuclear reaction rates of relevance to astrophysics with improved accuracy and reliability. (authors)

Estimation of the rate of volcanism on Venus from reaction rate measurements

Science.gov (United States)

Fegley, Bruce, Jr.; Prinn, Ronald G.

1989-01-01

Laboratory rate data for the reaction between SO2 and calcite to form anhydrite are presented. If this reaction rate represents the SO2 reaction rate on Venus, then all SO2 in the Venusian atmosphere will disappear in 1.9 Myr unless volcanism replenishes the lost SO2. The required volcanism rate, which depends on the sulfur content of the erupted material, is in the range 0.4-11 cu km of magma erupted per year. The Venus surface composition at the Venera 13, 14, and Vega 2 landing sites implies a volcanism rate of about 1 cu km/yr. This geochemically estimated rate can be used to determine if either (or neither) of two discordant geophysically estimated rates is correct. It also suggests that Venus may be less volcanically active than the earth.

Charged-particle thermonuclear reaction rates: IV. Comparison to previous work

International Nuclear Information System (INIS)

Iliadis, C.; Longland, R.; Champagne, A.E.; Coc, A.

2010-01-01

We compare our Monte Carlo reaction rates (see Paper II of this issue) to previous results that were obtained by using the classical method of computing thermonuclear reaction rates. For each reaction, the comparison is presented using two types of graphs: the first shows the change in reaction rate uncertainties, while the second displays our new results normalized to the previously recommended reaction rate. We find that the rates have changed significantly for almost all reactions considered here. The changes are caused by (i) our new Monte Carlo method of computing reaction rates (see Paper I of this issue), and (ii) newly available nuclear physics information (see Paper III of this issue).

Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

Science.gov (United States)

Liechty, Derek S.; Lewis, Mark J.

2010-01-01

Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

In-situ synchrotron PXRD study of spinel LiMn2O4 formation

DEFF Research Database (Denmark)

Birgisson, Steinar; Jensen, Kirsten Marie Ørnsbjerg; Christiansen, Troels Lindahl

structural properties for the reaction being studied. Normally the reactions are started by heating and a constant temperature is kept throughout the experiment. In this study the hydrothermal reaction previously shown to produce spinel LiMn2O4 nanoparticles is studied in-situ to learn more about the phase......O4, depending on the initial concentration if Li-ions. An impurity phase, identified as Mn3O4, is also detected in different concentrations depending on reaction time and temperature. We have developed an experimental technique for in-situ measurements of solvothermal reactions under sub...... in the in-situ measurements it gives a unique opportunity to study reaction kinetics and thermodynamic quantities of the reactions. A temperature study of the reaction has been conducted to see how the formation rate and particle growth is affected by temperature while the precursor concentration is kept...

The Role of Compliance and Reaction Rate in Dehydration Weakening and Frictional Stability of Antigorite

Science.gov (United States)

Burdette, E.; Okazaki, K.; Hirth, G.

2017-12-01

The complicated brittle-ductile rheology of antigorite at subduction zone pressures and temperatures, resulting from its anisotropic mechanical properties, low dehydration temperature, and high water content has made interpretation of dehydration weakening problematic. Recent analyses indicate that antigorite is both ductile and brittle at high temperatures, and follows effective pressure frictional laws while dehydrating. In this study we focus on the role of rig compliance and reaction kinetics on frictional weakening and frictional stability. In addition, we correlate the evolution of mechanical behavior with AE activity at conditions within and above the thermal stability limit of antigorite. We conducted experiments at confining pressures from 0.25 GPa to 1GPa in a Griggs apparatus and modified rig compliance by including compliant components within the loading frame. We also modeled in-situ reaction progress using parameters from Sawai et al. (2013) to quantify relationships between weakening and fluid production. Without modifying the compliance, low pressure runs show stable dehydration weakening. With a modified, low compliance, results were nearly identical to stable weakening at standard compliance at 1 GPa. However, at lower pressures, many acoustic emissions were recorded at peak reaction rates during temperature ramping, with a rapid failure event occurring several minutes afterward (with the caveat that we still need to verify that AEs occur within the sample). No AEs are observed during room temperature experiments in samples that fault, nor were any observed in the high temperature experiments at conditions within the antigorite stability field - consistent with prior studies. Our results demonstrate that understanding in-situ dehydration reaction kinetics and their feedback with rheology and system compliance are key to scaling laboratory antigorite rheology to earth.

APUAMA: a software tool for reaction rate calculations.

Science.gov (United States)

Euclides, Henrique O; P Barreto, Patricia R

2017-06-01

APUAMA is a free software designed to determine the reaction rate and thermodynamic properties of chemical species of a reagent system. With data from electronic structure calculations, the APUAMA determine the rate constant with tunneling correction, such as Wigner, Eckart and small curvature, and also, include the rovibrational level of diatomic molecules. The results are presented in the form of Arrhenius-Kooij form, for the reaction rate, and the thermodynamic properties are written down in the polynomial form. The word APUAMA means "fast" in Tupi-Guarani Brazilian language, then the code calculates the reaction rate on a simple and intuitive graphic interface, the form fast and practical. As program output, there are several ASCII files with tabulated information for rate constant, rovibrational levels, energy barriers and enthalpy of reaction, Arrhenius-Kooij coefficient, and also, the option to the User save all graphics in BMP format.

Improved predictions of nuclear reaction rates for astrophysics applications with the TALYS reaction code

International Nuclear Information System (INIS)

Goriely, S.; Hilaire, S.; Koning, A.J.

2008-01-01

Nuclear reaction rates for astrophysics applications are traditionally determined on the basis of Hauser-Feshbach reaction codes, like MOST. These codes use simplified schemes to calculate the capture reaction cross section on a given target nucleus, not only in its ground state but also on the different thermally populated states of the stellar plasma at a given temperature. Such schemes include a number of approximations that have never been tested, such as an approximate width fluctuation correction, the neglect of delayed particle emission during the electromagnetic decay cascade or the absence of the pre-equilibrium contribution at increasing incident energies. New developments have been brought to the reaction code TALYS to estimate the Maxwellian-averaged reaction rates of astrophysics relevance. These new developments give us the possibility to calculate with an improved accuracy the reaction cross sections and the corresponding astrophysics rates. The TALYS predictions for the thermonuclear rates of astrophysics relevance are presented and compared with those obtained with the MOST code on the basis of the same nuclear ingredients for nuclear structure properties, optical model potential, nuclear level densities and γ-ray strength. It is shown that, in particular, the pre-equilibrium process significantly influences the astrophysics rates of exotic neutron-rich nuclei. The reciprocity theorem traditionally used in astrophysics to determine photo-rates is also shown no to be valid for exotic nuclei. The predictions obtained with different nuclear inputs are also analyzed to provide an estimate of the theoretical uncertainties still affecting the reaction rate prediction far away from the experimentally known regions. (authors)

Charged particle induced thermonuclear reaction rates: a compilation for astrophysics

International Nuclear Information System (INIS)

Grama, C.

1999-01-01

We report on the results of the European network NACRE (Nuclear Astrophysics Compilation of REaction rates). The principal reason for setting up the NACRE network has been the necessity of building up a well-documented and detailed compilation of rates for charged-particle induced reactions on stable targets up to Si and on unstable nuclei of special significance in astrophysics. This work is meant to supersede the only existing compilation of reaction rates issued by Fowler and collaborators. The main goal of NACRE network was the transparency in the procedure of calculating the rates. More specifically this compilation aims at: 1. updating the experimental and theoretical data; 2. distinctly identifying the sources of the data used in rate calculation; 3. evaluating the uncertainties and errors; 4. providing numerically integrated reaction rates; 5. providing reverse reaction rates and analytical approximations of the adopted rates. The cross section data and/or resonance parameters for a total of 86 charged-particle induced reactions are given and the corresponding reaction rates are calculated and given in tabular form. Uncertainties are analyzed and realistic upper and lower bounds of the rates are determined. The compilation is concerned with the reaction rates that are large enough for the target lifetimes shorter than the age of the Universe, taken equal to 15 x 10 9 y. The reaction rates are provided for temperatures lower than T = 10 10 K. In parallel with the rate compilation a cross section data base has been created and located at the site http://pntpm.ulb.ac.be/nacre..htm. (authors)

The path to improved reaction rates for astrophysics

International Nuclear Information System (INIS)

Rauscher, T.

2011-01-01

This review focuses on nuclear reactions in astrophysics and, more specifically, on reactions with light ions (nucleons and α particles) proceeding via the strong interaction. It is intended to present the basic definitions essential for studies in nuclear astrophysics, to point out the differences between nuclear reactions taking place in stars and in a terrestrial laboratory, and to illustrate some of the challenges to be faced in theoretical and experimental studies of those reactions. The discussion revolves around the relevant quantities for astrophysics, which are the astrophysical reaction rates. The sensitivity of the reaction rates to the uncertainties in the prediction of various nuclear properties is explored and some guidelines for experimentalists are also provided. (author)

Design, development, and demonstration of a fully LabVIEW controlled in situ electrochemical Fourier transform infrared setup combined with a wall-jet electrode to investigate the electrochemical interface of nanoparticulate electrocatalysts under reaction conditions.

Science.gov (United States)

Nesselberger, Markus; Ashton, Sean J; Wiberg, Gustav K H; Arenz, Matthias

2013-07-01

We present a detailed description of the construction of an in situ electrochemical ATR-FTIR setup combined with a wall-jet electrode to investigate the electrocatalytic properties of nanoparticulate catalysts in situ under controlled mass transport conditions. The presented setup allows the electrochemical interface to be probed in combination with the simultaneous determination of reaction rates. At the same time, the high level of automation allows it to be used as a standard tool in electrocatalysis research. The performance of the setup was demonstrated by probing the oxygen reduction reaction on a platinum black catalyst in sulfuric electrolyte.

Analysis of hepcidin expression: in situ hybridization and quantitative polymerase chain reaction from paraffin sections.

Science.gov (United States)

Sakuraoka, Yuhki; Sawada, Tokihiko; Shiraki, Takayuki; Park, Kyunghwa; Sakurai, Yuhichiro; Tomosugi, Naohisa; Kubota, Keiichi

2012-07-28

To establish methods for quantitative polymerase chain reaction (PCR) for hepcidin using RNAs isolated from paraffin-embedded sections and in situ hybridization of hepatocellular carcinoma (HCC). Total RNA from paraffin-embedded sections was isolated from 68 paraffin-embedded samples of HCC. Samples came from 54 male and 14 female patients with a mean age of 66.8 ± 7.8 years. Quantitative PCR was performed. Immunohistochemistry and in situ hybridization for hepcidin were also performed. Quantitative PCR for hepcidin using RNAs isolated from paraffin-embedded sections of HCC was performed successfully. The expression level of hepcidin mRNA in cancer tissues was significantly higher than that in non-cancer tissues. A method of in situ hybridization for hepcidin was established successfully, and this demonstrated that hepcidin mRNA was expressed in non-cancerous tissue but absent in cancerous tissue. We have established novel methods for quantitative PCR for hepcidin using RNAs isolated from paraffin-embedded sections and in situ hybridization of HCC.

Raman Spectral Determination of Chemical Reaction Rate Characteristics

Science.gov (United States)

Balakhnina, I. A.; Brandt, N. N.; Mankova, A. A.; Chikishev, A. Yu.; Shpachenko, I. G.

2017-09-01

The feasibility of using Raman spectroscopy to determine chemical reaction rates and activation energies has been demonstrated for the saponification of ethyl acetate. The temperature dependence of the reaction rate was found in the range from 15 to 45°C.

Investigation of CaO-CO₂ reaction kinetics by in-situ XRD using synchrotron radiation

Energy Technology Data Exchange (ETDEWEB)

Biasin, A.; Segre, C. U.; Salviulo, G.; Zorzi, F.; Strumendo, M. [Padova; (IIT)

2015-02-05

In this work, in-situ synchrotron radiation x-ray powder diffraction (SR-XRPD), performed at the Advanced Photon Source (APS) facilities of the Argonne National Laboratory, was applied to investigate the CaO–CO₂ reaction. A set of CO₂ absorption experiments were conducted in a high temperature reaction capillary with a controlled atmosphere (CO₂ partial pressure of 1 bar), in the temperature range between 450 °C and 750 °C using CaO based sorbents obtained by calcination of commercial calcium carbonate. The evolution of the crystalline phases during CO₂ uptake by the CaO solid sorbents was monitored for a carbonation time of 20 min as a function of the carbonation temperature and of the calcination conditions. The Rietveld refinement method was applied to estimate the calcium oxide conversion during the reaction progress and the average size of the initial (at the beginning of carbonation) calcium oxide crystallites. The measured average initial carbonation rate (in terms of conversion time derivative) of 0.280 s^-1 (±13.2% standard deviation) is significantly higher than the values obtained by thermo-gravimetric analysis and reported thus far in the literature. Additionally, a dependence of the conversion versus time curves on the initial calcium oxide crystallite size was observed and a linear relationship between the initial CaO crystallite size and the calcium oxide final conversion was identified.

Chemical changes in groundwater and their reaction rates

International Nuclear Information System (INIS)

Talma, A.S.

1981-01-01

The evolution of the major ion concentrations of groundwater (Na, K, Ca, Mg, HCO 3 , SO 4 , Cl and NO 3 ) can be described as the consequence of a number of competing chemical reactions. With the aid of the naturally occuring radioactive and stable isotopes some of these reactions can be separated, identified and followed in space and time. In some field studies, especialy of artesian water, the rates of reactions can be estimated. A number of processes observed in South African sandstones aquifers are discussed and the variable reaction rates demonstrated. Reactions that can be identified include carbonate solution, chemical weathering, salt leaching, cation exchange and redox processes

Design of a facility for the in situ measurement of catalytic reaction by neutron scattering spectroscopy

Science.gov (United States)

Tan, Shuai; Cheng, Yongqiang; Daemen, Luke L.; Lutterman, Daniel A.

2018-01-01

Catalysis is a critical enabling science for future energy needs. The next frontier of catalysis is to evolve from catalyst discovery to catalyst design, and for this next step to be realized, we must develop new techniques to better understand reaction mechanisms. To do this, we must connect catalytic reaction rates and selectivities to the kinetics, energetics, and dynamics of individual elementary steps and relate these to the structure and dynamics of the catalytic sites involved. Neutron scattering spectroscopies offer unique capabilities that are difficult or impossible to match by other techniques. The current study presents the development of a compact and portable instrumental design that enables the in situ investigation of catalytic samples by neutron scattering techniques. The developed apparatus was tested at the Spallation Neutron Source (SNS) in Oak Ridge National Laboratory and includes a gas handling panel that allows for computer hookups to control the panel externally and online measurement equipment such as coupled GC-FID/TCD (Gas Chromatography-Flame Ionization Detector/Thermal Conductivity Detector) and MS (Mass Spectrometry) to characterize offgassing while the sample is in the neutron scattering spectrometer. This system is flexible, modular, compact, and portable enabling its use for many types of gas-solid and liquid-solid reactions at the various beamlines housed at the SNS.

Reaction Order Ambiguity in Integrated Rate Plots

Science.gov (United States)

Lee, Joe

2008-01-01

Integrated rate plots are frequently used in reaction kinetics to determine orders of reactions. It is often emphasised, when using this methodology in practice, that it is necessary to monitor the reaction to a substantial fraction of completion for these plots to yield unambiguous orders. The present article gives a theoretical and statistical…

Numerical Simulation of In Situ Combustion of Oil Shale

Directory of Open Access Journals (Sweden)

Huan Zheng

2017-01-01

Full Text Available This paper analyzes the process of in situ combustion of oil shale, taking into account the transport and chemical reaction of various components in porous reservoirs. The physical model is presented, including the mass and energy conservation equations and Darcy’s law. The oxidation reactions of oil shale combustion are expressed by adding source terms in the conservation equations. The reaction rate of oxidation satisfies the Arrhenius law. A numerical method is established for calculating in situ combustion, which is simulated numerically, and the results are compared with the available experiment. The profiles of temperature and volume fraction of a few components are presented. The temperature contours show the temperature variation in the combustion tube. It is found that as combustion reaction occurs in the tube, the concentration of oxygen decreases rapidly, while the concentration of carbon dioxide and carbon monoxide increases contrarily. Besides, the combustion front velocity is consistent with the experimental value. Effects of gas injection rate, permeability of the reservoir, initial oil content, and injected oxygen content on the ISC process were investigated in this study. Varying gas injection rate and oxygen content is important in the field test of ISC.

Effective dynamics along given reaction coordinates, and reaction rate theory.

Science.gov (United States)

Zhang, Wei; Hartmann, Carsten; Schütte, Christof

2016-12-22

In molecular dynamics and related fields one considers dynamical descriptions of complex systems in full (atomic) detail. In order to reduce the overwhelming complexity of realistic systems (high dimension, large timescale spread, limited computational resources) the projection of the full dynamics onto some reaction coordinates is examined in order to extract statistical information like free energies or reaction rates. In this context, the effective dynamics that is induced by the full dynamics on the reaction coordinate space has attracted considerable attention in the literature. In this article, we contribute to this discussion: we first show that if we start with an ergodic diffusion process whose invariant measure is unique then these properties are inherited by the effective dynamics. Then, we give equations for the effective dynamics, discuss whether the dominant timescales and reaction rates inferred from the effective dynamics are accurate approximations of such quantities for the full dynamics, and compare our findings to results from approaches like Mori-Zwanzig, averaging, or homogenization. Finally, by discussing the algorithmic realization of the effective dynamics, we demonstrate that recent algorithmic techniques like the "equation-free" approach and the "heterogeneous multiscale method" can be seen as special cases of our approach.

Back Reaction And Local Cosmological Expansion Rate

CERN Document Server

Geshnizjani, G; Geshnizjani, Ghazal; Brandenberger, Robert

2002-01-01

We calculate the back reaction of cosmological perturbations on a general relativistic variable which measures the local expansion rate of the Universe. Specifically, we consider a cosmological model in which matter is described by a single field. We analyze back reaction both in a matter dominated Universe and in a phase of scalar field-driven chaotic inflation. In both cases, we find that the leading infrared terms contributing to the back reaction vanish when the local expansion rate is measured at a fixed value of the matter field which is used as a clock, whereas they do not appear to vanish if the expansion rate is evaluated at a fixed value of the background time. We discuss possible implications for more realistic models with a more complicated matter sector.

In situ characterization of the nitridation of dysprosium during mechanochemical processing

Energy Technology Data Exchange (ETDEWEB)

Jaques, Brian J.; Osterberg, Daniel D.; Alanko, Gordon A.; Tamrakar, Sumit; Smith, Cole R.; Hurley, Michael F.; Butt, Darryl P., E-mail: DarrylButt@BoiseState.edu

2015-01-15

Highlights: • A nitridation reaction in a high energy planetary ball mill was monitored in situ. • Dysprosium mononitride was synthesized from Dy at low temperatures in short times. • Ideal gas law and in situ temperature and pressure used to assess reaction extent. • It is proposed that reaction rate is proportional to the creation of new surface. - Abstract: Processing of advanced nitride ceramics traditionally requires long durations at high temperatures and, in some cases, in hazardous atmospheres. In this study, dysprosium mononitride (DyN) was rapidly formed from elemental dysprosium in a closed system at ambient temperatures. An experimental procedure was developed to quantify the progress of the nitridation reaction during mechanochemical processing in a high energy planetary ball mill (HEBM) as a function of milling time and intensity using in situ temperature and pressure measurements, SEM, XRD, and particle size analysis. No intermediate phases were formed. It was found that the creation of fresh dysprosium surfaces dictates the rate of the nitridation reaction, which is a function of milling intensity and the number of milling media. These results show clearly that high purity nitrides can be synthesized with short processing times at low temperatures in a closed system requiring a relatively small processing footprint.

Rates for some reactions involving 42Ca and 44Ca

International Nuclear Information System (INIS)

Cheng, C.W.; King, J.D.

1980-01-01

Ground-state reaction rates have been deduced from recent cross section measurements for the 42 CA(α, n) 45 Ti, 42 Ca(p, γ) 43 Sc, and 44 Ca(p, n) 44 Sc reactions. Comparison of these rates with those calculated from a statistical model of nuclear reactions. (Woosley et al) shows good agreement for the first two, but the 44 Ca(p, n) rate is more than a factor of 2 less than the theoretical prediction. Stellar reaction rates have been derived from the ground-state rates by multiplying the ground-state rates by the ratio of stellar to ground-state rates given by the statistical model. Both ground-state and stellar rates have been represented by analytic functions of the temperature. The role of these reactions in the approach to quasi-equilibrium during explosive silicon burning is discussed

In Situ Apparatus to Study Gas-Metal Reactions and Wettability at High Temperatures for Hot-Dip Galvanizing Applications

Science.gov (United States)

Koltsov, A.; Cornu, M.-J.; Scheid, J.

2018-02-01

The understanding of gas-metal reactions and related surface wettability at high temperatures is often limited due to the lack of in situ surface characterization. Ex situ transfers at low temperature between annealing furnace, wettability device, and analytical tools induce noticeable changes of surface composition distinct from the reality of the phenomena.Therefore, a high temperature wettability device was designed in order to allow in situ sample surface characterization by x-rays photoelectron spectroscopy after gas/metal and liquid metal/solid metal surface reactions. Such airless characterization rules out any contamination and oxidation of surfaces and reveals their real composition after heat treatment and chemical reaction. The device consists of two connected reactors, respectively, dedicated to annealing treatments and wettability measurements. Heat treatments are performed in an infrared lamp furnace in a well-controlled atmosphere conditions designed to reproduce gas-metal reactions occurring during the industrial recrystallization annealing of steels. Wetting experiments are carried out in dispensed drop configuration with the precise control of the deposited droplets kinetic energies. The spreading of drops is followed by a high-speed CCD video camera at 500-2000 frames/s in order to reach information at very low contact time. First trials have started to simulate phenomena occurring during recrystallization annealing and hot-dip galvanizing on polished pure Fe and FeAl8 wt.% samples. The results demonstrate real surface chemistry of steel samples after annealing when they are put in contact with liquid zinc alloy bath during hot-dip galvanizing. The wetting results are compared to literature data and coupled with the characterization of interfacial layers by FEG-Auger. It is fair to conclude that the results show the real interest of such in situ experimental setup for interfacial chemistry studies.

Temperature dependence of muonium reaction rates in the gas phase

International Nuclear Information System (INIS)

Fleming, D.G.; Garner, D.M.; Mikula, R.J.; British Columbia Univ., Vancouver

1981-01-01

A study of the temperature dependence of reaction rates has long been an important tool in establishing reaction pathways in chemical reactions. This is particularly true for the reactions of muonium (in comparison with those of hydrogen) since a measurement of the activation energy for chemical reaction is sensitive to both the height and the position of the potential barrier in the reaction plane. For collision controlled reactions, on the other hand, the reaction rate is expected to exhibit a weak T 1 sup(/) 2 dependence characteristic of the mean collision velocity. These concepts are discussed and their effects illustrated in a comparison of the chemical and spin exchange reaction rates of muonium and hydrogen in the temperature range approx.300-approx.500 K. (orig.)

Reaction rate of 24Mg(p,γ)25Al

International Nuclear Information System (INIS)

Powell, D.C.; Iliadis, C.; Champagne, A.E.; Grossmann, C.A.; Hale, S.E.; Hansper, V.Y.; McLean, L.K.

1999-01-01

The proton-capture reaction on 24 Mg has been investigated in the bombarding energy range of E p =0.2-1.7 MeV. Resonance properties (strengths, branching ratios and lifetimes) of low-energy resonances have been measured. From the experimental results, accurate proton partial widths, γ-ray partial widths and total widths (Γ p , Γ γ , and Γ) have been deduced. The present experimental information establishes the 24 Mg+p reaction rates over the temperature range T=0.02-2.0 GK with statistical uncertainties of 5% to 21%. Our recommended reaction rates deviate from previous estimates by 18% to 45%. Based on our results, we can rule out the recent suggestion that the total width of the E R =223 keV resonance has a significant influence on the reaction rates. We also discuss several effects that might give rise to systematic uncertainties in the reaction rates. The astrophysical implications for hydrogen burning of 24 Mg at low stellar temperatures are presented

General properties of astrophysical reaction rates in explosive nucleosynthesis

International Nuclear Information System (INIS)

Rauscher, Thomas

2013-01-01

Fundamental differences in the prediction of reaction rates with intermediate and heavy target nuclei compared to the ones with light nuclei are discussed, with special emphasis on stellar modifications of the rates. Ground and excited state contributions to the stellar rates are quantified, deriving a linear weighting of excited state contributions despite of a Boltzmann population of the nuclear states. A Coulomb suppression effect of the excited state contributions is identified, acting against the usual Q-value rule in some reactions. The proper inclusion of experimental data in revised stellar rates is shown, containing revised uncertainties. An application to the s-process shows that the actual uncertainties in the neutron capture rates are larger than would be expected from the experimental errors alone. Sensitivities of reaction rates and cross sections are defined and their application in reaction studies is discussed. The conclusion provides a guide to experiment as well as theory on how to best improve the rates used in astrophysical simulations and how to assess their uncertainties.

Quantitative in situ monitoring of an elevated temperature reaction using a water-cooled mid-infrared fiber-optic probe.

Science.gov (United States)

Maclaurin, P; Crabb, N C; Wells, I; Worsfold, P J; Coombs, D

1996-04-01

A novel water-cooled mid-infrared fiber-optic probe is described which is heatable to 230 °C. The probe has chalcogenide fibers and a ZnSe internal reflection element and is compact and fully flexible, allowing access to a wide range of standard laboratory reaction vessels and fume cupboard arrangements. Performance is demonstrated via the in situ analysis of an acid-catalyzed esterification reaction in toluene at 110 °C, and the results are compared with those from a conventional extractive sampling loop flow cell arrangement. Particular emphasis is given to the quantitative interpretation of the spectroscopic data, using gas chromatographic reference data. Calibration data are presented for univariate and partial least squares models, with an emphasis on procedures for improving the quality of interpreparation calibration and prediction through the use of focused reference analysis regimes. Subset univariate procedures are presented that yield relative errors of spectroscopy combined with bias correction partial least squares procedures for the efficient in situ quantitative analysis of laboratory scale reactions.

Supramolecular Assembly of Comb-like Macromolecules Induced by Chemical Reactions that Modulate the Macromolecular Interactions In Situ.

Science.gov (United States)

Xia, Hongwei; Fu, Hailin; Zhang, Yanfeng; Shih, Kuo-Chih; Ren, Yuan; Anuganti, Murali; Nieh, Mu-Ping; Cheng, Jianjun; Lin, Yao

2017-08-16

Supramolecular polymerization or assembly of proteins or large macromolecular units by a homogeneous nucleation mechanism can be quite slow and require specific solution conditions. In nature, protein assembly is often regulated by molecules that modulate the electrostatic interactions of the protein subunits for various association strengths. The key to this regulation is the coupling of the assembly process with a reversible or irreversible chemical reaction that occurs within the constituent subunits. However, realizing this complex process by the rational design of synthetic molecules or macromolecules remains a challenge. Herein, we use a synthetic polypeptide-grafted comb macromolecule to demonstrate how the in situ modulation of interactions between the charged macromolecules affects their resulting supramolecular structures. The kinetics of structural formation was studied and can be described by a generalized model of nucleated polymerization containing secondary pathways. Basic thermodynamic analysis indicated the delicate role of the electrostatic interactions between the charged subunits in the reaction-induced assembly process. This approach may be applicable for assembling a variety of ionic soft matters that are amenable to chemical reactions in situ.

Quantifying Chemical and Electrochemical Reactions in Liquids by in situ Electron Microscopy

DEFF Research Database (Denmark)

Canepa, Silvia

and developing a robust imaging analysis method for quantitatively understand chemical and electrochemical process during in situ liquid electron microscopy. By using two custom-made liquid cells (an electrochemical scanning electron microscopy (EC-SEM) platform and Liquid Flow S/TEM holder) beam...... of electrochemical deposition of copper (Cu) by electrochemical liquid scanning electron microscopy (EC-SEM) was done in order to direct observe the formation of dendritic structures. Finally the shape evolution from solid to hollow structures through galvanic replacement reactions were observed for different silver...

Accurate and approximate thermal rate constants for polyatomic chemical reactions

International Nuclear Information System (INIS)

Nyman, Gunnar

2007-01-01

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

Synthesis of Citric-Acrylate Oligomer and its in-Situ Reaction with Chrome Tanned Collagen (hide powder)

International Nuclear Information System (INIS)

Haroun, A.A.; Masoud, R.A.; Bronco, S.; Ciardelli, F.

2005-01-01

The purpose of this study was to formulate the new combined system of acrylic and citric acids, which has been prepared by free radical polymerization and esterification reaction at the same time to form citric acrylate (CAC) oligomer through ester linkage and low molecular weight (Mw 2241), in compared with polyacrylic acid. The chemical structure and the reaction mechanism of this oligomer were confirmed by different spectroscopic tools (1 H , 13 C-NMR, ATR-IR), gel permeation chromatography and thermogravimetric analysis (TGA/DTA). The problem of the effect of the masking agents in the chrome tanning of the collagen and the pickling of the hide has been approached from the study of the hydrothermal and mechanical properties, using this new eco-friendly oligomer, which was carried out in-situ treated/grafted chrome tanned collagen (hide powder), and pickled hide. The microemulsion grafting copolymerization of (CAC) using 2.2-azo-bis isobutyronitrile (ABIN), via direct coupling reaction, onto the chrome tanned collagen showed that the free amino groups of the collagen were considered to be a potential site for the in-situ reaction with (CAC) oligomer. Also, using of citric-acrylate (CAC) oligomer, during chrome tanning of leather, instead of the traditional strong acids (sulfuric, hydrochloric and formic) resulted in significant improvement in chrome exhaustion and physical properties

Rates of the main thermonuclear reactions

International Nuclear Information System (INIS)

Abramovich, S.N.; Guzhovskii, B.Ya.; Dunaeva, S.A.; Fomushkin, E.F.

1992-01-01

The data on the cross sections of main thermonuclear reactions have been estimated with an account of the latest experimental results in a form of S-factor spline presentation. Based on this estimation, the reates of these reactions in 0.0001-1 MeV temperature range in the supposition of Maxwell distribution of relative velocities have been computed. The Maxwell-Boltzmann averaged -factors were calculated according to the table values of the reaction rates. Then the -factors were approximated with the 3 order spline-function. The necessity of the account of electron shielding and intramolecular movement at low temperatures is discussed (orig.)

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.

Nanoparticle-triggered in situ catalytic chemical reactions for tumour-specific therapy.

Science.gov (United States)

Lin, Han; Chen, Yu; Shi, Jianlin

2018-03-21

Tumour chemotherapy employs highly cytotoxic chemodrugs, which kill both cancer and normal cells by cellular apoptosis or necrosis non-selectively. Catalysing/triggering the specific chemical reactions only inside tumour tissues can generate abundant and special chemicals and products locally to initiate a series of unique biological and pathologic effects, which may enable tumour-specific theranostic effects to combat cancer without bringing about significant side effects on normal tissues. Nevertheless, chemical reaction-initiated selective tumour therapy strongly depends on the advances in chemistry, materials science, nanotechnology and biomedicine. This emerging cross-disciplinary research area is substantially different from conventional cancer-theranostic modalities in clinics. In response to the fast developments in cancer theranostics based on intratumoural catalytic chemical reactions, this tutorial review summarizes the very-recent research progress in the design and synthesis of representative nanoplatforms with intriguing nanostructures, compositions, physiochemical properties and biological behaviours for versatile catalytic chemical reaction-enabled cancer treatments, mainly by either endogenous tumour microenvironment (TME) triggering or exogenous physical irradiation. These unique intratumoural chemical reactions can be used in tumour-starving therapy, chemodynamic therapy, gas therapy, alleviation of tumour hypoxia, TME-responsive diagnostic imaging and stimuli-responsive drug release, and even externally triggered versatile therapeutics. In particular, the challenges and future developments of such a novel type of cancer-theranostic modality are discussed in detail to understand the future developments and prospects in this research area as far as possible. It is highly expected that this kind of unique tumour-specific therapeutics by triggering specific in situ catalytic chemical reactions inside tumours would provide a novel but efficient

A review of reaction rates in high temperature air

Science.gov (United States)

Park, Chul

1989-01-01

The existing experimental data on the rate coefficients for the chemical reactions in nonequilibrium high temperature air are reviewed and collated, and a selected set of such values is recommended for use in hypersonic flow calculations. For the reactions of neutral species, the recommended values are chosen from the experimental data that existed mostly prior to 1970, and are slightly different from those used previously. For the reactions involving ions, the recommended rate coefficients are newly chosen from the experimental data obtained more recently. The reacting environment is assumed to lack thermal equilibrium, and the rate coefficients are expressed as a function of the controlling temperature, incorporating the recent multitemperature reaction concept.

High-precision (p,t) reactions to determine reaction rates of explosive stellar processes

NARCIS (Netherlands)

Matić, Andrija

2007-01-01

The aim of my study was to investigate the nuclear structure of 22Mg and 26Si. These two nuclei play a significant role in stellar reaction processes at high temperatures. On base of the obtained nuclear structure we calculated the stellar reaction rates for the following reactions: 18Ne(α,p)21Na,

Reaction-rate formula in out of equilibrium quantum field theory

OpenAIRE

Niegawa, A.; Okano, K.; Ozaki, H.

1999-01-01

A complete derivation, from first principles, of the reaction-rate formula for a generic reaction taking place in an out of equilibrium quantum-field system is given. It is shown that the formula involves no finite-volume correction. Each term of the reaction-rate formula represents a set of physical processes that contribute to the reaction under consideration.

New approaches investigating production rates of in-situ produced terrestrial cosmogenic nuclides

Energy Technology Data Exchange (ETDEWEB)

Merchel, Silke [CEREGE, CNRS-IRD-Universite Aix-Marseille, Aix-en-Provence (France); FZD, Dresden (Germany); Braucher, Regis; Benedetti, Lucilla; Bourles, Didier [CEREGE, CNRS-IRD-Universite Aix-Marseille, Aix-en-Provence (France)

2010-07-01

In-situ produced cosmogenic nuclides have proved to be valuable tools for environmental and Earth sciences. However, accurate application of this method is only possible, if terrestrial production rates in a certain environment over a certain time period and their depth-dependence within the exposed material are exactly known. Unfortunately, the existing data and models differ up to several tens of percent. Thus, one of the European project CRONUS-EU goals is the high quality calibration of the {sup 36}Cl production rate by spallation at independently dated surfaces. As part of fulfilling this task we have investigated calcite-rich samples from four medieval landslide areas in the Alps: Mont Granier, Le Claps, Dobratsch, and Veliki Vrh (330-1620 m, 1248-1442 AD). For investigating the depth-dependence of the different nuclear reactions, especially, the muon- and thermal neutron-induced contributions, we have analysed mixtures of carbonates and siliceous conglomerate samples - for {sup 10}Be, {sup 26}Al, and {sup 36}Cl - exposed at different shielding depths and taken from a core drilled in 2005 at La Ciotat, France (from surface to 11 m shielding). AMS of {sup 36}Cl was performed at LLNL and ETH, {sup 10}Be and {sup 26}Al at ASTER.

Cross sections and thermonuclear reaction rates of proton-induced reactions on 37Cl

International Nuclear Information System (INIS)

Weber, R.O.; Tingwell, C.I.W.; Mitchell, L.W.; Sevior, M.E.; Sargood, D.G.

1984-01-01

The yields of γ-rays from the reactions of 37 Cl(p,γ) 38 Ar and 37 Cl(p,αγ) 34 S have been measured as a of bombarding energy over the ranges 0.65 - 2.15 MeV and 1.25 -2.15 MeV respectively, and the yield of neutrons from 37 Cl(p,n) 37 Ar from threshold to 2.50 MeV. The results are compared with global statistical-model calculations and thermonuclear reaction rates are calculated for the temperature range 5 x 10 8 - 10 10 K. The significance of these thermonuclear reaction rates for stellar nucleosynthesis calculations is discussed

Charged-particle induced thermonuclear reaction rates: a compilation for astrophysics

International Nuclear Information System (INIS)

Grama, Cornelia; Angulo, C.; Arnould, M.

2000-01-01

The rapidly growing wealth of nuclear data becomes less and less easily accessible to the astrophysics community. Mastering this volume of information and making it available in an accurate and usable form for incorporation into stellar evolution or nucleosynthesis models become urgent goals of prime necessity. we report on the results of the European network NACRE (Nuclear Astrophysics Compilation of REaction rates). The principal motivation for the setting-up of the NACRE network has been the necessity of building up a well-documented and detailed compilation of rates for charged-particle induced reactions on stable targets up to Si and on unstable nuclei of special significance in astrophysics. This work is meant to supersede the only existing compilation of reaction rates issued by Fowler and collaborators. The cross section data and/or resonance parameters for a total of 86 charged-particle induced reactions are given and the corresponding reaction rates are calculated and given in tabular form. When cross section data are not available in the whole needed range of energies, the theoretical predictions obtained in the framework of the Hauser-Feshbach model is used. Uncertainties are analyzed and realistic upper and lower bounds of the rates are determined. Reverse reaction rates and analytical approximations of the adopted rates are also provided. (authors)

Charged-particle induced thermonuclear reaction rates: a compilation for astrophysics

International Nuclear Information System (INIS)

Grama, Cornelia

1999-01-01

The rapidly growing wealth of nuclear data becomes less and less easily accessible to the astrophysics community. Mastering this volume of information and making it available in an accurate and usable form for incorporation into stellar evolution or nucleosynthesis models become urgent goals of prime necessity. We report on the results of the European network NACRE (Nuclear Astrophysics Compilation of REaction rates). The principal motivation for the setting-up of the NACRE network has been the necessity of building up a well-documented and detailed compilation of rates for charged -particle induced reactions on stable targets up to Si and on unstable nuclei of special significance in astrophysics. This work is meant to supersede the only existing compilation of reaction rates issued by Fowler and collaborators. The cross section data and/or resonance parameters for a total of 86 charged-particle induced reactions are given and the corresponding reaction rates are calculated and given in tabular form. When cross section data are not available in the whole needed range of energies the theoretical predictions obtained in the framework of the Hauser-Feshbach model are used. Uncertainties are analyzed and realistic upper and lower bounds of the rates are determined. Reverse reaction rates and analytical approximations of the adopted rates are also provided. (author)

BAYESIAN ESTIMATION OF THERMONUCLEAR REACTION RATES

Energy Technology Data Exchange (ETDEWEB)

Iliadis, C.; Anderson, K. S. [Department of Physics and Astronomy, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3255 (United States); Coc, A. [Centre de Sciences Nucléaires et de Sciences de la Matière (CSNSM), CNRS/IN2P3, Univ. Paris-Sud, Université Paris–Saclay, Bâtiment 104, F-91405 Orsay Campus (France); Timmes, F. X.; Starrfield, S., E-mail: iliadis@unc.edu [School of Earth and Space Exploration, Arizona State University, Tempe, AZ 85287-1504 (United States)

2016-11-01

The problem of estimating non-resonant astrophysical S -factors and thermonuclear reaction rates, based on measured nuclear cross sections, is of major interest for nuclear energy generation, neutrino physics, and element synthesis. Many different methods have been applied to this problem in the past, almost all of them based on traditional statistics. Bayesian methods, on the other hand, are now in widespread use in the physical sciences. In astronomy, for example, Bayesian statistics is applied to the observation of extrasolar planets, gravitational waves, and Type Ia supernovae. However, nuclear physics, in particular, has been slow to adopt Bayesian methods. We present astrophysical S -factors and reaction rates based on Bayesian statistics. We develop a framework that incorporates robust parameter estimation, systematic effects, and non-Gaussian uncertainties in a consistent manner. The method is applied to the reactions d(p, γ ){sup 3}He, {sup 3}He({sup 3}He,2p){sup 4}He, and {sup 3}He( α , γ ){sup 7}Be, important for deuterium burning, solar neutrinos, and Big Bang nucleosynthesis.

Taoshan uranium ore fields in situ blasting heap leaching rate influence factors to investigate

International Nuclear Information System (INIS)

Xie Wangnan; Dong Chunming

2014-01-01

Taoshan ore field ore in situ blasting heap leaching out build industrial test and production process, stope leaching rate and leaching cycle is large than that, after analysis, blasting method and cloth liquid way is to affect leaching rate and leaching cycle of the main factors. This paper holds that as far as possible using stratified deep hole blasting of squeezing up ways to reduce the building pile of in-situ leaching ore block rate; Adopting effective cloth tube way, increase the leaching agent and ore contact comprehensive; Introduction of bacterial leaching, and other means to improve leaching rate, shorten production cycle, etc to solve it. (authors)

Back reaction and the local cosmological expansion rate

CERN Document Server

Geshnizjani, G

2002-01-01

We calculate the back reaction of cosmological perturbations on a general relativistic variable which measures the local expansion rate of the Universe. Specifically, we consider a cosmological model in which matter is described by a single field. We analyze back reaction both in a matter-dominated Universe and in a phase of scalar field-driven chaotic inflation. In both cases, we find that the leading infrared terms contributing to the back reaction vanish when the local expansion rate is measured at a fixed value of the matter field which is used as a clock, whereas they do not appear to vanish if the expansion rate is evaluated at a fixed value of the background time. We discuss possible implications for more realistic models with a more complicated matter sector.

Enhancement of D-T reaction rate due to D-T contact

International Nuclear Information System (INIS)

Hitoki, Shigehisa; Ogasawara, Masatada; Aono, Osamu.

1979-09-01

The reaction rate that is appropriate for magnetized nonuniform plasma is numerically calculated to investigate the enhancement of the D-T reaction rate. Spatial separation of the guiding center distributions of D and T enhances the reaction rate. Cases of several guiding center configurations are investigated. The largest enhancement is obtained, when both guiding center distributions are delta-functions which are separated by a length that corresponds to the Gamow peak energy. As compared with the case of no separation of D and T, the maximum enhancing factors obtained are 2.3 for total reaction rate and 1.6 for local reaction rate. Cases of the guiding center distributions with finite widths are also investigated. (author)

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.

Experimental study and numerical modelling of geochemical reactions occurring during uranium in situ recovery (ISR) mining

International Nuclear Information System (INIS)

Ben Simon, R.

2011-09-01

The in situ Recovery (ISR) method consists of ore mining by in situ chemical leaching with acid or alkaline solutions. ISR takes place underground and is therefore limited to the analysis of the pumped solutions, hence ISR mine management is still empirical. Numerical modelling has been considered to achieve more efficient management of this process. Three different phenomena have to be taken into account for numerical simulations of uranium ISR mining: (1) geochemical reactions; (2) the kinetics of these reactions, and (3) hydrodynamic transport with respect to the reaction kinetics. Leaching tests have been conducted on ore samples from an uranium mine in Tortkuduk (Kazakhstan) where ISR is conducted by acid leaching. Two types of leaching experiments were performed: (1) tests in batch reactors; and (2) extraction in flow through columns. The assumptions deduced from the leaching tests were tested and validated by modelling the laboratory experiments with the numerical codes CHESS and HYTEC, both developed at the Geosciences research center of Mines ParisTech. A well-constrained 1D hydrogeochemical transport model of the ISR process at laboratory-scale was proposed. It enables to translate the chemical release sequence that is observed during experiments into a geochemical reaction sequence. It was possible to highlight the controlling factors of uranium dissolution, and the precipitation of secondary mineral phase in the deposit, as well as the determination of the relative importance of these factors. (author)

Rate coefficients for hydrogen abstraction reaction of pinonaldehyde

Indian Academy of Sciences (India)

The H abstraction reaction from the –CHO group was found to be the most dominant reaction channelamong all the possible reaction pathways and its corresponding rate coefficient at 300 K is kEckart's unsymmetrical= 3.86 ×10-10 cm3 molecule-1 s-1. Whereas the channel with immediate lower activation energy is the ...

Al-Si/Al2O3 in situ composite prepared by displacement reaction of CuO/Al system

Directory of Open Access Journals (Sweden)

Zhang Jing

2010-02-01

Full Text Available Al2O3 particle-reinforced ZL109 composite was prepared by in situ reaction between CuO and Al. The microstructure was observed by means of OM, SEM and TEM. The Al2O3 particles in sub-micron sizes distribute uniformly in the matrix, and the Cu displaced from the in situ reaction forms net-like alloy phases with other alloy elements. The hardness and the tensile strength of the composites at room temperature have a slight increase as compared to that of the matrix. However, the tensile strength at 350 ℃ has reached 90.23 MPa, or 16.92 MPa higher than that of the matrix. The mechanism of the reaction in the CuO/Al system was studied by using of differential scanning calorimetry(DSC and thermodynamic calculation. The reaction between CuO and Al involves two steps. First, CuO reacts with Al to form Cu2O and Al2O3 at the melting temperature of the matrix alloy, and second, Cu2O reacts with Al to form Cu and Al2O3 at a higher temperature. At ZL109 casting temperature of 750–780 ℃, the second step can also take place because of the effect of exothermic reaction of the first step.

Charged-particle thermonuclear reaction rates: I. Monte Carlo method and statistical distributions

International Nuclear Information System (INIS)

Longland, R.; Iliadis, C.; Champagne, A.E.; Newton, J.R.; Ugalde, C.; Coc, A.; Fitzgerald, R.

2010-01-01

A method based on Monte Carlo techniques is presented for evaluating thermonuclear reaction rates. We begin by reviewing commonly applied procedures and point out that reaction rates that have been reported up to now in the literature have no rigorous statistical meaning. Subsequently, we associate each nuclear physics quantity entering in the calculation of reaction rates with a specific probability density function, including Gaussian, lognormal and chi-squared distributions. Based on these probability density functions the total reaction rate is randomly sampled many times until the required statistical precision is achieved. This procedure results in a median (Monte Carlo) rate which agrees under certain conditions with the commonly reported recommended 'classical' rate. In addition, we present at each temperature a low rate and a high rate, corresponding to the 0.16 and 0.84 quantiles of the cumulative reaction rate distribution. These quantities are in general different from the statistically meaningless 'minimum' (or 'lower limit') and 'maximum' (or 'upper limit') reaction rates which are commonly reported. Furthermore, we approximate the output reaction rate probability density function by a lognormal distribution and present, at each temperature, the lognormal parameters μ and σ. The values of these quantities will be crucial for future Monte Carlo nucleosynthesis studies. Our new reaction rates, appropriate for bare nuclei in the laboratory, are tabulated in the second paper of this issue (Paper II). The nuclear physics input used to derive our reaction rates is presented in the third paper of this issue (Paper III). In the fourth paper of this issue (Paper IV) we compare our new reaction rates to previous results.

Analysis of reaction schemes using maximum rates of constituent steps

Science.gov (United States)

Motagamwala, Ali Hussain; Dumesic, James A.

2016-01-01

We show that the steady-state kinetics of a chemical reaction can be analyzed analytically in terms of proposed reaction schemes composed of series of steps with stoichiometric numbers equal to unity by calculating the maximum rates of the constituent steps, rmax,i, assuming that all of the remaining steps are quasi-equilibrated. Analytical expressions can be derived in terms of rmax,i to calculate degrees of rate control for each step to determine the extent to which each step controls the rate of the overall stoichiometric reaction. The values of rmax,i can be used to predict the rate of the overall stoichiometric reaction, making it possible to estimate the observed reaction kinetics. This approach can be used for catalytic reactions to identify transition states and adsorbed species that are important in controlling catalyst performance, such that detailed calculations using electronic structure calculations (e.g., density functional theory) can be carried out for these species, whereas more approximate methods (e.g., scaling relations) are used for the remaining species. This approach to assess the feasibility of proposed reaction schemes is exact for reaction schemes where the stoichiometric coefficients of the constituent steps are equal to unity and the most abundant adsorbed species are in quasi-equilibrium with the gas phase and can be used in an approximate manner to probe the performance of more general reaction schemes, followed by more detailed analyses using full microkinetic models to determine the surface coverages by adsorbed species and the degrees of rate control of the elementary steps. PMID:27162366

Modular rate laws for enzymatic reactions: thermodynamics, elasticities and implementation.

Science.gov (United States)

Liebermeister, Wolfram; Uhlendorf, Jannis; Klipp, Edda

2010-06-15

Standard rate laws are a key requisite for systematically turning metabolic networks into kinetic models. They should provide simple, general and biochemically plausible formulae for reaction velocities and reaction elasticities. At the same time, they need to respect thermodynamic relations between the kinetic constants and the metabolic fluxes and concentrations. We present a family of reversible rate laws for reactions with arbitrary stoichiometries and various types of regulation, including mass-action, Michaelis-Menten and uni-uni reversible Hill kinetics as special cases. With a thermodynamically safe parameterization of these rate laws, parameter sets obtained by model fitting, sampling or optimization are guaranteed to lead to consistent chemical equilibrium states. A reformulation using saturation values yields simple formulae for rates and elasticities, which can be easily adjusted to the given stationary flux distributions. Furthermore, this formulation highlights the role of chemical potential differences as thermodynamic driving forces. We compare the modular rate laws to the thermodynamic-kinetic modelling formalism and discuss a simplified rate law in which the reaction rate directly depends on the reaction affinity. For automatic handling of modular rate laws, we propose a standard syntax and semantic annotations for the Systems Biology Markup Language. An online tool for inserting the rate laws into SBML models is freely available at www.semanticsbml.org. Supplementary data are available at Bioinformatics online.

In Situ Monitoring of Chemical Reactions at a Solid-Water Interface by Femtosecond Acoustics.

Science.gov (United States)

Shen, Chih-Chiang; Weng, Meng-Yu; Sheu, Jinn-Kong; Yao, Yi-Ting; Sun, Chi-Kuang

2017-11-02

Chemical reactions at a solid-liquid interface are of fundamental importance. Interfacial chemical reactions occur not only at the very interface but also in the subsurface area, while existing monitoring techniques either provide limited spatial resolution or are applicable only for the outmost atomic layer. Here, with the aid of the time-domain analysis with femtosecond acoustics, we demonstrate a subatomic-level-resolution technique to longitudinally monitor chemical reactions at solid-water interfaces, capable of in situ monitoring even the subsurface area under atmospheric conditions. Our work was proven by monitoring the already-known anode oxidation process occurring during photoelectrochemical water splitting. Furthermore, whenever the oxide layer thickness equals an integer  number of the effective atomic layer thickness, the measured acoustic echo will show higher signal-to-noise ratios with reduced speckle noise, indicating the quantum-like behavior of this coherent-phonon-based technique.

Astrophysical Nuclear Reaction Rates in the Dense Metallic Environments

Science.gov (United States)

Kilic, Ali Ihsan

2017-09-01

Nuclear reaction rates can be enhanced by many orders of magnitude in dense and relatively cold astrophysical plasmas such as in white dwarfs, brown dwarfs, and giant planets. Similar conditions are also present in supernova explosions where the ignition conditions are vital for cosmological models. White dwarfs are compact objects that have both extremely high interior densities and very strong local magnetic fields. For the first time, a new formula has been developed to explain cross section and reaction rate quantities for light elements that includes not only the nuclear component but also the material dependence, magnetic field, and crystal structure dependency in dense metallic environments. I will present the impact of the developed formula on the cross section and reaction rates for light elements. This could have possible technological applications in energy production using nuclear fusion reactions.

In situ57Fe Moessbauer Investigation of Solid-State Redox Reactions of Lithium Insertion Electrodes for Advanced Batteries

International Nuclear Information System (INIS)

Sakai, Yoichi; Ariyoshi, Kingo; Ohzuku, Tsutomu

2002-01-01

A novel in situ electrochemical cell for 57 Fe Moessbauer measurements was developed in order to clarify the mechanisms of solid-state redox reactions in lithium insertion materials containing iron. Our in situ Moessbauer technique was successfully applied to the determination as to which transition metal ion was a redox center in the insertion electrodes, such as LiFe 0.5 Mn 1.5 O 4 , LiFeTiO 4 , or LiFe 0.25 Ni 0.75 O 2 , for the lithium-ion batteries.

In Situ Environmental TEM in Imaging Gas and Liquid Phase Chemical Reactions for Materials Research.

Science.gov (United States)

Wu, Jianbo; Shan, Hao; Chen, Wenlong; Gu, Xin; Tao, Peng; Song, Chengyi; Shang, Wen; Deng, Tao

2016-11-01

Gas and liquid phase chemical reactions cover a broad range of research areas in materials science and engineering, including the synthesis of nanomaterials and application of nanomaterials, for example, in the areas of sensing, energy storage and conversion, catalysis, and bio-related applications. Environmental transmission electron microscopy (ETEM) provides a unique opportunity for monitoring gas and liquid phase reactions because it enables the observation of those reactions at the ultra-high spatial resolution, which is not achievable through other techniques. Here, the fundamental science and technology developments of gas and liquid phase TEM that facilitate the mechanistic study of the gas and liquid phase chemical reactions are discussed. Combined with other characterization tools integrated in TEM, unprecedented material behaviors and reaction mechanisms are observed through the use of the in situ gas and liquid phase TEM. These observations and also the recent applications in this emerging area are described. The current challenges in the imaging process are also discussed, including the imaging speed, imaging resolution, and data management. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diffusion-controlled reaction. V. Effect of concentration-dependent diffusion coefficient on reaction rate in graft polymerization

International Nuclear Information System (INIS)

Imre, K.; Odian, G.

1979-01-01

The effect of diffusion on radiation-initiated graft polymerization has been studied with emphasis on the single- and two-penetrant cases. When the physical properties of the penetrants are similar, the two-penetrant problems can be reduced to the single-penetrant problem by redefining the characteristic parameters of the system. The diffusion-free graft polymerization rate is assumed to be proportional to the upsilon power of the monomer concentration respectively, and, in which the proportionality constant a = k/sub p/R/sub i//sup w//k/sub t//sup z/, where k/sub p/ and k/sub t/ are the propagation and termination rate constants, respectively, and R/sub i/ is the initiation rate. The values of upsilon, w, and z depend on the particular reaction system. The results of earlier work were generalized by allowing a non-Fickian diffusion rate which predicts an essentially exponential dependence on the monomer concentration of the diffusion coefficient, D = D 0 [exp(deltaC/M)], where M is the saturation concentration. A reaction system is characterized by the three dimensionless parameters, upsilon, delta, and A = (L/2)[aM/sup (upsilon--1)//D 0 ]/sup 1/2/, where L is the polymer film thickness. Graft polymerization tends to become diffusion controlled as A increases. Larger values of delta and ν cause a reaction system to behave closer to the diffusion-free regime. Transition from diffusion-free to diffusion-controlled reaction involves changes in the dependence of the reaction rate on film thickness, initiation rate, and monomer concentration. Although the diffusion-free rate is w order in initiation rate, upsilon order in monomer, and independent of film thickness, the diffusion-controlled rate is w/2 order in initiator rate and inverse first-order in film thickness. Dependence of the diffusion-controlled rate on monomer is dependent in a complex manner on the diffusional characteristics of the reaction system. 11 figures, 4 tables

Rate coefficient for the reaction N + NO

Science.gov (United States)

Fox, J. L.

1994-01-01

Evidence has been advanced that the rate coefficient for the reaction N + NO right arrow N2 + O has a small positive temperature dependence at the high temperatures (900 to 1500 K) that prevail in the terrestrial middle and upper thermosphere by Siskind and Rusch (1992), and at the low temperatures (100 to 200 K) of the Martian lower thermosphere by Fox (1993). Assuming that the rate coefficient recommended by the Jet Propulsion Laboratory evaluation (DeMore et al., 1992) is accurate at 300 K, we derive here the low temperature value of the activation energy for this reaction and thus the rate coefficient that best fits the Viking 1 measured NO densities. We find that the fit is acceptable for a rate coefficient of about 1.3 x 10(exp -10)(T/300)(exp 0.5)exp(-400/T) and better for a value of about 2.5 x 10(exp -10)(T/300)(exp 0.5)exp(-600/T)cu cm/s.

Estimating the Backup Reaction Wheel Orientation Using Reaction Wheel Spin Rates Flight Telemetry from a Spacecraft

Science.gov (United States)

Rizvi, Farheen

2013-01-01

A report describes a model that estimates the orientation of the backup reaction wheel using the reaction wheel spin rates telemetry from a spacecraft. Attitude control via the reaction wheel assembly (RWA) onboard a spacecraft uses three reaction wheels (one wheel per axis) and a backup to accommodate any wheel degradation throughout the course of the mission. The spacecraft dynamics prediction depends upon the correct knowledge of the reaction wheel orientations. Thus, it is vital to determine the actual orientation of the reaction wheels such that the correct spacecraft dynamics can be predicted. The conservation of angular momentum is used to estimate the orientation of the backup reaction wheel from the prime and backup reaction wheel spin rates data. The method is applied in estimating the orientation of the backup wheel onboard the Cassini spacecraft. The flight telemetry from the March 2011 prime and backup RWA swap activity on Cassini is used to obtain the best estimate for the backup reaction wheel orientation.

REACLIB: A Reaction Rate Library for the Era of Collaborative Science

Science.gov (United States)

Meisel, Zachary

2008-10-01

Thermonuclear reaction rates and weak decay rates are of great importance to modern nuclear astrophysics. They are critical in the study of many topics such as Big Bang Nucleosynthesis, X-ray bursts, Supernovae, and S-process element formation, among others. The Joint Institute for Nuclear Astrophysics (JINA) has been created to increase connectivity amongst nuclear astrophysicists in our modern age of highly collaborative science. Within JINA there has been an effort to create a frequently updated and readily accessible database of thermonuclear reactions and weak decay rates. This database is the REACLIB library, which can be accessed at the web address: http://www.nscl.msu.edu/˜nero/db/. Here I will discuss the JINA REACLIB Project, including a new procedure to fit reaction rates as a function of temperature that takes full advantage of physicality. With these updated reaction rates, astrophysical modelers will no longer have to worry about the adverse effects of using obsolete reaction rate libraries lacking physical behavior.

Thermonuclear reaction rate of 17O(p,γ)18F

International Nuclear Information System (INIS)

Fox, C.; Iliadis, C.; Champagne, A.E.; Fitzgerald, R.P.; Longland, R.; Newton, J.; Pollanen, J.; Runkle, R.

2005-01-01

The 17 O(p,γ) 18 F and 17 O(p,α) 14 N reactions have a profound influence on hydrogen-burning nucleosynthesis in a number of stellar sites, including red giants, asymptotic giant branch (AGB) stars, massive stars, and classical novae. Previously evaluated thermonuclear rates for both reactions carry large uncertainties. We investigated the proton-capture reaction on 17 O in the bombarding energy range of E p lab = 180-540 keV. We observed a previously undiscovered resonance at E R lab = 193.2 ± 0.9 keV. The resonance strength amounts to (ωγ) pγ (1.2±0.2)x10 -6 eV. With this value, the uncertainties of the 17 O(p,γ) 18 F reaction rates are reduced by orders of magnitude in the peak temperature range of classical novae (T=0.1-0.4 GK). We also report on a reevaluation of the 17 O(p,γ) 18 F reaction rates at lower temperatures that are pertinent to red giants, AGB stars, or massive stars. The present work establishes the 17 O(p,γ) 18 F reaction rates over a temperature range of T= 0.01-1.5 GK with statistical uncertainties of 10-50%. The new recommended reaction rates deviate from the previously accepted values by an order of magnitude around T≅0.2 GK and by factors of 2-3 at T < 0.1 GK

Effective reaction rates in diffusion-limited phosphorylation-dephosphorylation cycles

Science.gov (United States)

Szymańska, Paulina; Kochańczyk, Marek; Miekisz, Jacek; Lipniacki, Tomasz

2015-02-01

We investigate the kinetics of the ubiquitous phosphorylation-dephosphorylation cycle on biological membranes by means of kinetic Monte Carlo simulations on the triangular lattice. We establish the dependence of effective macroscopic reaction rate coefficients as well as the steady-state phosphorylated substrate fraction on the diffusion coefficient and concentrations of opposing enzymes: kinases and phosphatases. In the limits of zero and infinite diffusion, the numerical results agree with analytical predictions; these two limits give the lower and the upper bound for the macroscopic rate coefficients, respectively. In the zero-diffusion limit, which is important in the analysis of dense systems, phosphorylation and dephosphorylation reactions can convert only these substrates which remain in contact with opposing enzymes. In the most studied regime of nonzero but small diffusion, a contribution linearly proportional to the diffusion coefficient appears in the reaction rate. In this regime, the presence of opposing enzymes creates inhomogeneities in the (de)phosphorylated substrate distributions: The spatial correlation function shows that enzymes are surrounded by clouds of converted substrates. This effect becomes important at low enzyme concentrations, substantially lowering effective reaction rates. Effective reaction rates decrease with decreasing diffusion and this dependence is more pronounced for the less-abundant enzyme. Consequently, the steady-state fraction of phosphorylated substrates can increase or decrease with diffusion, depending on relative concentrations of both enzymes. Additionally, steady states are controlled by molecular crowders which, mostly by lowering the effective diffusion of reactants, favor the more abundant enzyme.

Effect of Graphene Oxide on the Reaction Kinetics of Methyl Methacrylate In Situ Radical Polymerization via the Bulk or Solution Technique

Directory of Open Access Journals (Sweden)

Ioannis S. Tsagkalias

2017-09-01

Full Text Available The synthesis of nanocomposite materials based on poly(methyl methacrylate and graphene oxide (GO is presented using the in situ polymerization technique, starting from methyl methacrylate, graphite oxide, and an initiator, and carried out either with (solution or without (bulk in the presence of a suitable solvent. Reaction kinetics was followed gravimetrically and the appropriate characterization of the products took place using several experimental techniques. X-ray diffraction (XRD data showed that graphite oxide had been transformed to graphene oxide during polymerization, whereas FTIR spectra revealed no significant interactions between the polymer matrix and GO. It appears that during polymerization, the initiator efficiency was reduced by the presence of GO, resulting in a reduction of the reaction rate and a slight increase in the average molecular weight of the polymer formed, measured by gel permeation chromatography (GPC, along with an increase in the glass transition temperature obtained from differential scanning calorimetry (DSC. The presence of the solvent results in the suppression of the gel-effect in the reaction rate curves, the synthesis of polymers with lower average molecular weights and polydispersities of the Molecular Weight Distribution, and lower glass transition temperatures. Finally, from thermogravimetric analysis (TG, it was verified that the presence of GO slightly enhances the thermal stability of the nano-hybrids formed.

Nitrogen removal from landfill leachate via ex situ nitrification and sequential in situ denitrification

International Nuclear Information System (INIS)

Zhong Qi; Li Daping; Tao Yong; Wang Xiaomei; He Xiaohong; Zhang Jie; Zhang Jinlian; Guo Weiqiang; Wang Lan

2009-01-01

Ex situ nitrification and sequential in situ denitrification represents a novel approach to nitrogen management at landfills. Simultaneous ammonia and organics removal was achieved in a continuous stirred tank reactor (CSTR). The results showed that the maximum nitrogen loading rate (NLR) and the maximum organic loading rate (OLR) was 0.65 g N l -1 d -1 and 3.84 g COD l -1 d -1 , respectively. The ammonia and chemical oxygen demand (COD) removal was over 99% and 57%, respectively. In the run of the CSTR, free ammonia (FA) inhibition and low dissolved oxygen (DO) were found to be key factors affecting nitrite accumulation. In situ denitrification was studied in a municipal solid waste (MSW) column by recalculating nitrified leachate from CSTR. The decomposition of MSW was accelerated by the recirculation of nitrified leachate. Complete reduction of total oxidized nitrogen (TON) was obtained with maximum TON loading of 28.6 g N t -1 TS d -1 and denitrification was the main reaction responsible. Additionally, methanogenesis inhibition was observed while TON loading was over 11.4 g N t -1 TS d -1 and the inhibition was enhanced with the increase of TON loading

One ligand capable of in situ reaction in a mixed-ligand system with two new different frameworks

KAUST Repository

Wang, Xiaofang

2017-12-24

The in situ ligand 2,3-pyrazinedicarboxylic acid (2,3-H2pzdc) mixed with 1,1′-(1,4-butanediyl)bis(benzimidazole) (bbbi) is used to form two coordination polymers ([Cd(2,3-pzdc)(bbbi)] (1) and [Cd2Cl3(2-pzc)(bbbi)2] (2)) under hydrothermal conditions. Complex 1 was obtained in the absence of in situ reaction and 2 was synthesized with 2,3-H2pzdc in situ generating 2-pyrazinecarboxylate (2-pzc−). The structural details reveal that 1 has a 3D framework with dia topology, and 2 is a 2D layer structure and develops a 3D supramolecular structure via strong π⋯π stacking interactions. The ligand effects were compared for the two frameworks. In addition, fluorescence properties and thermal stabilities of 1 and 2 in the solid were studied.

In situ Spectroscopy of Solid-State Chemical Reaction in PbBr2-Deposited CsBr Crystals

Science.gov (United States)

Kondo, Shin-ichi; Matsunaga, Toshihiro; Saito, Tadaaki; Asada, Hiroshi

2003-09-01

It is possible to measure the fundamental optical absorption spectra of CsPbBr3 and Cs4PbBr6, whose stability is predicted by the study of phase diagram in the binary system CsBr-PbBr2, by means of in situ optical absorption and reflection spectroscopy of thermally induced solid-state chemical reaction in PbBr2-deposited CsBr crystals. On heavy annealing of the crystals, the Pb2+ ions are uniformly dispersed in the crystal matrix. The present experiment provides a novel method for measuring intrinsic optical absorption of ternary metal halides and also for in situ monitoring of doping metal halide crystal with impurities (metal ions or halogen ions).

Hydrogen isotope exchange reaction rates in tritium, hydrogen and deuterium mixed gases

International Nuclear Information System (INIS)

Uda, Tatsuhiko

1992-01-01

Hydrogen isotope exchange reaction rates in H 2 +T 2 , D 2 +T 2 and H 2 +D 2 +T 2 mixed gases, as induced by tritium decay and beta radiation, were experimentally measured by laser Raman spectrometry. Initially a glass cell was filled with T 2 gas to a pressure of 30-40 kPa, and an equivalent partial pressure of H 2 and/or D 2 was added. The first-order hydrogen isotope exchange reaction rates were 5.54x10 -2 h -1 for H 2 +T 2 mixed gas and 4.76x10 -2 h -1 for D 2 +T 2 . The actual HT producing rate was nearly equivalent to the rate of DT, but the reverse reaction rate of HT was faster than that of DT. The exchange reaction rates between H, D and T showed the isotope effect, HD>HT>DT. The hydrogen isotope exchange reaction rates observed were about twenty times larger than ion formation rates by beta radiation. This result suggests that a free radical chain reaction in hydrogen isotopes is occurring. (orig.)

Relationship among reaction rate, release rate and efficiency of nanomachine-based targeted drug delivery.

Science.gov (United States)

Zhao, Qingying; Li, Min; Luo, Jun

2017-12-04

In nanomachine applications towards targeted drug delivery, drug molecules released by nanomachines propagate and chemically react with tumor cells in aqueous environment. If the nanomachines release drug molecules faster than the tumor cells react, it will result in loss and waste of drug molecules. It is a potential issue associated with the relationship among reaction rate, release rate and efficiency. This paper aims to investigate the relationship among reaction rate, release rate and efficiency based on two drug reception models. We expect to pave a way for designing a control method of drug release. We adopted two analytical methods that one is drug reception process based on collision with tumors and another is based on Michaelis Menten enzymatic kinetics. To evaluate the analytical formulations, we used the well-known simulation framework N3Sim to establish simulations. The analytical results of the relationship among reaction rate, release rate and efficiency is obtained, which match well with the numerical simulation results in a 3-D environment. Based upon two drug reception models, the results of this paper would be beneficial for designing a control method of nanomahine-based drug release.

Non-resonant triple alpha reaction rate at low temperature

Energy Technology Data Exchange (ETDEWEB)

Itoh, T.; Tamii, A.; Aoi, N.; Fujita, H.; Hashimoto, T.; Miki, K.; Ogata, K. [Research Center for Nuclear Physics, Osaka University, Ibaraki, Osaka 567-0047 (Japan); Carter, J.; Donaldson, L.; Sideras-Haddad, E. [Schools of Physics, University of Witwatersrand, Johannesburg 2050 (South Africa); Furuno, T.; Kawabata, T. [Departments of Physics, Kyoto University, Sakyo, Kyoto, 606-8502 (Japan); Kamimura, M. [RIKEN Nishina Center, Wako, Saitama, 351-0198 (Japan); Nemulodi, F.; Neveling, R.; Smit, F. D.; Swarts, C. [iThemba Laboratory for Accelerator Based Sciences Somerset, West, 7129 (South Africa)

2014-05-02

Our experimental goal is to study the non-resonant triple alpha reaction rate at low temperture (T < 10{sup 8} K). The {sup 13}C(p,d) reaction at 66 MeV has been used to probe the alpha-unbound continuum state in {sup 12}C just below the 2{sup nd} 0{sup +} state at 7.65 MeV. The transition strength to the continuum state is predicted to be sensitive to the non-resonant triple alpha reaction rate. The experiment has been performed at iThemba LABS. We report the present status of the experiment.

Reactions and reaction rates in the regional aquifer beneath the Pajarito Plateau, north-central New Mexico, USA

Science.gov (United States)

Hereford, Anne G.; Keating, Elizabeth H.; Guthrie, George D.; Zhu, Chen

2007-05-01

Reactions and reaction rates within aquifers are fundamental components of critical hydrological processes. However, reactions simulated in laboratory experiments typically demonstrate rates that are much faster than those observed in the field. Therefore, it is necessary to conduct more reaction rate analyses in natural settings. This study of geochemical reactions in the regional aquifer in the Pajarito Plateau near Los Alamos, New Mexico combines modeling with petrographic assessment to further knowledge and understanding of complex natural hydrologic systems. Groundwater geochemistry shows marked evolution along assumed flow paths. The flow path chosen for this study was evaluated using inverse mass balance modeling to calculate the mass transfer. X-ray diffraction and field emission gun scanning electron microscopy were used to identify possible reactants and products. Considering the mineralogy of the aquifer and saturation indices for the regional water refined initial interpretations. Calculations yielded dissolution rates for plagioclase on the order of 10-15 mol s-1 m-2 and for K-feldspar on the order of 10-17 mol s-1 m-2, orders of magnitude slower than laboratory rates. While these rates agree with other aquifer studies, they must be considered in the light of the uncertainty associated with geometric surface area estimates, 14C ages, and aquifer properties.

DEPENDENCE OF X-RAY BURST MODELS ON NUCLEAR REACTION RATES

Energy Technology Data Exchange (ETDEWEB)

Cyburt, R. H.; Keek, L.; Schatz, H. [National Superconducting Cyclotron Laboratory, Michigan State University, East Lansing, MI 48824 (United States); Amthor, A. M. [Department of Physics and Astronomy, Bucknell University, Lewisburg, PA 17837 (United States); Heger, A.; Meisel, Z.; Smith, K. [Joint Institute for Nuclear Astrophysics (JINA), Michigan State University, East Lansing, MI 48824 (United States); Johnson, E. [Department of Physics and Astronomy, Michigan State University, East Lansing, MI 48824 (United States)

2016-10-20

X-ray bursts are thermonuclear flashes on the surface of accreting neutron stars, and reliable burst models are needed to interpret observations in terms of properties of the neutron star and the binary system. We investigate the dependence of X-ray burst models on uncertainties in (p, γ ), ( α , γ ), and ( α , p) nuclear reaction rates using fully self-consistent burst models that account for the feedbacks between changes in nuclear energy generation and changes in astrophysical conditions. A two-step approach first identified sensitive nuclear reaction rates in a single-zone model with ignition conditions chosen to match calculations with a state-of-the-art 1D multi-zone model based on the Kepler stellar evolution code. All relevant reaction rates on neutron-deficient isotopes up to mass 106 were individually varied by a factor of 100 up and down. Calculations of the 84 changes in reaction rate with the highest impact were then repeated in the 1D multi-zone model. We find a number of uncertain reaction rates that affect predictions of light curves and burst ashes significantly. The results provide insights into the nuclear processes that shape observables from X-ray bursts, and guidance for future nuclear physics work to reduce nuclear uncertainties in X-ray burst models.

In situ measurements of dose rates from terrestrial gamma rays

International Nuclear Information System (INIS)

Horng, M.C.; Jiang, S.H.

2002-01-01

A portable, high purity germanium (HPGe) detector was employed for the performance of in situ measurements of radionuclide activity concentrations in the ground in Taiwan, at altitudes ranging from sea level to 3900 m. The absolute peak efficiency of the HPGe detector for a gamma-ray source uniformly distributed in the semi-infinite ground was determined using a semi-empirical method. The gamma-ray dose rates from terrestrial radionuclides were calculated from the measured activity levels using recently published dose rate conversion factors. The absorbed dose rate in air due to cosmic rays was derived by subtracting the terrestrial gamma-ray dose rate from the overall absorbed dose rate in air measured using a high-pressure ionization chamber. The cosmic-ray dose rate calculated as a function of altitude, was found to be in good agreement with the data reported by UNSCEAR. (orig.)

RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

KAUST Repository

Suleimanov, Yu.V.

2013-03-01

We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

KAUST Repository

Suleimanov, Yu.V.; Allen, J.W.; Green, W.H.

2013-01-01

We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.

In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

Science.gov (United States)

Zhang, Kaige; Li, Gongke; Hu, Yuling

2015-10-28

The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

Diagnosis of In Situ Metabolic State and Rates of Microbial Metabolism During In Situ Uranium Bioremediation with Molecular Techniques

Energy Technology Data Exchange (ETDEWEB)

Lovley, Derek R. [University of Massachusetts, Amherst

2012-11-28

The goal of these projects was to develop molecule tools to tract the metabolic activity and physiological status of microorganisms during in situ uranium bioremediation. Such information is important in able to design improved bioremediation strategies. As summarized below, the research was highly successful with new strategies developed for estimating in situ rates of metabolism and diagnosing the physiological status of the predominant subsurface microorganisms. This is a first not only for groundwater bioremediation studies, but also for subsurface microbiology in general. The tools and approaches developed in these studies should be applicable to the study of microbial communities in a diversity of soils and sediments.

Effect and Modeling of Glucose Inhibition and In Situ Glucose Removal During Enzymatic Hydrolysis of Pretreated Wheat Straw

DEFF Research Database (Denmark)

Andric, Pavle; Meyer, Anne S.; Jensen, Peter Arendt

2010-01-01

The enzymatic hydrolysis of lignocellulosic biomass is known to be product-inhibited by glucose. In this study, the effects on cellulolytic glucose yields of glucose inhibition and in situ glucose removal were examined and modeled during extended treatment of heat-pretreated wheat straw......, during 96 h of reaction. When glucose was removed by dialysis during the enzymatic hydrolysis, the cellulose conversion rates and glucose yields increased. In fact, with dialytic in situ glucose removal, the rate of enzyme-catalyzed glucose release during 48-72 h of reaction recovered from 20......-40% to become approximate to 70% of the rate recorded during 6-24 h of reaction. Although Michaelis-Menten kinetics do not suffice to model the kinetics of the complex multi-enzymatic degradation of cellulose, the data for the glucose inhibition were surprisingly well described by simple Michaelis...

BIG-10 fission product generation and reaction rates

International Nuclear Information System (INIS)

Rogers, J.W.

1976-01-01

Fission product generation rates for high quality fission foils and reaction rates of nonfission foils have been measured by gamma ray activation analyses. These foils were irradiated in the BIG-10 facility and the activities were measured by NaI counting techniques

The Investors- Reaction to Investment Rating Change Announcements

OpenAIRE

Chih-Hsiang Chang; Liang-Chien Lee; Shu-Ling Wu

2012-01-01

This study investigates the investors- behavioral reaction to the investment rating change announcements from the views of behavioral finance. The empirical results indicate that self-interest does affect the intention of securities firms to release investment ratings for individual stocks. In addition, behavioral pitfalls are also found in the response of retail investors to investment rating change announcements.

Effect of the heating rate on the microstructure of in situ Al2O3 particle-reinforced Al matrix composites prepared via displacement reactions in an Al/CuO system

International Nuclear Information System (INIS)

Zhao, Ge; Shi, Zhiming; Ta, Na; Ji, Guojun; Zhang, Ruiying

2015-01-01

Highlights: • The heating rate has a significant effect on the microstructures of composites. • The microstructure is determined by the diffusion rate of O and Cu in the heating stage. • The diffusion of Cu and O atoms is influenced by the heating rate. • With increasing heating rate, the Al 2 O 3 particle distribution becomes more uniformly. • With increasing heating rate, the form of Al 2 Cu changes from network to block-like. - Abstract: In this study, an in situ Al 2 O 3 particle-reinforced Al(Cu) matrix composite was successfully synthesized using a displacement reaction between Al and CuO powders. The powders were mixed at a weight ratio of 4:1 Al to CuO, cold-pressed and holding time at 900 °C for 1 h using varying heating rates. The effects of the heating rate on the microstructures of the composites were investigated using differential scanning calorimetry (DSC), X-ray diffraction (XRD), optical microscopy (MO), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS). The results indicate that all of the composites contain Al, Al 2 O 3 particles and Al 2 Cu phases. Although the heating rate does not significantly affect the phase compositions of the composites, it has a significant effect on their microstructures, most likely because it strongly influences the diffusion rates of the Cu and O atoms. As the heating rate is increased, the Al 2 O 3 particles become more dispersed, and they have a more uniform particle size distribution. Meanwhile, the Al 2 Cu structure transforms from the network (Al + Al 2 Cu) eutectic to the block-like Al 2 Cu phase. The ∼2 μm Al 2 O 3 particles and the block-like Al 2 Cu phase are distributed uniformly in the Al matrix when the sample is placed directly into a 900 °C furnace. This sample has a relative higher Rockwell hardness B (HRB) value of 87

Effects of ion and electron screening on thermonuclear reaction rates

International Nuclear Information System (INIS)

Brady, L.R. Jr.

1977-01-01

The effects of screening by ions and electrons on thermonuclear reaction rates in stellar plasmas are considered. The enhancement of the reaction rate ranges from negligible to extremely large (on the order of 10 26 or greater). In order to calculate these effects, the potential about a given reacting nucleus is determined. First, Boltzmann-Vlasov and Poisson-Boltzmann equations are solved to yield a Yukawa potential. A suitable approximation to this potential is integrated in the action integral to give the barrier penetration. The screened reaction rate is then found by the saddle-point method. In developing a general formalism to calculate the screened reaction rate and the screening factor, effects due to the finite size of the nucleus are considered and found to be negligible. An expression for the screening factor for resonant reaction rates is also derived. A different and relatively simple approach, based on work of Stewart and Pyatt (1966), is used to find the barrier penetration from the action integral in two approximations: a modified Coulomb potential and a constant-shift potential. Screening factors are calculated for carbon burning at T 6 = 100 and T 6 = 400 for a wide range of densities and also for several examples in late stellar evolution. These screening factors are, for the most part, greater than those given by most others by a few percent at low density to 4 or more orders of magnitude at T 6 = 100 and rho = 10 10 g/cm 3 . Near the edge of the crystalline lattice region, however, they are significantly lower than those of some others. The increase in reaction rates for carbon burning indicates that carbon ignition may occur at lower densities than previously thought and may affect the density at which a supernova shock may occur

X particle effect for 6Li reaction rates calculations

International Nuclear Information System (INIS)

Kocak, G.; Balantekin, A. B.

2009-01-01

The inferred primordial 6 L i-7 L i abundances are different from standard big bang nucleosynthesis results, 6 L i is 1000 times larger and 7 L i is 3 times smaller than the big bang prediction. In big bang nucleosynthesis, negatively charged massive X particles a possible solution to explain this primordial Li abundances problem [1]. In this study, we consider only X particle effect for nuclear reactions to obtain S-factor and reaction rates for Li. All S-factors calculated within the Optical Model framework for d(α,γ)6 L i system. We showed that the enhancement effect of massive negatively charged X particle for 6 L i system reaction rate.(author)

Deposition and characteristics of PbS thin films by an in-situ solution chemical reaction process

Energy Technology Data Exchange (ETDEWEB)

Ji, Junna; Ji, Huiming; Wang, Jian; Zheng, Xuerong; Lai, Junyun; Liu, Weiyan; Li, Tongfei [School of Materials Science and Engineering, Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072 (China); Ma, Yuanliang; Li, Haiqin; Zhao, Suqin [College of Physics and Electronic Information Engineering, Qinghai University for Nationalities, Xining 810007 (China); Jin, Zhengguo, E-mail: zhgjin@tju.edu.cn [School of Materials Science and Engineering, Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin 300072 (China)

2015-09-01

Preferential oriented and uniform PbS thin films were deposited by a room temperature in-situ solution chemical reaction process, in which the lead nitrate as precursor in a form of thin solid films from lead precursor solution was used to react with ammonium sulfide ethanol solution. Influence of 1-butanol addition in the lead precursor solution, Pb:S molar ratios in the separate cationic and anionic solutions, deposition cycle numbers and annealing treatment in Ar atmosphere on structure, morphology, chemical composition and optical absorption properties of the deposited PbS films were investigated based on X-ray diffraction, field emission scanning electron microscopy, energy dispersive spectrometer, atomic force microscopy, selected area electron diffraction, UV–vis, near infrared ray and fourier transform infrared spectroscopy measurements. The results showed that the deposited PbS thin films had a cubic structure and highly preferred orientation along with the plane (100). The deposition rate of single-layer was stable, about 30 nm in thickness per deposition cycle. - Highlights: • Time-efficiency synthetic method for the preparation of lead sulfide (PbS) films • Effect of 1-butanol addition into cationic precursor solution is discussed. • Growth rate of the PbS films is stable at about 30 nm per cycle.

In situ Raman scattering study on a controllable plasmon-driven surface catalysis reaction on Ag nanoparticle arrays

International Nuclear Information System (INIS)

Dai, Z G; Xiao, X H; Zhang, Y P; Ren, F; Wu, W; Zhang, S F; Zhou, J; Jiang, C Z; Mei, F

2012-01-01

Control of the plasmon-driven chemical reaction for the transformation of 4-nitrobenzenethiol to p,p′-dimercaptoazobenzene by Ag nanoparticle arrays was studied. The Ag nanoparticle arrays were fabricated by means of nanosphere lithography. By changing the PS particle size, the localized surface plasmon resonance (LSPR) peaks of the Ag nanoparticle arrays can be tailored from 460 to 560 nm. The controlled reaction process was monitored by in situ surface-enhanced Raman scattering. The reaction can be dramatically influenced by varying the duration of laser exposure, Ag nanoparticle size, laser power and laser excitation wavelength. The maximum reaction speed was achieved when the LSPR wavelength of the Ag nanoparticle arrays matched the laser excitation wavelength. The experimental results reveal that the strong LSPR can effectively drive the transfer of the ‘hot’ electrons that decay from the plasmon to the reactants. The experimental results were confirmed by theoretical calculations. (paper)

Mechanically activated SHS reaction in the Fe-Al system: in-situ time resolved diffraction using synchrotron radiation

International Nuclear Information System (INIS)

Gaffet, E.; Charlot, F.; Klein, D.; Bernard, F.; Niepce, J.C.

1998-01-01

The mechanical activation self propagating high temperature synthesis (M.A.S.H.S.) processing is a new way to produce nanocrystalline iron aluminide intermetallic compounds. This process is maily the combination of two steps; in the one hand, a mechanical activation where the Fe - Al powder mixture was milled during a short time at given energy and frequency of shocks and in the other hand, a self propagating high temperature synthesis (S.H.S.) reaction, for which the exothermicity of the Fe + Al reaction is used. This fast propagated MASHS reaction has been in-situ investigated using the time resolved X-ray diffraction (TRXRD) using a X-ray synchrotron beam and an infrared thermography camera, allowing the coupling of the materials structure and the temperature field. The effects of the initial mean compositions, of the milling conditions as well as of the compaction parameters on the MASHS reaction are reported. (orig.)

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

International Nuclear Information System (INIS)

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

1982-01-01

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

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

NARCIS (Netherlands)

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

2002-01-01

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

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

NARCIS (Netherlands)

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

2000-01-01

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

Nuclear reaction rates and the nova outburst

International Nuclear Information System (INIS)

Starrfield, S.G.; Iliadis, C.

2000-01-01

In this paper we examined the consequences of improving the nuclear reaction library on our simulations of TNRs on 1.25M, WD and 1.35M, WDS. We have found that the changes in the rates have affected the nucleosynthesis predictions of our calculations but not, to any great extent, the gross features. In addition, we have used a lower mass accretion rate than in our previous studies in order to accrete (and eject) more material. This has, as expected, caused the peak values of some important parameters to increase over our previous studies at the same WD mass. However, because some important reaction rates have declined in the new compilation this has not increased the abundances for nuclei above aluminum and, in fact, they have declined while the abundances of both 26 Al and 27 Al have increased at both WD masses. In contrast, the abundance of 22 Na has declined at both WD masses over the values predicted in our earlier work. This has important implications with respect to predictions of the observability of novae with INTEGRAL

In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism

Science.gov (United States)

Kirshenbaum, Kevin; Bock, David C.; Lee, Chia-Ying; Zhong, Zhong; Takeuchi, Kenneth J.; Marschilok, Amy C.; Takeuchi, Esther S.

2015-01-01

The functional capacity of a battery is observed to decrease, often quite dramatically, as discharge rate demands increase. These capacity losses have been attributed to limited ion access and low electrical conductivity, resulting in incomplete electrode use. A strategy to improve electronic conductivity is the design of bimetallic materials that generate a silver matrix in situ during cathode reduction. Ex situ x-ray absorption spectroscopy coupled with in situ energy-dispersive x-ray diffraction measurements on intact lithium/silver vanadium diphosphate (Li/Ag2VP2O8) electrochemical cells demonstrate that the metal center preferentially reduced and its location in the bimetallic cathode are rate-dependent, affecting cell impedance. This work illustrates that spatial imaging as a function of discharge rate can provide needed insights toward improving realizable capacity of bimetallic cathode systems.

Multiscale Investigation on Biofilm Distribution and Its Impact on Macroscopic Biogeochemical Reaction Rates: BIOFILM DISTRIBUTION AND RATE SCALING

Energy Technology Data Exchange (ETDEWEB)

Yan, Zhifeng [Institute of Surface-Earth System Science, Tianjin University, Tianjin China; Pacific Northwest National Laboratory, Richland WA USA; Liu, Chongxuan [Pacific Northwest National Laboratory, Richland WA USA; School of Environmental Science and Engineering, Southern University of Science and Technology, Shenzhen China; Liu, Yuanyuan [Pacific Northwest National Laboratory, Richland WA USA; School of Earth Science and Engineering, Nanjing University, Nanjing China; Bailey, Vanessa L. [Pacific Northwest National Laboratory, Richland WA USA

2017-11-01

Biofilms are critical locations for biogeochemical reactions in the subsurface environment. The occurrence and distribution of biofilms at microscale as well as their impacts on macroscopic biogeochemical reaction rates are still poorly understood. This paper investigated the formation and distributions of biofilms in heterogeneous sediments using multiscale models, and evaluated the effects of biofilm heterogeneity on local and macroscopic biogeochemical reaction rates. Sediment pore structures derived from X-ray computed tomography were used to simulate the microscale flow dynamics and biofilm distribution in the sediment column. The response of biofilm formation and distribution to the variations in hydraulic and chemical properties was first examined. One representative biofilm distribution was then utilized to evaluate its effects on macroscopic reaction rates using nitrate reduction as an example. The results revealed that microorganisms primarily grew on the surfaces of grains and aggregates near preferential flow paths where both electron donor and acceptor were readily accessible, leading to the heterogeneous distribution of biofilms in the sediments. The heterogeneous biofilm distribution decreased the macroscopic rate of biogeochemical reactions as compared with those in homogeneous cases. Operationally considering the heterogeneous biofilm distribution in macroscopic reactive transport models such as using dual porosity domain concept can significantly improve the prediction of biogeochemical reaction rates. Overall, this study provided important insights into the biofilm formation and distribution in soils and sediments as well as their impacts on the macroscopic manifestation of reaction rates.

The effect of sintering time on synthesis of in situ submicron {alpha}-Al{sub 2}O{sub 3} particles by the exothermic reactions of CuO particles in molten pure Al

Energy Technology Data Exchange (ETDEWEB)

Dikici, Burak, E-mail: burakdikici@yyu.edu.tr [Yuzuncu Yil University, Department of Mechanical Engineering, 65080 Van (Turkey); Gavgali, Mehmet [Ataturk University, Department of Mechanical Engineering, 25240 Erzurum (Turkey)

2013-02-25

Highlights: Black-Right-Pointing-Pointer Al-Cu/Al{sub 2}O{sub 3} composites were prepared successfully by means of hot pressing method. Black-Right-Pointing-Pointer Sintering time of the Al-CuO system effect the reaction rate and formation of Al{sub 2}O{sub 3}. Black-Right-Pointing-Pointer Increase in sintering time accelerates formation of submicron in situ {alpha}-Al{sub 2}O{sub 3} phase. Black-Right-Pointing-Pointer Hardness of the sintered composite for 30 min at 1000 Degree-Sign C increased from 60 to 174 HV. - Abstract: In this study, in situ {alpha}-Al{sub 2}O{sub 3} reinforcing particles have been successfully synthesised in an Al-Cu matrix alloy by means of the conventional Hot Pressing (HP) method. The effect of sintering time on the forming of the {alpha}-Al{sub 2}O{sub 3} phase at 1000 Degree-Sign C was investigated using Differential Thermal Analysis (DTA), X-ray Diffraction (XRD) and a Scanning Electron Microscope (SEM). The sintered composites contained thermodynamically stable {alpha}-Al{sub 2}O{sub 3} particles and {theta}-Al{sub 2}Cu eutectic phases, which were embedded in the Al-Cu matrix. The in situ {alpha}-Al{sub 2}O{sub 3} particles were generally spherical and their mean size was observed to be less than 0.5 {mu}m. The results showed that sintering time influences not only the reaction rate of copper and the formation of Al{sub 2}O{sub 3}. Also, an increase in the sintering time accelerates the formation of submicron in situ {alpha}-Al{sub 2}O{sub 3} particles and decreases the quantity of {theta}-Al{sub 2}Cu intermetallic phase in the liquid aluminium. Additionally, sintering of composite for 30 min at 1000 Degree-Sign C increased the hardness from 60 to 174 HV.

In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts.

Science.gov (United States)

Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A

2016-10-24

The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The reaction rates of electrons with native and irradiated ribonuclease

International Nuclear Information System (INIS)

Schuessler, H.; Ebert, M.; Davies, J.V.

1977-01-01

The rate of reaction of hydrated electrons with proteins depends, amongst other things, on the conformational structure of the protein, and irradiation itself causes conformational changes in proteins. A study has been made of variations in the reaction rates of hydrated electrons with RNase pre-irradiated by the Linac or by a 60 Co γ-source. The reaction rate constants varied with the pre-irradiation dose, the concentration of phosphate buffer, the enzyme concentration and also the presence of 10 -2 M ethanol. These variations serve to emphasize the importance of the tertiary structure of biological molecules in irradiation processes and have significant implications in the mathematical analysis of the inactivation of enzymes in steady-state irradiation processes. (U.K.)

On the mechanism of effective chemical reactions with turbulent mixing of reactants and finite rate of molecular reactions

Energy Technology Data Exchange (ETDEWEB)

Vorotilin, V. P., E-mail: VPVorotilin@yandex.ru [Russian Academy of Sciences, Institute of Applied Mechanics (Russian Federation)

2017-01-15

A generalization of the theory of chemical transformation processes under turbulent mixing of reactants and arbitrary values of the rate of molecular reactions is presented that was previously developed for the variant of an instantaneous reaction [13]. The use of the features of instantaneous reactions when considering the general case, namely, the introduction of the concept of effective reaction for the reactant volumes and writing a closing conservation equation for these volumes, became possible due to the partition of the whole amount of reactants into “active” and “passive” classes; the reactants of the first class are not mixed and react by the mechanism of instantaneous reactions, while the reactants of the second class approach each other only through molecular diffusion, and therefore their contribution to the reaction process can be neglected. The physical mechanism of reaction for the limit regime of an ideal mixing reactor (IMR) is revealed and described. Although formally the reaction rate in this regime depends on the concentration of passive fractions of the reactants, according to the theory presented, the true (hidden) mechanism of the reaction is associated only with the reaction of the active fractions of the reactants with vanishingly small concentration in the volume of the reactor. It is shown that the rate constant of fast chemical reactions can be evaluated when the mixing intensity of reactants is much less than that needed to reach the mixing conditions in an IMR.

Non extensive corrections to stellar nuclear reactions rate

Energy Technology Data Exchange (ETDEWEB)

Assuncao, M. [Universidade Federal de Sao Paulo (DCET/UNIFESP), Diadema, SP (Brazil). Dept. de Ciencias Exatas e da Terra; Silveira, F.E.M. [Universidade Federal do ABC, Santo Andre, SP (Brazil). Centro de Ciencias Naturais e Humanas; Lima, J.A.S. [Universidade de Sao Paulo (IAG/USP), SP (Brazil). Inst. de Astronomia, Geofisica e Ciencias Atmosfericas

2010-07-01

Full text: Stellar nucleosynthesis is widely accepted as the basic mechanism for creation of chemical elements in the Universe. In particular, nuclear reactions occurring in the Sun are recognized as responsible for its energy generation. The problem of to determine the energy generation mechanism in stars was firstly attacked by Gamow in the framework of his quantum mechanical theory of potential barrier penetration. According to that approach, the reactions rate is calculated by averaging the penetration factor over the velocity distribution of the plasma particles. A randomization of that distribution is expected as a consequence of the reactions. However, diffusion processes in the macroscopic environment should balance the resulting particles number depletion. Therefore, matter, energy, and momentum might steadily flow. In other words, a quasi-stationary equilibrium state must be attained. In this work, the potential barrier penetration approach to stellar nuclear reactions rate has been rediscussed with basis on Tsallis nonextensive statistics. The investigation has been restricted to non-resonant reactions, for which the S-factor can be regarded as a constant. It has been found that, within the extended formulation, the nonextensive q-parameter is constrained to a maximum value. Accordingly, the q-energy has been shown to exhibit a minimum. The q-Gamow peak has been derived and, in connection with the usual Gaussian approximation, the corresponding half q-width has been also estimated. Plots of the q-energy, q-Gamow peak and half q-width for some reactions with stellar physics interest have been produced. (author)

Matching of experimental and statistical-model thermonuclear reaction rates at high temperatures

International Nuclear Information System (INIS)

Newton, J. R.; Longland, R.; Iliadis, C.

2008-01-01

We address the problem of extrapolating experimental thermonuclear reaction rates toward high stellar temperatures (T>1 GK) by using statistical model (Hauser-Feshbach) results. Reliable reaction rates at such temperatures are required for studies of advanced stellar burning stages, supernovae, and x-ray bursts. Generally accepted methods are based on the concept of a Gamow peak. We follow recent ideas that emphasized the fundamental shortcomings of the Gamow peak concept for narrow resonances at high stellar temperatures. Our new method defines the effective thermonuclear energy range (ETER) by using the 8th, 50th, and 92nd percentiles of the cumulative distribution of fractional resonant reaction rate contributions. This definition is unambiguous and has a straightforward probability interpretation. The ETER is used to define a temperature at which Hauser-Feshbach rates can be matched to experimental rates. This matching temperature is usually much higher compared to previous estimates that employed the Gamow peak concept. We suggest that an increased matching temperature provides more reliable extrapolated reaction rates since Hauser-Feshbach results are more trustwhorthy the higher the temperature. Our ideas are applied to 21 (p,γ), (p,α), and (α,γ) reactions on A=20-40 target nuclei. For many of the cases studied here, our extrapolated reaction rates at high temperatures differ significantly from those obtained using the Gamow peak concept

Compilation and R-matrix analysis of Big Bang nuclear reaction rates

International Nuclear Information System (INIS)

Descouvemont, Pierre; Adahchour, Abderrahim; Angulo, Carmen; Coc, Alain; Vangioni-Flam, Elisabeth

2004-01-01

We use the R-matrix theory to fit low-energy data on nuclear reactions involved in Big Bang nucleosynthesis. Special attention is paid to the rate uncertainties which are evaluated on statistical grounds. We provide S factors and reaction rates in tabular and graphical formats

Densification of Ce0.9Gd0.1O1.95 barrier layer by in-situ solid state reaction

DEFF Research Database (Denmark)

Ni, De Wei; Esposito, Vincenzo

2014-01-01

A novel methodology, called in-situ solid state reaction (SSR), is developed and achieved for the densification of gadolinia doped ceria (CGO) barrier layer (BL) within the solid oxide fuel cell (SOFC) technology. The method is based on the combined use of impregnation technique and a designed two...

Students' Ideas about Reaction Rate and Its Relationship with Concentration or Pressure

Science.gov (United States)

Cakmakci, Gultekin; Leach, John; Donnelly, James

2006-01-01

This cross-sectional study identifies key conceptual difficulties experienced by upper secondary school and pre-service chemistry teachers (N = 191) in the area of reaction rates. Students' ideas about reaction rates were elicited through a series of written tasks and individual interviews. In this paper, students' ideas related to reaction rate…

Quantum theory of enhanced unimolecular reaction rates below the ergodicity threshold

International Nuclear Information System (INIS)

Leitner, David M.; Wolynes, Peter G.

2006-01-01

A variety of unimolecular reactions exhibit measured rates that exceed Rice-Ramsperger-Kassel-Marcus (RRKM) predictions. We show using the local random matrix theory (LRMT) of vibrational energy flow how the quantum localization of the vibrational states of a molecule, by violating the ergodicity assumption, can give rise to such an enhancement of the apparent reaction rate. We present an illustrative calculation using LRMT for a model 12-vibrational mode organic molecule to show that below the ergodicity threshold the reaction rate may exceed many times the RRKM prediction due to quantum localization of vibrational states

Neutron detector for fusion reaction-rate measurements

International Nuclear Information System (INIS)

Lerche, R.A.; Phillion, D.W.; Tietbohl, G.L.

1993-01-01

We have developed a fast, sensitive neutron detector for recording the fusion reaction-rate history of inertial-confinement fusion (ICF) experiments. The detector is based on the fast rise-time of a commercial plastic scintillator (BC-422) and has a response 7 neutrons

Reaction rates for neutrino processes

International Nuclear Information System (INIS)

Shalitin, D.

1978-01-01

Some integrals involved in neutrino processes are evaluated by transformation to a special system of reference - usually to the center of mass system (CM). Rather simple analytic expressions are obtained for reaction rates and, though less simple, for moments. An interesting result thus obtained is for an isotropic interaction (in CM) of a neutrino with a monoenergetic isotropic gas of extreme relativistic electrons: it is found that the probability of the scattered neutrino to have energy in a certain range is independent of this energy. (Auth.)

Liquid Film Diffusion on Reaction Rate in Submerged Biofilters

DEFF Research Database (Denmark)

Christiansen, Pia; Hollesen, Line; Harremoës, Poul

1995-01-01

Experiments were carried out in order to investigate the influence of liquid film diffusion on reaction rate in a submerged biofilter with denitrification and in order to compare with a theoretical study of the mass transfer coefficient. The experiments were carried out with varied flow, identified...... by the empty bed velocity of inflow and recirculation, respectively 1.3, 2.8, 5.6 and 10.9 m/h. The filter material consisted of 3 mm biostyren spheres. The results indicate that the influence of liquid film diffusion on reaction rate can be ignored....

Astrophysical reaction rate for α(αn,γ)9Be by photodisintegration

International Nuclear Information System (INIS)

Sumiyoshi, K.; Utsunomiya, H.; Goko, S.; Kajino, T.

2002-01-01

We study the astrophysical reaction rate for the formation of 9 Be through the three body reaction α(αn,γ). This reaction is one of the key reactions which could bridge the mass gap at A=8 nuclear systems to produce intermediate-to-heavy mass elements in alpha- and neutron-rich environments such as r-process nucleosynthesis in supernova explosions, s-process nucleosynthesis in asymptotic giant branch (AGB) stars, and primordial nucleosynthesis in baryon inhomogeneous cosmological models. To calculate the thermonuclear reaction rate in a wide range of temperatures, we numerically integrate the thermal average of cross sections assuming a two-steps formation through a metastable 8 Be, α+α[rlhar2] 8 Be(n,γ) 9 Be. Off-resonant and on-resonant contributions from the ground state in 8 Be are taken into account. As input cross section, we adopt the latest experimental data by photodisintegration of 9 Be with laser-electron photon beams, which covers all relevant resonances in 9 Be. Experimental data near the neutron threshold are added with γ-ray flux corrections and a new least-squares analysis is made to deduce resonance parameters in the Breit-Wigner formulation. Based on the photodisintegration cross section, we provide the reaction rate for α(αn,γ) 9 Be in the temperature range from T 9 =10 -3 to T 9 =10 1 (T 9 is the temperature in units of 10 9 K) both in the tabular form and in the analytical form for potential usage in nuclear reaction network calculations. The calculated reaction rate is compared with the reaction rates of the CF88 and the NACRE compilations. The CF88 rate, which is based on the photoneutron cross section for the 1/2 + state in 9 Be by Berman et al., is valid at T 9 >0.028 due to lack of the off-resonant contribution. The CF88 rate differs from the present rate by a factor of two in a temperature range T 9 ≥0.1. The NACRE rate, which adopted different sources of experimental information on resonance states in 9 Be, is 4-12 times

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

Energy Technology Data Exchange (ETDEWEB)

Maher, K.; Steefel, C. I.; White, A.F.; Stonestrom, D.A.

2009-02-25

In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka marine terrace chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized (White et al., 2008, GCA) and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisser and [2006] or the aluminum inhibition model proposed by Oelkers et al. [1994], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO{sub 2}(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total

Effects of network dissolution changes on pore-to-core upscaled reaction rates for kaolinite and anorthite reactions under acidic conditions

KAUST Repository

Kim, Daesang

2013-11-01

We have extended reactive flow simulation in pore-network models to include geometric changes in the medium from dissolution effects. These effects include changes in pore volume and reactive surface area, as well as topological changes that open new connections. The computed changes were based upon a mineral map from an X-ray computed tomography image of a sandstone core. We studied the effect of these changes on upscaled (pore-scale to core-scale) reaction rates and compared against the predictions of a continuum model. Specifically, we modeled anorthite and kaolinite reactions under acidic flow conditions during which the anorthite reactions remain far from equilibrium (dissolution only), while the kaolinite reactions can be near-equilibrium. Under dissolution changes, core-scale reaction rates continuously and nonlinearly evolved in time. At higher injection rates, agreement with predictions of the continuum model degraded significantly. For the far-from-equilibrium reaction, our results indicate that the ability to correctly capture the heterogeneity in dissolution changes in the reactive mineral surface area is critical to accurately predict upscaled reaction rates. For the near-equilibrium reaction, the ability to correctly capture the heterogeneity in the saturation state remains critical. Inclusion of a Nernst-Planck term to ensure neutral ionic currents under differential diffusion resulted in at most a 9% correction in upscaled rates.

On the existence of and mechanism for microwave-specific reaction rate enhancement.

Science.gov (United States)

Dudley, Gregory B; Richert, Ranko; Stiegman, A E

2015-04-01

The use of microwave radiation to drive chemical reactions has become ubiquitous in almost all fields of chemistry. In all of these areas it is principally due to rapid and convenient heating resulting in significantly higher rates of reaction, with other advantages including enhanced product selectivity and control of materials properties. Although microwave heating continues to grow as an enabling technology, fundamental research into the nature of microwave heating has not grown at the same rate. In the case of chemical reactions run in homogeneous solution, particularly synthetic organic reactions, there is considerable controversy over the origins of rate enhancement, with a fundamental question being whether there exist microwave-specific effects, distinct from what can be attained under conventional convective heating, that can accelerate a reaction rate. In this Perspective, we discuss unique aspects of microwave heating of molecules in solution and discuss the origin and nature of microwave-specific effects arising from the process of "selective heating" of reactants in solution. Integral to this discussion is work from the field of dielectric relaxation spectroscopy, which provides a model for selective heating by Debye relaxation processes. The Perspective also includes a critical discussion of hypotheses of non-thermal effects (alternatively classified here as resonant processes) and an outline of specific reaction parameters for chemical systems in which microwave-specific Debye relaxation processes can result in observable reaction rate enhancement.

Nuclear-reaction rates in the thermonuclear runaway phase of accreting neutron stars

International Nuclear Information System (INIS)

Wiescher, M.; Barnard, V.; Goerres, J.; Fisker, J.L.; Martinez-Pinedo, G.; Langanke, K.; Rembges, F.; Thielemann, F.K.; Schatz, H.

2002-01-01

The rp-process has been suggested as the dominant nucleosynthesis process in explosive hydrogen burning at high temperature and density conditions. The process is characterized by a sequence of fast proton capture reactions and subsequent β-decays. The reaction path of the rp-process runs along the drip line up to Z∼50. Most of the charged-particle reaction rates for the reaction path are presently based on statistical Hauser-Feshbach calculations. While these rates are supposed to be reliable within a factor of two for conditions of high density in the compound nuclei, discrepancies may occur for nuclei near closed shells or near the proton drip line where the Q-values of proton capture processes are typically very small. It has been argued that the thermonuclear runaway is less sensitive to the reaction rates because of the rapid time-scale of the event. However, since these processes may operate at the same time-scale as fast mixing and convection processes, a change in reaction rates indeed may have a significant impact. In this paper we present two examples, the break-out from the hot CNO cycles, and the thermonuclear runaway in X-ray bursts itself, where changes in reaction rates have a direct impact on time-scale, energy generation and nucleosynthesis predictions for the explosive event. (orig.)

In situ release rates of Cu and Zn from commercial antifouling paints at different salinities.

Science.gov (United States)

Lagerström, Maria; Lindgren, J Fredrik; Holmqvist, Albin; Dahlström, Mia; Ytreberg, Erik

2018-02-01

Antifouling paints are environmentally risk assessed based on their biocidal release rates to the water phase. In situ release rates of copper (Cu) and zinc (Zn) were derived for five commercial paints in two recreational marinas with different salinities (5 and 14 PSU) using an X-Ray Fluorescence spectrometer (XRF). Salinity was found to significantly affect the Cu release, with twice the amount of Cu released at the higher salinity, while its influence on the Zn release was paint-specific. Site-specific release rates for water bodies with salinity gradients, e.g. the Baltic Sea, are therefore necessary for more realistic risk assessments of antifouling paints. Furthermore, the in situ release rates were up to 8 times higher than those generated using standardized laboratory or calculation methods. The environmental risk assessment repeated with the field release rates concludes that it is questionable whether the studied products should be allowed on the Swedish market. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Thermonuclear 19F(p, {{\\boldsymbol{\\alpha }}}_{0})16O reaction rate

Science.gov (United States)

He, Jian-Jun; Lombardo, Ivano; Dell'Aquila, Daniele; Xu, Yi; Zhang, Li-Yong; Liu, Wei-Ping

2018-01-01

The thermonuclear 19F(p, {{{α }}}0)16O reaction rate in the temperature region 0.007-10 GK has been derived by re-evaluating the available experimental data, together with the low-energy theoretical R-matrix extrapolations. Our new rate deviates by up to about 30% compared to the previous results, although all rates are consistent within the uncertainties. At very low temperature (e.g. 0.01 GK) our reaction rate is about 20% lower than the most recently published rate, because of a difference in the low energy extrapolated S-factor and a more accurate estimate of the reduced mass used in the calculation of the reaction rate. At temperatures above ˜1 GK, our rate is lower, for instance, by about 20% around 1.75 GK, because we have re-evaluated the previous data (Isoya et al., Nucl. Phys. 7, 116 (1958)) in a meticulous way. The present interpretation is supported by the direct experimental data. The uncertainties of the present evaluated rate are estimated to be about 20% in the temperature region below 0.2 GK, and are mainly caused by the lack of low-energy experimental data and the large uncertainties in the existing data. Asymptotic giant branch (AGB) stars evolve at temperatures below 0.2 GK, where the 19F(p, {{α }})16O reaction may play a very important role. However, the current accuracy of the reaction rate is insufficient to help to describe, in a careful way, the fluorine over-abundances observed in AGB stars. Precise cross section (or S factor) data in the low energy region are therefore needed for astrophysical nucleosynthesis studies. Supported by National Natural Science Foundation of China (11490562, 11490560, 11675229) and National Key Research and Development Program of China (2016YFA0400503)

Method and apparatus for obtaining enhanced production rate of thermal chemical reactions

Science.gov (United States)

Tonkovich, Anna Lee Y [Pasco, WA; Wang, Yong [Richland, WA; Wegeng, Robert S [Richland, WA; Gao, Yufei [Kennewick, WA

2003-04-01

The present invention is a method and apparatus (vessel) for providing a heat transfer rate from a reaction chamber through a wall to a heat transfer chamber substantially matching a local heat transfer rate of a catalytic thermal chemical reaction. The key to the invention is a thermal distance defined on a cross sectional plane through the vessel inclusive of a heat transfer chamber, reaction chamber and a wall between the chambers. The cross sectional plane is perpendicular to a bulk flow direction of the reactant stream, and the thermal distance is a distance between a coolest position and a hottest position on the cross sectional plane. The thermal distance is of a length wherein the heat transfer rate from the reaction chamber to the heat transfer chamber substantially matches the local heat transfer rate.

A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.

Science.gov (United States)

Gallis, Michael A; Bond, Ryan B; Torczynski, John R

2009-09-28

Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.

Computational and experimental studies on stabilities, reactions and reaction rates of cations and ion-dipole complexes

NARCIS (Netherlands)

Ervasti, H.K.

2008-01-01

In this thesis, ion stability, ion-molecule reactions and reaction rates are studied using mass spectrometry and molecular modelling. In Chapter 2 the effect of functional group substitution on neutral and ionised ketene are studied. Electron-donating substituents show a stabilising positive

A mesoscopic reaction rate model for shock initiation of multi-component PBX explosives.

Science.gov (United States)

Liu, Y R; Duan, Z P; Zhang, Z Y; Ou, Z C; Huang, F L

2016-11-05

The primary goal of this research is to develop a three-term mesoscopic reaction rate model that consists of a hot-spot ignition, a low-pressure slow burning and a high-pressure fast reaction terms for shock initiation of multi-component Plastic Bonded Explosives (PBX). Thereinto, based on the DZK hot-spot model for a single-component PBX explosive, the hot-spot ignition term as well as its reaction rate is obtained through a "mixing rule" of the explosive components; new expressions for both the low-pressure slow burning term and the high-pressure fast reaction term are also obtained by establishing the relationships between the reaction rate of the multi-component PBX explosive and that of its explosive components, based on the low-pressure slow burning term and the high-pressure fast reaction term of a mesoscopic reaction rate model. Furthermore, for verification, the new reaction rate model is incorporated into the DYNA2D code to simulate numerically the shock initiation process of the PBXC03 and the PBXC10 multi-component PBX explosives, and the numerical results of the pressure histories at different Lagrange locations in explosive are found to be in good agreements with previous experimental data. Copyright © 2016 Elsevier B.V. All rights reserved.

Rapid thermal processing chamber for in-situ x-ray diffraction

International Nuclear Information System (INIS)

Ahmad, Md. Imteyaz; Van Campen, Douglas G.; Yu, Jiafan; Pool, Vanessa L.; Van Hest, Maikel F. A. M.; Toney, Michael F.; Fields, Jeremy D.; Parilla, Philip A.; Ginley, David S.

2015-01-01

Rapid thermal processing (RTP) is widely used for processing a variety of materials, including electronics and photovoltaics. Presently, optimization of RTP is done primarily based on ex-situ studies. As a consequence, the precise reaction pathways and phase progression during the RTP remain unclear. More awareness of the reaction pathways would better enable process optimization and foster increased adoption of RTP, which offers numerous advantages for synthesis of a broad range of materials systems. To achieve this, we have designed and developed a RTP instrument that enables real-time collection of X-ray diffraction data with intervals as short as 100 ms, while heating with ramp rates up to 100 °Cs −1 , and with a maximum operating temperature of 1200 °C. The system is portable and can be installed on a synchrotron beamline. The unique capabilities of this instrument are demonstrated with in-situ characterization of a Bi 2 O 3 -SiO 2 glass frit obtained during heating with ramp rates 5 °C s −1 and 100 °C s −1 , revealing numerous phase changes

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-03-01

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

Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Niobium

CERN Document Server

American Society for Testing and Materials. Philadelphia

2008-01-01

1.1 This test method describes procedures for measuring reaction rates by the activation reaction 93Nb(n,n′)93mNb. 1.2 This activation reaction is useful for monitoring neutrons with energies above approximately 0.5 MeV and for irradiation times up to about 30 years. 1.3 With suitable techniques, fast-neutron reaction rates for neutrons with energy distribution similar to fission neutrons can be determined in fast-neutron fluences above about 1016cm−2. In the presence of high thermal-neutron fluence rates (>1012cm−2·s−1), the transmutation of 93mNb due to neutron capture should be investigated. In the presence of high-energy neutron spectra such as are associated with fusion and spallation sources, the transmutation of 93mNb by reactions such as (n,2n) may occur and should be investigated. 1.4 Procedures for other fast-neutron monitors are referenced in Practice E 261. 1.5 Fast-neutron fluence rates can be determined from the reaction rates provided that the appropriate cross section information ...

Scaling in situ cosmogenic nuclide production rates using analytical approximations to atmospheric cosmic-ray fluxes

Science.gov (United States)

Lifton, Nathaniel; Sato, Tatsuhiko; Dunai, Tibor J.

2014-01-01

Several models have been proposed for scaling in situ cosmogenic nuclide production rates from the relatively few sites where they have been measured to other sites of interest. Two main types of models are recognized: (1) those based on data from nuclear disintegrations in photographic emulsions combined with various neutron detectors, and (2) those based largely on neutron monitor data. However, stubborn discrepancies between these model types have led to frequent confusion when calculating surface exposure ages from production rates derived from the models. To help resolve these discrepancies and identify the sources of potential biases in each model, we have developed a new scaling model based on analytical approximations to modeled fluxes of the main atmospheric cosmic-ray particles responsible for in situ cosmogenic nuclide production. Both the analytical formulations and the Monte Carlo model fluxes on which they are based agree well with measured atmospheric fluxes of neutrons, protons, and muons, indicating they can serve as a robust estimate of the atmospheric cosmic-ray flux based on first principles. We are also using updated records for quantifying temporal and spatial variability in geomagnetic and solar modulation effects on the fluxes. A key advantage of this new model (herein termed LSD) over previous Monte Carlo models of cosmogenic nuclide production is that it allows for faster estimation of scaling factors based on time-varying geomagnetic and solar inputs. Comparing scaling predictions derived from the LSD model with those of previously published models suggest potential sources of bias in the latter can be largely attributed to two factors: different energy responses of the secondary neutron detectors used in developing the models, and different geomagnetic parameterizations. Given that the LSD model generates flux spectra for each cosmic-ray particle of interest, it is also relatively straightforward to generate nuclide-specific scaling

DDE in sediments of the Palos Verdes shelf, California: In situ transformation rates and geochemical fate

Science.gov (United States)

Eganhouse, R.P.; Pontolillo, J.

2008-01-01

From 1947 to 1971 the world's largest manufacturer of DDT discharged process wastes into the sewers of Los Angeles County. Roughly 870-1450 t of DDT were released to the ocean off Palos Verdes, CA, a portion of which (???100 t) resides in sediments on the continental shelf and slope. The most abundant DDT compound in the sediments, p,p???-DDE, is degrading by reductive dechlorination, butthe rate of transformation and factors controlling it are not well understood. In order to estimate in situ transformation rates and predict the long-term fate of p,p???-DDE, box cores were collected in 1992 and 2003 from a single location on the Palos Verdes Shelf and analyzed for 8 DDT compounds and 84 polychlorinated biphenyl (PCB) congeners. The PCBs show no evidence of dechlorination, and inventories did not change between 1992 and 2003. By contrast, the inventory of p,p???-DDE decreased by 43%, whereas that of p,p???-DDMU, the putative reductive dechlorination product increased by 34%. The first-order transformation rate for p,p???-DDE at the study site is 0.051 ?? 0.006 yr-1. A multistep reaction model suggests that inventories of p,p???-DDE and p,p???-DDMU will continue to decline, whereas that of p,p???-DDNU will reach a maximum around 2014.

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.

Pycnonuclear reaction rates for binary ionic mixtures

Science.gov (United States)

Ichimaru, S.; Ogata, S.; Van Horn, H. M.

1992-01-01

Through a combination of compositional scaling arguments and examinations of Monte Carlo simulation results for the interparticle separations in binary-ionic mixture (BIM) solids, we have derived parameterized expressions for the BIM pycnonuclear rates as generalizations of those in one-component solids obtained previously by Salpeter and Van Horn and by Ogata et al. We have thereby discovered a catalyzing effect of the heavier elements, which enhances the rates of reactions among the lighter elements when the charge ratio exceeds a critical value of approximately 2.3.

[Incidence rate of adverse reaction/event by Qingkailing injection: a Meta-analysis of single rate].

Science.gov (United States)

Ai, Chun-ling; Xie, Yan-ming; Li, Ming-quan; Wang, Lian-xin; Liao, Xing

2015-12-01

To systematically review the incidence rate of adverse drug reaction/event by Qingkailing injection. Such databases as the PubMed, EMbase, the Cochrane library, CNKI, VIP WanFang data and CBM were searched by computer from foundation to July 30, 2015. Two reviewers independently screened literature according to the inclusion and exclusion criteria, extracted data and cross check data. Then, Meta-analysis was performed by using the R 3.2.0 software, subgroup sensitivity analysis was performed based on age, mode of medicine, observation time and research quality. Sixty-three studies involving 9,793 patients with Qingkailing injection were included, 367 cases of adverse reactions/events were reported in total. The incidence rate of adverse reaction in skin and mucosa group was 2% [95% CI (0.02; 0.03)]; the digestive system adverse reaction was 6% [95% CI(0.05; 0.07); the injection site adverse reaction was 4% [95% CI (0.02; 0.07)]. In the digestive system as the main types of adverse reactions/events, incidence of children and adults were 4.6% [0.021 1; 0.097 7] and 6.9% [0.053 5; 0.089 8], respectively. Adverse reactions to skin and mucous membrane damage as the main performance/event type, the observation time > 7 days and ≤ 7 days incidence of 3% [0.012 9; 0.068 3] and 1.9% [0.007 8; 0.046 1], respectively. Subgroup analysis showed that different types of adverse reactions, combination in the incidence of adverse reactions/events were higher than that of single drug, the difference was statistically significant (P reactions occur, and clinical rational drug use, such as combination, age and other fators, and the influence factors vary in different populations. Therefore, clinical doctors for children and the elderly use special care was required for a clear and open spirit injection, the implementation of individualized medication.

Interlaboratory reaction rate program. 12th progress report, November 1976-October 1979

International Nuclear Information System (INIS)

Lippincott, E.P.; McElroy, W.N.; Preston, C.C.

1980-09-01

The Interlaboratory Reaction Rate UILRR) program is establishing the capability to accurately measure neutron-induced reactions and reaction rates for reactor fuels and materials development programs. The goal for the principal fission reactions, 235 U, 238 U and 239 Pu, is an accuracy to within +- 5% at the 95% confidence level. Accurate measurement of other fission and nonfission reactions is also required, but to a lesser accuracy, between +- 5% and 10% at the 95% confidence level. A secondary program objective is improvement in knowledge of the nuclear parameters involved in the standarization of fuels and materials dosimetry measurements of neutron flux, spectra, fluence and burnup

Simulation of biochemical reactions with time-dependent rates by the rejection-based algorithm

Energy Technology Data Exchange (ETDEWEB)

Thanh, Vo Hong, E-mail: vo@cosbi.eu [The Microsoft Research - University of Trento Centre for Computational and Systems Biology, Piazza Manifattura 1, Rovereto 38068 (Italy); Priami, Corrado, E-mail: priami@cosbi.eu [The Microsoft Research - University of Trento Centre for Computational and Systems Biology, Piazza Manifattura 1, Rovereto 38068 (Italy); Department of Mathematics, University of Trento, Trento (Italy)

2015-08-07

We address the problem of simulating biochemical reaction networks with time-dependent rates and propose a new algorithm based on our rejection-based stochastic simulation algorithm (RSSA) [Thanh et al., J. Chem. Phys. 141(13), 134116 (2014)]. The computation for selecting next reaction firings by our time-dependent RSSA (tRSSA) is computationally efficient. Furthermore, the generated trajectory is exact by exploiting the rejection-based mechanism. We benchmark tRSSA on different biological systems with varying forms of reaction rates to demonstrate its applicability and efficiency. We reveal that for nontrivial cases, the selection of reaction firings in existing algorithms introduces approximations because the integration of reaction rates is very computationally demanding and simplifying assumptions are introduced. The selection of the next reaction firing by our approach is easier while preserving the exactness.

Analyzing Reaction Rates with the Distortion/Interaction-Activation Strain Model

NARCIS (Netherlands)

Bickelhaupt, F. Matthias; Houk, Kendall N.

2017-01-01

The activation strain or distortion/interaction model is a tool to analyze activation barriers that determine reaction rates. For bimolecular reactions, the activation energies are the sum of the energies to distort the reactants into geometries they have in transition states plus the interaction

Pop-It Beads to Introduce Catalysis of Reaction Rate and Substrate Depletion Effects

Science.gov (United States)

Gehret, Austin U.

2017-01-01

A kinesthetic classroom activity was designed to help students understand enzyme activity and catalysis of reaction rate. Students served the role of enzymes by manipulating Pop-It Beads as the catalytic event. This activity illuminates the relationship between reaction rate and reaction progress by allowing students to experience first-hand the…

Metabolic control analysis of biochemical pathways based on a thermokinetic description of reaction rates

DEFF Research Database (Denmark)

Nielsen, Jens Bredal

1997-01-01

Metabolic control analysis is a powerful technique for the evaluation of flux control within biochemical pathways. Its foundation is the elasticity coefficients and the flux control coefficients (FCCs). On the basis of a thermokinetic description of reaction rates it is here shown...... that the elasticity coefficients can be calculated directly from the pool levels of metabolites at steady state. The only requirement is that one thermodynamic parameter be known, namely the reaction affinity at the intercept of the tangent in the inflection point of the curve of reaction rate against reaction...... of the thermokinetic description of reaction rates to include the influence of effecters. Here the reaction rate is written as a linear function of the logarithm of the metabolite concentrations. With this type of rate function it is shown that the approach of Delgado and Liao [Biochem. J. (1992) 282, 919-927] can...

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

International Nuclear Information System (INIS)

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

1976-01-01

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

Multiscale Investigation on Biofilm Distribution and Its Impact on Macroscopic Biogeochemical Reaction Rates

Science.gov (United States)

Yan, Zhifeng; Liu, Chongxuan; Liu, Yuanyuan; Bailey, Vanessa L.

2017-11-01

Biofilms are critical locations for biogeochemical reactions in the subsurface environment. The occurrence and distribution of biofilms at microscale as well as their impacts on macroscopic biogeochemical reaction rates are still poorly understood. This paper investigated the formation and distributions of biofilms in heterogeneous sediments using multiscale models and evaluated the effects of biofilm heterogeneity on local and macroscopic biogeochemical reaction rates. Sediment pore structures derived from X-ray computed tomography were used to simulate the microscale flow dynamics and biofilm distribution in the sediment column. The response of biofilm formation and distribution to the variations in hydraulic and chemical properties was first examined. One representative biofilm distribution was then utilized to evaluate its effects on macroscopic reaction rates using nitrate reduction as an example. The results revealed that microorganisms primarily grew on the surfaces of grains and aggregates near preferential flow paths where both electron donor and acceptor were readily accessible, leading to the heterogeneous distribution of biofilms in the sediments. The heterogeneous biofilm distribution decreased the macroscopic rate of biogeochemical reactions as compared with those in homogeneous cases. Operationally considering the heterogeneous biofilm distribution in macroscopic reactive transport models such as using dual porosity domain concept can significantly improve the prediction of biogeochemical reaction rates. Overall, this study provided important insights into the biofilm formation and distribution in soils and sediments as well as their impacts on the macroscopic manifestation of reaction rates.

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.

Coloring Rate of Phenolphthalein by Reaction with Alkaline Solution Observed by Liquid-Droplet Collision.

Science.gov (United States)

Takano, Yuuka; Kikkawa, Shigenori; Suzuki, Tomoko; Kohno, Jun-ya

2015-06-11

Many important chemical reactions are induced by mixing two solutions. This paper presents a new way to measure rates of rapid chemical reactions induced by mixing two reactant solutions using a liquid-droplet collision. The coloring reaction of phenolphthalein (H2PP) by a reaction with NaOH is investigated kinetically. Liquid droplets of H2PP/ethanol and NaOH/H2O solutions are made to collide, which induces a reaction that transforms H2PP into a deprotonated form (PP(2-)). The concentration of PP(2-) is evaluated from the RGB values of pixels in the colored droplet images, and is measured as a function of the elapsed time from the collision. The obtained rate constant is (2.2 ± 0.7) × 10(3) M(-1) s(-1), which is the rate constant for the rate-determining step of the coloring reaction of H2PP. This method was shown to be applicable to determine rate constants of rapid chemical reactions between two solutions.

Rate of reaction of dimethylmercury with oxygen atoms in the gas phase

DEFF Research Database (Denmark)

Egsgaard, Helge

1986-01-01

The rate constant for the reaction of atomic oxygen (O(3P)) with dimethylmercury has been measured at room temperature at a pressure of about 1 Torr using a fast flow system with electron paramagnetic resonance and mass spectrometric detection. Some reaction products were identified. The rate...

Neutron Scattering in Hydrogenous Moderators, Studied by Time Dependent Reaction Rate Method

Energy Technology Data Exchange (ETDEWEB)

Larsson, L G; Moeller, E; Purohit, S N

1966-03-15

The moderation and absorption of a neutron burst in water, poisoned with the non-1/v absorbers cadmium and gadolinium, has been followed on the time scale by multigroup calculations, using scattering kernels for the proton gas and the Nelkin model. The time dependent reaction rate curves for each absorber display clear differences for the two models, and the separation between the curves does not depend much on the absorber concentration. An experimental method for the measurement of infinite medium reaction rate curves in a limited geometry has been investigated. This method makes the measurement of the time dependent reaction rate generally useful for thermalization studies in a small geometry of a liquid hydrogenous moderator, provided that the experiment is coupled to programs for the calculation of scattering kernels and time dependent neutron spectra. Good agreement has been found between the reaction rate curve, measured with cadmium in water, and a calculated curve, where the Haywood kernel has been used.

Absolute and relative-rate measurement of the rate coefficient for reaction of perfluoro ethyl vinyl ether (C2F5OCF[double bond, length as m-dash]CF2) with OH.

Science.gov (United States)

Srinivasulu, G; Bunkan, A J C; Amedro, D; Crowley, J N

2018-01-31

The rate coefficient (k 1 ) for the reaction of OH radicals with perfluoro ethyl vinyl ether (PEVE, C 2 F 5 OCF[double bond, length as m-dash]CF 2 ) has been measured as a function of temperature (T = 207-300 K) using the technique of pulsed laser photolysis with detection of OH by laser-induced fluorescence (PLP-LIF) at pressures of 50 or 100 Torr N 2 bath gas. In addition, the rate coefficient was measured at 298 K and in one atmosphere of air by the relative-rate technique with loss of PEVE and reference reactant monitored in situ by IR absorption spectroscopy. The rate coefficient has a negative temperature dependence which can be parameterized as: k 1 (T) = 6.0 × 10 -13  exp[(480 ± 38/T)] cm 3 molecule -1 s -1 and a room temperature value of k 1 (298 K) = (3.0 ± 0.3) × 10 -12 cm 3 molecule -1 s -1 . Highly accurate rate coefficients from the PLP-LIF experiments were achieved by optical on-line measurements of PEVE and by performing the measurements at two different apparatuses. The large rate coefficient and the temperature dependence indicate that the reaction proceeds via OH addition to the C[double bond, length as m-dash]C double bond, the high pressure limit already being reached at 50 Torr N 2 . Based on the rate coefficient and average OH levels, the atmospheric lifetime of PEVE was estimated to be a few days.

Reaction of atomic bromine with acetylene and loss rate of atmospheric acetylene due to reaction with OH, Cl, O, and Br

Science.gov (United States)

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

1986-01-01

The first-order, diffusion, and bimolecular rate constants for the reaction Br + C2H2 yields C2H3Br are evaluated. The rate constants are measured at 210, 248, 298, and 393 K and at pressures between 15-100 torr Ar using flash photolysis combined with time-resolved detection of atomic bromine via Br resonance radiation. It is observed that the reaction is not affected by pressure or temperature and the bimolecular constant = (4.0 + or - 0.8) x 10 to the -15th cu cm/sec with an error of two standard deviations. The C2H2 + Br reaction rates are compared with reactions of C2H2 with Cl, OH, NH2, and H. The loss rates for atmospheric C2H2 for reactions with OH, Cl, O, and Br are calculated as a function of altitude.

Comparing transfusion reaction rates for various plasma types: a systematic review and meta-analysis/regression.

Science.gov (United States)

Saadah, Nicholas H; van Hout, Fabienne M A; Schipperus, Martin R; le Cessie, Saskia; Middelburg, Rutger A; Wiersum-Osselton, Johanna C; van der Bom, Johanna G

2017-09-01

We estimated rates for common plasma-associated transfusion reactions and compared reported rates for various plasma types. We performed a systematic review and meta-analysis of peer-reviewed articles that reported plasma transfusion reaction rates. Random-effects pooled rates were calculated and compared between plasma types. Meta-regression was used to compare various plasma types with regard to their reported plasma transfusion reaction rates. Forty-eight studies reported transfusion reaction rates for fresh-frozen plasma (FFP; mixed-sex and male-only), amotosalen INTERCEPT FFP, methylene blue-treated FFP, and solvent/detergent-treated pooled plasma. Random-effects pooled average rates for FFP were: allergic reactions, 92/10 5 units transfused (95% confidence interval [CI], 46-184/10 5 units transfused); febrile nonhemolytic transfusion reactions (FNHTRs), 12/10 5 units transfused (95% CI, 7-22/10 5 units transfused); transfusion-associated circulatory overload (TACO), 6/10 5 units transfused (95% CI, 1-30/10 5 units transfused); transfusion-related acute lung injury (TRALI), 1.8/10 5 units transfused (95% CI, 1.2-2.7/10 5 units transfused); and anaphylactic reactions, 0.8/10 5 units transfused (95% CI, 0-45.7/10 5 units transfused). Risk differences between plasma types were not significant for allergic reactions, TACO, or anaphylactic reactions. Methylene blue-treated FFP led to fewer FNHTRs than FFP (risk difference = -15.3 FNHTRs/10 5 units transfused; 95% CI, -24.7 to -7.1 reactions/10 5 units transfused); and male-only FFP led to fewer cases of TRALI than mixed-sex FFP (risk difference = -0.74 TRALI/10 5 units transfused; 95% CI, -2.42 to -0.42 injuries/10 5 units transfused). Meta-regression demonstrates that the rate of FNHTRs is lower for methylene blue-treated compared with FFP, and the rate of TRALI is lower for male-only than for mixed-sex FFP; whereas no significant differences are observed between plasma types for allergic reactions, TACO

The effect of composition of mixture on rate of radiation initiation of chain reactions

International Nuclear Information System (INIS)

Poluehktov, V.A.; Begishev, I.R.; Podkhalyuzin, A.T.; Babkina, Eh.I.; Morozov, V.A.; Shapovalov, V.V.

1977-01-01

The effect of the composition of starting components on the rate of a number of chain liquid-phase reactions initiated by γ-quanta of Co 60 has been investigated at constant temperature and dosage rate. In regard to 1,1-difluoroethane chlorination, cyclohexene phosphorylation and adamantane alkylation with hexafluoropropylene reactions, abnormal effect of the reagent compositions on reaction rates has been discovered. The possible radical - starting molecule complexing reaction and molecular complexing from the starting components have been considered

IVO, a device for In situ Volatilization and On-line detection of products from heavy ion reactions

CERN Document Server

Duellmann, C E; Eichler, R; Gäggeler, H W; Jost, D T; Piguet, D; Türler, A

2002-01-01

A new gaschromatographic separation system to rapidly isolate heavy ion reaction products in the form of highly volatile species is described. Reaction products recoiling from the target are stopped in a gas volume and converted in situ to volatile species, which are swept by the carrier gas to a chromatography column. Species that are volatile under the given conditions pass through the column. In a cluster chamber, which is directly attached to the exit of the column, the isolated volatile species are chemically adsorbed to the surface of aerosol particles and transported to an on-line detection system. The whole set-up was tested using short-lived osmium (Os) and mercury (Hg) nuclides produced in heavy ion reactions to model future chemical studies with hassium (Hs, Z=108) and element 112. By varying the temperature of the isothermal section of the chromatography column between room temperature and -80 deg. C, yield measurements of given species can be conducted, yielding information about the volatility o...

Accurate label-free reaction kinetics determination using initial rate heat measurements

Science.gov (United States)

Ebrahimi, Kourosh Honarmand; Hagedoorn, Peter-Leon; Jacobs, Denise; Hagen, Wilfred R.

2015-01-01

Accurate label-free methods or assays to obtain the initial reaction rates have significant importance in fundamental studies of enzymes and in application-oriented high throughput screening of enzyme activity. Here we introduce a label-free approach for obtaining initial rates of enzyme activity from heat measurements, which we name initial rate calorimetry (IrCal). This approach is based on our new finding that the data recorded by isothermal titration calorimetry for the early stages of a reaction, which have been widely ignored, are correlated to the initial rates. Application of the IrCal approach to various enzymes led to accurate enzyme kinetics parameters as compared to spectroscopic methods and enabled enzyme kinetic studies with natural substrate, e.g. proteases with protein substrates. Because heat is a label-free property of almost all reactions, the IrCal approach holds promise in fundamental studies of various enzymes and in use of calorimetry for high throughput screening of enzyme activity. PMID:26574737

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

Science.gov (United States)

Maher, K.; Steefel, Carl; White, A.F.; Stonestrom, David A.

2009-01-01

the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO2(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws. ?? 2009 Elsevier Ltd.

Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study; Hydratation des argiles gonflantes et influence des bacteries. Etude experimentale de reaction in situ

Energy Technology Data Exchange (ETDEWEB)

Berger, J

2008-01-15

This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour

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.

Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

Science.gov (United States)

Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

2017-02-09

The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

Putting Reaction Rates and Collision Theory in the Hands of Your Students.

Science.gov (United States)

Evenson, Andy

2002-01-01

Describes a simulation that can be used to give concrete analogies of collision theory and the factors that affect reaction rates including temperature, concentration, catalyst, and molecular orientation. The simulation works best if done as an introduction to the concepts to help prevent misconceptions about reaction rates and collision theory.…

Accurate quantum calculations of the reaction rates for H/D+ CH4

NARCIS (Netherlands)

Harrevelt, R. van; Nyman, G.; Manthe, U.

2007-01-01

In previous work [T. Wu, H. J. Werner, and U. Manthe, Science 306, 2227 (2004)], accurate quantum reaction rate calculations of the rate constant for the H+CH4 -> CH3+H-2 reaction have been presented. Both the electronic structure calculations and the nuclear dynamics calculations are converged with

Study on the fabrication of Al matrix composites strengthened by combined in-situ alumina particle and in-situ alloying elements

International Nuclear Information System (INIS)

Huang Zanjun; Yang Bin; Cui Hua; Zhang Jishan

2003-01-01

A new idea to fabricate aluminum matrix composites strengthened by combined in-situ particle strengthening and in-situ alloying has been proposed. Following the concept of in-situ alloying and in-situ particle strengthening, aluminum matrix composites reinforced by Cu and α-Al 2 O 3 particulate (material I) and the same matrix reinforced by Cu, Si alloying elements and α-Al 2 O 3 particulate (material II) have been obtained. SEM observation, EDS and XRD analysis show that the alloy elements Cu and Si exist in the two materials, respectively. In-situ Al 2 O 3 particulates are generally spherical and their mean size is less than 0.5 μm. TEM observation shows that the in-situ α-Al 2 O 3 particulates have a good cohesion with the matrix. The reaction mechanism of the Al 2 O 3 particulate obtained by this method was studied. Thermodynamic considerations are given to the in-situ reactions and the distribution characteristic of in-situ the α-Al 2 O 3 particulate in the process of solidification is also discussed

In situ composition measurements of Bunsen reaction solution by radiation probes

Energy Technology Data Exchange (ETDEWEB)

Kubo, Shinji; Nagaya, Yasunobu [Japan Atomic Energy Agency (Japan)

2010-07-01

Measuring equipments are integral to chemical process controls. A stable hydrogen production by the Iodine-Sulfur thermochemical water-splitting process is relatively difficult because of lack of existing in situ composition measurement techniques for multiple components and corrosive solution. Composition regulations of Bunsen reaction solution is particularly important, since a closed cycle system provided with this process causes that the many streams with different composition return to this section. Accordingly Bunsen solution becomes changeable composition. Radiation probes have a potential for applications to determine this multiple component solution while the non-contact approach avoids the corrosive issues. Moreover the probes have features of the promptness, contact-less and sequential use. Laboratory scale experiments to evaluate these possibilities of the measurement were conducted with use of simulated Bunsen solution, HIx solution and H{sub 2}SO{sub 4} solution, containing HI, I2, H{sub 2}SO{sub 4} and H{sub 2}O and sealed radiation sources. Radiations were counted, which were interacted with the solutions in various compositions around room temperature contained in vessels. For HIx solution, the obtained counting rates were correlated with hydrogen volume concentrations; moreover, the application of the Monte Carlo method suggests possibilities that the detector responses for HIx solution by the radiation probes are predictable. For H{sub 2}SO{sub 4} solution, iodine atoms had significant influences on the relationship between output values of two gamma-ray density meters, cesium source as higher energy and barium source as lower energy. This results suggest that the neutron ray probe, the gamma-ray probes of both lower energy and higher energy have possibilities to determine the composition of Bunsen solution of HIx and H{sub 2}SO{sub 4} solutions. (orig.)

In-situ investigation of hydrogen evolution behavior in vanadium redox flow batteries

International Nuclear Information System (INIS)

Wei, L.; Zhao, T.S.; Xu, Q.; Zhou, X.L.; Zhang, Z.H.

2017-01-01

Highlights: • An in-situ method to investigate hydrogen evolution in VRFBs is developed. • The rate of hydrogen evolution during battery operation is quantified. • The gas evolution behaviors in the charge process of VRFBs are observed. - Abstract: In this work, we conceived and fabricated a three-electrode electrochemical cell and transparent vanadium redox flow battery to in-situ investigate the hydrogen evolution reaction during battery operation. Experimental results show that operating temperature has a strong influence on the HER rate. In particular, compared with V"3"+ reduction reaction, HER is more sensitive to temperature variation. It is also found that, contrary to the conventional wisdom that side reactions occur at the late stage of the charge process, H_2 evolves at a relatively low SOC. About 0.26 and 1.94 mL H_2 were collected at an early (SOC lower than 20%) and end of the charge process, respectively, suggesting that attention to the hydrogen formation at the negative electrode in the early charge process should also be paid to during long-term battery operations. Moreover, the produced hydrogen gas at the negative side prefers to form macroscopically observable bubbles onto the electrode surface, covering the active sites for vanadium redox reactions, while oxygen evolution (including CO_2 production) at the positive side corrodes electrode surface and introduces certain oxygen-containing functional groups.

Material interactions with the Low Earth Orbital (LEO) environment: Accurate reaction rate measurements

Science.gov (United States)

Visentine, James T.; Leger, Lubert J.

1987-01-01

To resolve uncertainties in estimated LEO atomic oxygen fluence and provide reaction product composition data for comparison to data obtained in ground-based simulation laboratories, a flight experiment has been proposed for the space shuttle which utilizes an ion-neutral mass spectrometer to obtain in-situ ambient density measurements and identify reaction products from modeled polymers exposed to the atomic oxygen environment. An overview of this experiment is presented and the methodology of calibrating the flight mass spectrometer in a neutral beam facility prior to its use on the space shuttle is established. The experiment, designated EOIM-3 (Evaluation of Oxygen Interactions with Materials, third series), will provide a reliable materials interaction data base for future spacecraft design and will furnish insight into the basic chemical mechanisms leading to atomic oxygen interactions with surfaces.

Dynamical observation of lithium insertion/extraction reaction during charge-discharge processes in Li-ion batteries by in situ spatially resolved electron energy-loss spectroscopy.

Science.gov (United States)

Shimoyamada, Atsushi; Yamamoto, Kazuo; Yoshida, Ryuji; Kato, Takehisa; Iriyama, Yasutoshi; Hirayama, Tsukasa

2015-12-01

All-solid-state Li-ion batteries (LIBs) with solid electrolytes are expected to be the next generation devices to overcome serious issues facing conventional LIBs with liquid electrolytes. However, the large Li-ion transfer resistance at the electrode/solid-electrolyte interfaces causes low power density and prevents practical use. In-situ-formed negative electrodes prepared by decomposing the solid electrolyte Li(1+x+3z)Alx(Ti,Ge)(2-x)Si(3z)P(3-z)O12 (LASGTP) with an excess Li-ion insertion reaction are effective electrodes providing low Li-ion transfer resistance at the interfaces. Prior to our work, however, it had still been unclear how the negative electrodes were formed in the parent solid electrolytes. Here, we succeeded in dynamically visualizing the formation by in situ spatially resolved electron energy-loss spectroscopy in a transmission electron microscope mode (SR-TEM-EELS). The Li-ions were gradually inserted into the solid electrolyte region around 400 nm from the negative current-collector/solid-electrolyte interface in the charge process. Some of the ions were then extracted in the discharge process, and the rest were diffused such that the distribution was almost flat, resulting in the negative electrodes. The redox reaction of Ti(4+)/Ti(3+) in the solid electrolyte was also observed in situ during the Li insertion/extraction processes. The in situ SR-TEM-EELS revealed the mechanism of the electrochemical reaction in solid-state batteries. © The Author 2015. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

In-situ real time measurements of net erosion rates of copper during hydrogen plasma exposure

Science.gov (United States)

Kesler, Leigh; Wright, Graham; Peterson, Ethan; Whyte, Dennis

2013-10-01

In order to properly understand the dynamics of net erosion/deposition in fusion reactors, such as tokamaks, a diagnostic measuring the real time rates of net erosion/deposition during plasma exposure is necessary. The DIONISOS experiment produces real time measurements of net erosion/deposition by using Rutherford backscattering spectroscopy (RBS) ion beam analysis simultaneously with plasma exposure from a helicon plasma source. This in-situ method improves on ex-situ weight loss measurements by allowing measurement of possible synergistic effects of high ion implantation rates and net erosion rate and by giving a real time response to changes in plasma parameters. Previous work has validated this new technique for measuring copper (Cu) erosion from helium (He) plasma ion bombardment. This technique is now extended to measure copper erosion due to deuterium and hydrogen plasma ion exposure. Targets used were a 1.5 μm Cu layer on an aluminum substrate. Cu layer thickness is tracked in real time using 1.2 MeV proton RBS. Measured erosion rates will be compared to results from literature and He erosion rates. Supported by US DoE award DE-SC00-02060.

Effects of Surfactants on the Rate of Chemical Reactions

Directory of Open Access Journals (Sweden)

B. Samiey

2014-01-01

Full Text Available Surfactants are self-assembled compounds that depend on their structure and electric charge can interact as monomer or micelle with other compounds (substrates. These interactions which may catalyze or inhibit the reaction rates are studied with pseudophase, cooperativity, and stoichiometric (classical models. In this review, we discuss applying these models to study surfactant-substrate interactions and their effects on Diels-Alder, redox, photochemical, decomposition, enzymatic, isomerization, ligand exchange, radical, and nucleophilic reactions.

Conventional and in situ transesterification of sunflower seed oil for the production of biodiesel

Energy Technology Data Exchange (ETDEWEB)

Georgogianni, K.G.; Kontominas, M.G.; Pomonis, P.J. [Section of Industrial and Food Chemistry, Department of Chemistry, University of Ioannina 45110-Ioannina (Greece); Avlonitis, D. [Department of Petroleum Technology, TEI of Chalkida, 34600-Kavala (Greece); Gergis, V. [Department of Food Technology, TEI of Athens, 12210-Egaleo (Greece)

2008-05-15

In the present work the alkaline transesterification of sunflower seed oil with methanol and ethanol, for the production of biodiesel fuel was studied. Both conventional and in situ transesterification were investigated using low frequency ultrasonication (24 kHz) and mechanical stirring (600 rpm). Use of ultrasonication in conventional transesterification with methanol gave high yields of methyl esters (95%) after a short reaction time (20 min) similar to those using mechanical stirring. Use of ultrasonication in conventional transesterification with ethanol gave similar yields to those using mechanical stirring but significantly lower than respective yields using methanol. In the in situ transesterification the use of ultrasonication and mechanical stirring led to similar high yields (95%) of methyl esters after approximately 20 min of reaction time. In the presence of ethanol use of ultrasonication led to high ester yields (98%) in only 40 min of reaction time while use of mechanical stirring gave lower yields (88%) even after 4 h of reaction time. In situ transesterification gave similar ester yields to those obtained by conventional transesterification being an alternative, efficient and economical process. In all cases a concentration of 2.0% NaOH gave higher ester yields. Reaction rate constants were calculated, using first order reaction kinetics, to be equal to 3.1 x 10{sup -} {sup 3} s{sup -} {sup 1} for conventional transesterification using methanol and 2.0% NaOH, and 9.5 x 10{sup -} {sup 4} s{sup -} {sup 1} using ethanol. (author)

Rapid thermal processing chamber for in-situ x-ray diffraction

Energy Technology Data Exchange (ETDEWEB)

Ahmad, Md. Imteyaz; Van Campen, Douglas G.; Yu, Jiafan; Pool, Vanessa L.; Van Hest, Maikel F. A. M.; Toney, Michael F., E-mail: mftoney@slac.stanford.edu [SSRL, SLAC National Accelerator Laboratory, 2575, Sand Hill Road, Menlo Park, California 94025 (United States); Fields, Jeremy D.; Parilla, Philip A.; Ginley, David S. [National Renewable Energy Laboratory, Golden, Colorado 80401 (United States)

2015-01-15

Rapid thermal processing (RTP) is widely used for processing a variety of materials, including electronics and photovoltaics. Presently, optimization of RTP is done primarily based on ex-situ studies. As a consequence, the precise reaction pathways and phase progression during the RTP remain unclear. More awareness of the reaction pathways would better enable process optimization and foster increased adoption of RTP, which offers numerous advantages for synthesis of a broad range of materials systems. To achieve this, we have designed and developed a RTP instrument that enables real-time collection of X-ray diffraction data with intervals as short as 100 ms, while heating with ramp rates up to 100 °Cs{sup −1}, and with a maximum operating temperature of 1200 °C. The system is portable and can be installed on a synchrotron beamline. The unique capabilities of this instrument are demonstrated with in-situ characterization of a Bi{sub 2}O{sub 3}-SiO{sub 2} glass frit obtained during heating with ramp rates 5 °C s{sup −1} and 100 °C s{sup −1}, revealing numerous phase changes.

Reaction rate calculations via transmission coefficients

International Nuclear Information System (INIS)

Feit, M.D.; Alder, B.J.

1985-01-01

The transmission coefficient of a wavepacket traversing a potential barrier can be determined by steady state calculations carried out in imaginary time instead of by real time dynamical calculations. The general argument is verified for the Eckart barrier potential by a comparison of transmission coefficients calculated from real and imaginary time solutions of the Schroedinger equation. The correspondence demonstrated here allows a formulation for the reaction rate that avoids difficulties due to both rare events and explicitly time dependent calculations. 5 refs., 2 figs

"Depletion": A Game with Natural Rules for Teaching Reaction Rate Theory.

Science.gov (United States)

Olbris, Donald J.; Herzfeld, Judith

2002-01-01

Depletion is a game that reinforces central concepts of reaction rate theory through simulation. Presents the game with a set of follow-up questions suitable for either a quiz or discussion. Also describes student reaction to the game. (MM)

Estimation of the prevalence and rate of acute transfusion reactions occurring in Windhoek, Namibia

Science.gov (United States)

Meza, Benjamin P.L.; Lohrke, Britta; Wilkinson, Robert; Pitman, John P.; Shiraishi, Ray W.; Bock, Naomi; Lowrance, David W.; Kuehnert, Matthew J.; Mataranyika, Mary; Basavaraju, Sridhar V.

2014-01-01

Background Acute transfusion reactions are probably common in sub-Saharan Africa, but transfusion reaction surveillance systems have not been widely established. In 2008, the Blood Transfusion Service of Namibia implemented a national acute transfusion reaction surveillance system, but substantial under-reporting was suspected. We estimated the actual prevalence and rate of acute transfusion reactions occurring in Windhoek, Namibia. Methods The percentage of transfusion events resulting in a reported acute transfusion reaction was calculated. Actual percentage and rates of acute transfusion reactions per 1,000 transfused units were estimated by reviewing patients’ records from six hospitals, which transfuse >99% of all blood in Windhoek. Patients’ records for 1,162 transfusion events occurring between 1st January – 31st December 2011 were randomly selected. Clinical and demographic information were abstracted and Centers for Disease Control and Prevention National Healthcare Safety Network criteria were applied to categorize acute transfusion reactions1. Results From January 1 – December 31, 2011, there were 3,697 transfusion events (involving 10,338 blood units) in the selected hospitals. Eight (0.2%) acute transfusion reactions were reported to the surveillance system. Of the 1,162 transfusion events selected, medical records for 785 transfusion events were analysed, and 28 acute transfusion reactions were detected, of which only one had also been reported to the surveillance system. An estimated 3.4% (95% confidence interval [CI]: 2.3–4.4) of transfusion events in Windhoek resulted in an acute transfusion reaction, with an estimated rate of 11.5 (95% CI: 7.6–14.5) acute transfusion reactions per 1,000 transfused units. Conclusion The estimated actual rate of acute transfusion reactions is higher than the rate reported to the national haemovigilance system. Improved surveillance and interventions to reduce transfusion-related morbidity and mortality

A simple thermometric technique for reaction-rate determination of inorganic species, based on the iodide-catalysed cerium(IV)-arsenic(III) reaction.

Science.gov (United States)

Grases, F; Forteza, R; March, J G; Cerda, V

1985-02-01

A very simple reaction-rate thermometric technique is used for determination of iodide (5-20 ng ml ), based on its catalytic action on the cerium(IV)-arsenic(III) reaction, and for determination of mercury(II) (1.5-10 ng ml ) and silver(I) (2-10 ng ml ), based on their inhibitory effect on this reaction. The reaction is followed by measuring the rate of temperature increase. The method suffers from very few interferences and is applied to determination of iodide in biological and inorganic samples, and Hg(II) and Ag(I) in pharmaceutical products.

In-situ virtual metrology for the silicon-dioxide etch rate by using optical emission spectroscopy data

International Nuclear Information System (INIS)

Kim, Boomsoo; Hong, Sangjeen

2014-01-01

As a useful tool for process control in a high volume semiconductor manufacturing environment, virtual metrology for the etch rate in a plasma etch process is investigated using optical emission spectroscopy (OES) data. Virtual metrology is a surrogate measurement taken from the process instead of from direct measurement, and it can provide in-situ metrology of a wafer's geometry from a predictive model. A statistical regression model that correlates the selected wavelengths of the optical emission spectra to the etch rate is established using the OES data collected over 20 experimental runs. In addition, an argon actinometry study is employed to quantify the OES data, and it provides valuable insight into the analysis of the OES data. The established virtual metrology model is further verified with an additional 20 runs of data. As a result, the virtual metrology model with both process recipe tool data and in-situ data shows higher prediction accuracy by as much as 56% compared with either the process recipe tool data or the in-situ data alone.

Modification of Clays by Sol-Gel Reaction and Their Use in the Ethylene In Situ Polymerization for Obtaining Nanocomposites

Directory of Open Access Journals (Sweden)

E. Moncada

2012-01-01

Full Text Available The nanocomposites formation by in situ polymerization used a metallocene catalyst (butyl-2-cyclopentadienyl zirconium 2-chlorines and a hectorite synthetic clay type which is discussed. This research was carried out in two phases. The first phase consisted of mixing the components of the metallocenic polymerization reaction (metallocene-methylaluminoxane-ethylene with clay in a reactor. In the second phase, the metallocenic catalytic system was supported by clay particles and then a polymerization reaction was made. In this second phase, the clay particles were modified using a sol-gel reaction with different pH values: pH = 3, pH = 8, and pH = 12. The results were compared in terms of the catalytic activity in the different systems (phase 1 and phase 2 and the nanoparticle morphology of nanocomposites generated in this study.

Reaction rate constant for uranium in water and water vapor

Energy Technology Data Exchange (ETDEWEB)

TRIMBLE, D.J.

1998-11-09

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

Helium generation reaction rates for 6Li and 10B in benchmark facilities

International Nuclear Information System (INIS)

Farrar, Harry IV; Oliver, B.M.; Lippincott, E.P.

1980-01-01

The helium generation rates for 10 B and 6 Li have been measured in two benchmark reactor facilities having neutron spectra similar to those found in a breeder reactor. The irradiations took place in the Coupled Fast Reactivity Measurements Facility (CFRMF) and in the 10% enriched 235 U critical assembly, BIG-10. The helium reaction rates were obtained by precise high-sensitivity gas mass spectrometric analyses of the helium content of numerous small samples. Comparison of these reaction rates with other reaction rates measured in the same facilities, and with rates calculated from published cross sections and from best estimates of the neutron spectral shapes, indicate significant discrepancies in the calculated values. Additional irradiations in other benchmark facilities have been undertaken to better determine the energy ranges where the discrepancies lie

The Influence of Particle Charge on Heterogeneous Reaction Rate Coefficients

Science.gov (United States)

Aikin, A. C.; Pesnell, W. D.

2000-01-01

The effects of particle charge on heterogeneous reaction rates are presented. Many atmospheric particles, whether liquid or solid are charged. This surface charge causes a redistribution of charge within a liquid particle and as a consequence a perturbation in the gaseous uptake coefficient. The amount of perturbation is proportional to the external potential and the square of the ratio of debye length in the liquid to the particle radius. Previous modeling has shown how surface charge affects the uptake coefficient of charged aerosols. This effect is now included in the heterogeneous reaction rate of an aerosol ensemble. Extension of this analysis to ice particles will be discussed and examples presented.

Study on in-situ electrochemical impedance spectroscopy measurement of anodic reaction in SO_2 depolarized electrolysis process

International Nuclear Information System (INIS)

Xue Lulu; Zhang Ping; Chen Songzhe; Wang Laijun

2014-01-01

SO_2 depolarized electrolysis (SDE) is the pivotal reaction in hybrid sulfur process, one of the most promising approaches for mass hydrogen production without CO_2 emission. The net result of hybrid sulfur process is to split water into hydrogen and oxygen at a relatively low voltage, which will dramatically decrease the energy consumption for the production of hydrogen. The potential loss of SDE process could be separated into four components, i.e. reversible cell potential, anode overpotential, cathode overpotential and ohmic loss. So far, it has been identified that the total cell potential for the SO_2 depolarized electrolyzer is dominantly controlled by sulfuric acid concentration of the anolyte and electrolysis temperature of the electrolysis process. In this work, an in-situ Electrochemical Impedance Spectroscopy (EIS) measurement of the anodic SDE reaction was conducted. Results show that anodic overpotential is mainly resulted from the SO_2 oxidation reaction other than ohmic resistance or mass transfer limitation. This study extends the understanding to SDE process and gives suggestions for the further improvement of the SDE performance. (author)

Communication: Rate coefficients from quasiclassical trajectory calculations from the reverse reaction: The Mu + H2 reaction re-visited

Science.gov (United States)

Homayoon, Zahra; Jambrina, Pablo G.; Aoiz, F. Javier; Bowman, Joel M.

2012-07-01

In a previous paper [P. G. Jambrina et al., J. Chem. Phys. 135, 034310 (2011), 10.1063/1.3611400] various calculations of the rate coefficient for the Mu + H2 → MuH + H reaction were presented and compared to experiment. The widely used standard quasiclassical trajectory (QCT) method was shown to overestimate the rate coefficients by several orders of magnitude over the temperature range 200-1000 K. This was attributed to a major failure of that method to describe the correct threshold for the reaction owing to the large difference in zero-point energies (ZPE) of the reactant H2 and product MuH (˜0.32 eV). In this Communication we show that by performing standard QCT calculations for the reverse reaction and then applying detailed balance, the resulting rate coefficient is in very good agreement with the other computational results that respect the ZPE, (as well as with the experiment) but which are more demanding computationally.

Measurement and analysis of reaction rate distributions of cores with spectrum shifter region

International Nuclear Information System (INIS)

Matsuura, Shigekazu; Shiroya, Seiji; Unesaki, Hironobu; Takeda, Toshikazu; Aizawa, Otohiko; Kanda, Keiji.

1995-01-01

A study for the neutronic characteristics of the spectrum-controlled neutron irradiation fields using various reflector materials was performed. Spectrum shifter regions were constructed in the upper reflector region of the solid moderated core (B-Core) of the Kyoto University Critical Assembly (KUCA). Beryllium, graphite and aluminum were selected as the loading materials for the spectrum shifter. Two tight-pitch lattice cores with different moderator-to-fuel volume ratio (V m /V f ) of 0.97 and 0.65 have been used. Axial reaction rate distributions of gold, nickel and indium wires were measured, and the spectrum index was defined as the Cd ratio of the gold wire and the ratio of gold reaction rate to nickel reaction rate. Using the conventional design calculation procedure, the experimental and calculated reaction rate and spectrum index show several disagreements. Detailed treatment of the neutron streaming effect, heterogeneous cell structure and depression factor are shown to be necessary for improving the agreement between experimental and calculated values. (author)

Thermonuclear Reaction Rate Libraries and Software Tools for Nuclear Astrophysics Research

International Nuclear Information System (INIS)

Smith, Michael S.; Cyburt, Richard; Schatz, Hendrik; Smith, Karl; Warren, Scott; Ferguson, Ryan; Wiescher, Michael; Lingerfelt, Eric; Buckner, Kim; Nesaraja, Caroline D.

2008-01-01

Thermonuclear reaction rates are a crucial input for simulating a wide variety of astrophysical environments. A new collaboration has been formed to ensure that astrophysical modelers have access to reaction rates based on the most recent experimental and theoretical nuclear physics information. To reach this goal, a new version of the REACLIB library has been created by the Joint Institute for Nuclear Astrophysics (JINA), now available online at http://www.nscl.msu.edu/~nero/db. A complementary effort is the development of software tools in the Computational Infrastructure for Nuclear Astrophysics, online at nucastrodata.org, to streamline, manage, and access the workflow of the reaction evaluations from their initiation to peer review to incorporation into the library. Details of these new projects will be described

Facile Synthesis of In–Situ Nitrogenated Graphene Decorated by Few–Layer MoS2 for Hydrogen Evolution Reaction

International Nuclear Information System (INIS)

Dai, Xiaoping; Li, Zhanzhao; Du, Kangli; Sun, Hui; Yang, Ying; Zhang, Xin; Ma, Xingyu; Wang, Jie

2015-01-01

Graphical abstract: In–situ nitrogenated graphene–few layer MoS 2 composites are fabricated by combinating chemical and hydrothermal reduction. The resulting MoS 2 /N–rGO–HA by N 2 H 4 ·H 2 O and NH 3 ·H 2 O as co-reductant exhibits high activity and remarkable stability for hydrogen evolution reaction (HER). The excellent electro-catalytic performance is ascribed to the synergistic effects, confinement effects and highly dispersed MoS 2 nanosheets on N-doping rGO. Display Omitted -- Highlights: • In–situ nitrogenated graphene–few layer MoS 2 composites are fabricated by combinating chemical and hydrothermal co-reduction. • The resulting MoS 2 /N–rGO–HA exhibits high activity and remarkable stability for HER. • The excellent electro-catalytic performance is ascribed to the synergistic effects, confinement effects and highly dispersed MoS 2 nanosheets on N-doping rGO. -- Abstract: A facile one–step synthetic strategy by combinating chemical and hydrothermal reduction of graphene oxide and Mo precursor is proposed to fabricate in–situ nitrogenated graphene–few layer MoS 2 composite (MoS 2 /N–rGO–HA) for hydrogen evolution reaction (HER). The N–doping graphene nanosheets and highly dispersed MoS 2 nanosheets by ammonia and hydrozine as co–reductant have greatly promoted the N content, concentrations of pyridinic and graphitic N, the electron transport in electrodes, and assure high catalytic efficiency. The MoS 2 /N–rGO–HA composite exhibits extremely high activity in acidic solutions with a small onset potential of 100 mV and Tafel slope of 45 mV/dec, as well as a current density about 32.4 mA cm −2 at overpotential about 0.2 V. Moreover, such MoS 2 /N–rGO–HA electroncatalyst also shows an excellent stability during 1000 cycles with negligible loss of the cathodic current. This facile hydrothermal method could provide a promising strategy for the synthesis of in–situ nitrogen–doping graphene sheets and few�

The rate coefficients of unimolecular reactions in the systems with power-law distributions

Science.gov (United States)

Yin, Cangtao; Guo, Ran; Du, Jiulin

2014-08-01

The rate coefficient formulae of unimolecular reactions are generalized to the systems with the power-law distributions based on nonextensive statistics, and the power-law rate coefficients are derived in the high and low pressure limits, respectively. The numerical analyses are made of the rate coefficients as functions of the ν-parameter, the threshold energy, the temperature and the number of degrees of freedom. We show that the new rate coefficients depend strongly on the ν-parameter different from one (thus from a Boltzmann-Gibbs distribution). Two unimolecular reactions, CH3CO→CH3+CO and CH3NC→CH3CN, are taken as application examples to calculate their power-law rate coefficients, which obtained with the ν-parameters slightly different from one can be exactly in agreement with all the experimental studies on these two reactions in the given temperature ranges.

Ultraviolet-Visible (UV-Vis) Microspectroscopic System Designed for the In Situ Characterization of the Dehydrogenation Reaction Over Platinum Supported Catalytic Microchannel Reactor.

Science.gov (United States)

Suarnaba, Emee Grace Tabares; Lee, Yi Fuan; Yamada, Hiroshi; Tagawa, Tomohiko

2016-11-01

An ultraviolet visible (UV-Vis) microspectroscopic system was designed for the in situ characterization of the activity of the silica supported platinum (Pt) catalyst toward the dehydrogenation of 1-methyl-1,4-cyclohexadiene carried out in a custom-designed catalytic microreactor cell. The in situ catalytic microreactor cell (ICMC) with inlet/outlet ports was prepared using quartz cover as the optical window to facilitate UV-Vis observation. A fabricated thermometric stage was adapted to the UV-Vis microspectrophotometer to control the reaction temperature inside the ICMC. The spectra were collected by focusing the UV-Vis beam on a 30 × 30 µm area at the center of ICMC. At 393 K, the sequential measurement of the spectra recorded during the reaction exhibited a broad absorption peak with maximum absorbance at 260 nm that is characteristic for gaseous toluene. This result indicates that the silica supported Pt catalyst is active towards the dehydrogenation of 1-methyl-1,4-cyclohexadiene at the given experimental conditions. The onset of coke formation was also detected based on the appearance of absorption bands at 300 nm. The UV-Vis microspectroscopic system developed can be used further in studying the mechanism of the dehydrogenation reaction. © The Author(s) 2016.

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-01-28

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

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

International Nuclear Information System (INIS)

Prayitno

2007-01-01

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

Thermally activated reaction–diffusion-controlled chemical bulk reactions of gases and solids

Directory of Open Access Journals (Sweden)

S. Möller

2015-01-01

Full Text Available The chemical kinetics of the reaction of thin films with reactive gases is investigated. The removal of thin films using thermally activated solid–gas to gas reactions is a method to in-situ control deposition inventory in vacuum and plasma vessels. Significant scatter of experimental deposit removal rates at apparently similar conditions was observed in the past, highlighting the need for understanding the underlying processes. A model based on the presence of reactive gas in the films bulk and chemical kinetics is presented. The model describes the diffusion of reactive gas into the film and its chemical interaction with film constituents in the bulk using a stationary reaction–diffusion equation. This yields the reactive gas concentration and reaction rates. Diffusion and reaction rate limitations are depicted in parameter studies. Comparison with literature data on tokamak co-deposit removal results in good agreement of removal rates as a function of pressure, film thickness and temperature.

Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Titanium

CERN Document Server

American Society for Testing and Materials. Philadelphia

2008-01-01

1.1 This test method covers procedures for measuring reaction rates by the activation reactions 46Ti(n,p) 46Sc + 47Ti(n, np)46Sc. Note 1—Since the cross section for the (n,np) reaction is relatively small for energies less than 12 MeV and is not easily distinguished from that of the (n,p) reaction, this test method will refer to the (n,p) reaction only. 1.2 The reaction is useful for measuring neutrons with energies above approximately 4.4 MeV and for irradiation times up to about 250 days (for longer irradiations, see Practice E 261). 1.3 With suitable techniques, fission-neutron fluence rates above 109 cm–2·s–1 can be determined. However, in the presence of a high thermal-neutron fluence rate, 46Sc depletion should be investigated. 1.4 Detailed procedures for other fast-neutron detectors are referenced in Practice E 261. 1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard. 1.6 This standard does not purport to address all...

Thermodynamic and molecular origin of interfacial rate enhancements and endo-selectivities of a Diels-Alder reaction.

Science.gov (United States)

Beniwal, Vijay; Kumar, Anil

2017-02-08

Organic reactions in general display large rate accelerations when performed under interfacial conditions, such as on water or at ionic liquid interfaces. However, a clear picture of the physicochemical factors responsible for this large rate enhancements is not available. To gain an understanding of the thermodynamic and molecular origin of these large rate enhancements, we performed a Diels-Alder reaction between cyclopentadiene and methyl acrylate at ionic liquid/n-hexane interfaces. This study describes, for the first time, a methodology for the calculation of the activation parameters of an interfacial reaction. It has been seen that the energy of activation for an interfacial reaction is much smaller than that of the corresponding homogeneous reaction, resulting into the large rate acceleration for the interfacial reaction. Furthermore, the study describes the effects of the alkyl chain length of ionic liquid cations, the extent of heterogeneity, and the polarity of ionic liquids on the rate constants and stereoselectivity of the reaction.

Determination of rate constants for the oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

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

2008-07-01

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

A randomised controlled trial of two infusion rates to decrease reactions to antivenom.

Directory of Open Access Journals (Sweden)

Geoffrey K Isbister

Full Text Available BACKGROUND: Snake envenoming is a major clinical problem in Sri Lanka, with an estimated 40,000 bites annually. Antivenom is only available from India and there is a high rate of systemic hypersensitivity reactions. This study aimed to investigate whether the rate of infusion of antivenom reduced the frequency of severe systemic hypersensitivity reactions. METHODS AND FINDINGS: This was a randomized comparison trial of two infusion rates of antivenom for treatment of non-pregnant adult patients (>14 y with snake envenoming in Sri Lanka. Snake identification was by patient or hospital examination of dead snakes when available and confirmed by enzyme-immunoassay for Russell's viper envenoming. Patients were blindly allocated in a 11 randomisation schedule to receive antivenom either as a 20 minute infusion (rapid or a two hour infusion (slow. The primary outcome was the proportion with severe systemic hypersensitivity reactions (grade 3 by Brown grading system within 4 hours of commencement of antivenom. Secondary outcomes included the proportion with mild/moderate hypersensitivity reactions and repeat antivenom doses. Of 1004 patients with suspected snakebites, 247 patients received antivenom. 49 patients were excluded or not recruited leaving 104 patients allocated to the rapid antivenom infusion and 94 to the slow antivenom infusion. The median actual duration of antivenom infusion in the rapid group was 20 min (Interquartile range[IQR]:20-25 min versus 120 min (IQR:75-120 min in the slow group. There was no difference in severe systemic hypersensitivity reactions between those given rapid and slow infusions (32% vs. 35%; difference 3%; 95%CI:-10% to +17%;p = 0.65. The frequency of mild/moderate reactions was also similar. Similar numbers of patients in each arm received further doses of antivenom (30/104 vs. 23/94. CONCLUSIONS: A slower infusion rate would not reduce the rate of severe systemic hypersensitivity reactions from current high

MEMS Lubrication by In-Situ Tribochemical Reactions From the Vapor Phase.

Energy Technology Data Exchange (ETDEWEB)

Dugger, Michael Thomas; Asay, David B.; Kim, Seong H.

2008-01-01

Vapor Phase Lubrication (VPL) of silicon surfaces with pentanol has been demonstrated. Two potential show stoppers with respect to application of this approach to real MEMS devices have been investigated. Water vapor was found to reduce the effectiveness of VPL with alcohol for a given alcohol concentration, but the basic reaction mechanism observed in water-free environments is still active, and devices operated much longer in mixed alcohol and water vapor environments than with chemisorbed monolayer lubricants alone. Complex MEMS gear trains were successfully lubricated with alcohol vapors, resulting in a factor of 104 improvement in operating life without failure. Complex devices could be made to fail if operated at much higher frequencies than previously used, and there is some evidence that the observed failure is due to accumulation of reaction products at deeply buried interfaces. However, if hypothetical reaction mechanisms involving heated surfaces are valid, then the failures observed at high frequency may not be relevant to operation at normal frequencies. Therefore, this work demonstrates that VPL is a viable approach for complex MEMS devices in conventional packages. Further study of the VPL reaction mechanisms are recommended so that the vapor composition may be optimized for low friction and for different substrate materials with potential application to conventionally fabricated, metal alloy parts in weapons systems. Reaction kinetics should be studied to define effective lubrication regimes as a function of the partial pressure of the vapor phase constituent, interfacial shear rate, substrate composition, and temperature.

Simultaneous Transformation of Commingled Trichloroethylene, Tetrachloroethylene, and 1,4-Dioxane by a Microbially Driven Fenton Reaction in Batch Liquid Cultures

Science.gov (United States)

Sekar, Ramanan; Taillefert, Martial

2016-01-01

ABSTRACT Improper disposal of 1,4-dioxane and the chlorinated organic solvents trichloroethylene (TCE) and tetrachloroethylene (also known as perchloroethylene [PCE]) has resulted in widespread contamination of soil and groundwater. In the present study, a previously designed microbially driven Fenton reaction system was reconfigured to generate hydroxyl (HO˙) radicals for simultaneous transformation of source zone levels of single, binary, and ternary mixtures of TCE, PCE, and 1,4-dioxane. The reconfigured Fenton reaction system was driven by fed batch cultures of the Fe(III)-reducing facultative anaerobe Shewanella oneidensis amended with lactate, Fe(III), and contaminants and exposed to alternating anaerobic and aerobic conditions. To avoid contaminant loss due to volatility, the Fe(II)-generating, hydrogen peroxide-generating, and contaminant transformation phases of the microbially driven Fenton reaction system were separated. The reconfigured Fenton reaction system transformed TCE, PCE, and 1,4-dioxane either as single contaminants or as binary and ternary mixtures. In the presence of equimolar concentrations of PCE and TCE, the ratio of the experimentally derived rates of PCE and TCE transformation was nearly identical to the ratio of the corresponding HO˙ radical reaction rate constants. The reconfigured Fenton reaction system may be applied as an ex situ platform for simultaneous degradation of commingled TCE, PCE, and 1,4-dioxane and provides valuable information for future development of in situ remediation technologies. IMPORTANCE A microbially driven Fenton reaction system [driven by the Fe(III)-reducing facultative anaerobe S. oneidensis] was reconfigured to transform source zone levels of TCE, PCE, and 1,4-dioxane as single contaminants or as binary and ternary mixtures. The microbially driven Fenton reaction may thus be applied as an ex situ platform for simultaneous degradation of at least three (and potentially more) commingled contaminants

Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

International Nuclear Information System (INIS)

Schlautman, Mark A.

2013-01-01

Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibited due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not

Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

Energy Technology Data Exchange (ETDEWEB)

Schlautman, Mark A. [Clemson University, Clemson, SC (United States)

2013-07-14

Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibited due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not

Chromogenic in situ Hybridization Compared with Real time Quantitative Polymerase Chain Reaction to Evaluate HER2/neu Status in Breast Cancer.

Science.gov (United States)

Ayatollahi, Hossein; Fani, Azar; Ghayoor Karimiani, Ehsan; Homaee, Fateme; Shajiei, Arezoo; Sheikh, Maryam; Shakeri, Sepideh; Shams, Seyyede Fatemeh

2017-01-01

The assessment of human epidermal growth factor receptor 2 (HER2) status has become of great importance in the diagnosis of breast cancer. The aim of this study was to investigate the diagnostic value of quantitative Polymerase Chain Reaction (qPCR) and Chromogenic In Situ Hybridization (CISH) to assess HER2 status of biopsy specimens. To elucidate the status of HER2 gene amplification, biopsies of breast carcinoma from 120 patients with 2+ IHC status were analyzed by qPCR and CISH. The results of the two experiments were compared, and it was depicted that the concordance rate between CISH and qPCR assays was 88.1%.The quantification of HER2 gene with CISH and qPCR showed that there was a significant correlation (p value= 0.0001 and r= 0.808). The results of this research support the idea that qPCR is a precise and reproducible technique, which can be employed as a supplementary method to evaluate HER2 status.

A model for reaction rates in turbulent reacting flows

Science.gov (United States)

Chinitz, W.; Evans, J. S.

1984-01-01

To account for the turbulent temperature and species-concentration fluctuations, a model is presented on the effects of chemical reaction rates in computer analyses of turbulent reacting flows. The model results in two parameters which multiply the terms in the reaction-rate equations. For these two parameters, graphs are presented as functions of the mean values and intensity of the turbulent fluctuations of the temperature and species concentrations. These graphs will facilitate incorporation of the model into existing computer programs which describe turbulent reacting flows. When the model was used in a two-dimensional parabolic-flow computer code to predict the behavior of an experimental, supersonic hydrogen jet burning in air, some improvement in agreement with the experimental data was obtained in the far field in the region near the jet centerline. Recommendations are included for further improvement of the model and for additional comparisons with experimental data.

Benchmark calculations of thermal reaction rates. I - Quantal scattering theory

Science.gov (United States)

Chatfield, David C.; Truhlar, Donald G.; Schwenke, David W.

1991-01-01

The thermal rate coefficient for the prototype reaction H + H2 yields H2 + H with zero total angular momentum is calculated by summing, averaging, and numerically integrating state-to-state reaction probabilities calculated by time-independent quantum-mechanical scattering theory. The results are very carefully converged with respect to all numerical parameters in order to provide high-precision benchmark results for confirming the accuracy of new methods and testing their efficiency.

Eight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces.

Science.gov (United States)

Zhou, Yong; Zhang, Dong H

2014-11-21

Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH4 reaction and the H2+CH3 reaction are calculated. Simulations of the H+CH4 reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable high accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH4 rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H2+CH3 reaction are found to be in good consistency with experimental observations.

Reaction rate and composition dependence of the stability of thermonuclear burning on accreting neutron stars

International Nuclear Information System (INIS)

Keek, L.; Cyburt, R. H.; Heger, A.

2014-01-01

The stability of thermonuclear burning of hydrogen and helium accreted onto neutron stars is strongly dependent on the mass accretion rate. The burning behavior is observed to change from Type I X-ray bursts to stable burning, with oscillatory burning occurring at the transition. Simulations predict the transition at a 10 times higher mass accretion rate than observed. Using numerical models we investigate how the transition depends on the hydrogen, helium, and CNO mass fractions of the accreted material, as well as on the nuclear reaction rates of 3α and the hot-CNO breakout reactions 15 O(α, γ) 19 Ne and 18 Ne(α, p) 21 Na. For a lower hydrogen content the transition is at higher accretion rates. Furthermore, most experimentally allowed reaction rate variations change the transition accretion rate by at most 10%. A factor 10 decrease of the 15 O(α, γ) 19 Ne rate, however, produces an increase of the transition accretion rate of 35%. None of our models reproduce the transition at the observed rate, and depending on the true 15 O(α, γ) 19 Ne reaction rate, the actual discrepancy may be substantially larger. We find that the width of the interval of accretion rates with marginally stable burning depends strongly on both composition and reaction rates. Furthermore, close to the stability transition, our models predict that X-ray bursts have extended tails where freshly accreted fuel prolongs nuclear burning.

In-situ carboxylation and synthesis of two novel Sm(III) coordination polymers assembled from 5-hydroxyisophthalate and nitrate, chloride in hydrothermal reaction

International Nuclear Information System (INIS)

Huang Yan; Yan Bing; Shao Min

2008-01-01

By reactions of 5-hydroxyisophthalic acid (H 2 hisp) with Sm(NO 3 ) 3 .6H 2 O or SmCl 3 .6H 2 O in the presence of NaOH, two kinds of samarium coordination polymers, [Sm(H 2 hbtc)(ox) 0.5 (H 2 O) 3 ] n .nH 2 O (1) (H 2 hbtc 2- =6-hydroxy-1,2,4-benzenetricarboxylate) and [Sm(hisp)(Hhisp)(H 2 O) 2 ] n .2nH 2 O (2), have been hydrothermal synthesized and characterized. Single-crystal X-ray analyses reveal that compound 1 features a novel two-dimensional (2D) stair-like structure with oxalate ligands and the new organic ligand (H 2 hbtc 2- ) but without 5-hydroxyisophthalate ligands, while compound 2 gives the expected product and displays a novel layer structure. The oxalate ligands have been formed via the in-situ reductive coupling of CO 2 molecules released from the decomposition of carboxylate ligands with the reduction of NO 3 - and the new organic ligands have been formed via the in-situ carboxylation under the presence of NO 3 - . Reported herein are the syntheses of compounds 1 and 2, crystal structures and possible mechanism information regarding the in-situ carboxylation. - Graphical abstract: Hydrothermal reactions of Sm(NO 3 ) 3 .6H 2 O or SmCl 3 .6H 2 O with 5-hydroxyisophthalic acid (H 2 hisp) have given rise to two different kinds of Sm(III) coordination polymers. Single-crystal X-ray analyses reveal that compound 1 features a novel 2D stair-like structure with oxalate and a new organic ligand, 6-hydroxy-1,2,4-benzenetricarboxylate, while compound 2 gives the normal product and displays a novel 2D layer structure. Oxalate ligands have been formed via the in-situ reductive coupling of CO 2 molecules released from the decomposition of 5-hydroxyisophthalate ligands with the reduction of NO 3 - and the new organic ligands have been formed via the in-situ carboxylation under the presence of NO 3 -

Measurements of rates of some reactions related to radiolytic effect on aqueous iodide solution

International Nuclear Information System (INIS)

Shiraishi, H.; Okuda, H.; Ishigure, K.

1986-01-01

A number of reactions takes place concurrently when aqueous iodide solution is subjected to radiation field. In order to help analyze this complicated radiation effect measurements of rate constants were undertaken for several important reactions. One of these concerns reduction of hypoiodous acid by hydrogen peroxide. For this reaction catalytic effect was found to be significant, and old rate data was revised. Measurements on reactions involving radicals were carried out by use of pulse radiolysis technique, which also include reexamination of results by previous workers. The reactions studied are (1) oxidation of iodide ion by hydroxyl radical (2) recombination reactions of atomic iodine and diiodide ion and (3) reduction of atomic and molecular iodine either by superoxide ion or by hydroperoxyl radical

Corrosion potential detection method, potential characteristic simulation method for reaction rate and plant monitoring system using the same

International Nuclear Information System (INIS)

Sakai, Masanori; Onaka, Noriyuki; Takahashi, Tatsuya; Yamanaka, Hiroshi.

1995-01-01

In a calculation controlling device for a plant monitoring system, concentrations of materials concerning reaction materials in a certain state of a reaction process, and an actually measured value for the potential of a material in this state are substituted into a reaction rate equation obtained in accordance with a reaction process model. With such procedures, a relation between the reaction rate (current value) and the potential of the material can be obtained. A potential at which the reaction rates of an anode reaction and a cathode reaction contained in a corrosion reaction are made equal is determined by a numerical value calculation, based on an electrochemical hybrid potential logic by using the reaction rate equation, the reaction rate information relative to the corrosion reaction of the material and the concentration of the material concerning the corrosion reaction is obtained by a numerical value calculation. Then, simulation for the corrosion potential is enabled based on the handling corresponding to the actual reaction. Further, even for a portion which can not be measured actually, the corrosion potential can be recognized by simulation. (N.H.)

Reevaluation of the O+(2P) reaction rate coefficients derived from atmosphere explorer C observations

International Nuclear Information System (INIS)

Chang, T.; Torr, D.G.; Richards, P.G.; Solomon, S.C.

1993-01-01

O + ( 2 P) is an important species for studies of the ionosphere and thermosphere: its emission at 7320 angstrom can be used as a diagnostic of the thermospheric atomic oxygen density. Unfortunately, there are no laboratory measurements of the O and N 2 reaction rates which are needed to determine the major sinks of O + ( 2 P). The reaction rates that are generally used were determined from aeronomic data by Rusch et al. but there is evidence that several important inputs that they used should be changed. The authors have recalculated the O and N 2 reaction rates for O + ( 2 P) using recent improvements in the solar EUV flux, cross sections, and photoelectron fluxes. For the standard solar EUV flux, the new N 2 reaction rate of 3.4 ± 1.5 x 10 -10 cm 3 s -1 is close to the value obtained by Rusch et al., but the new O reaction rate of 4.0 ± 1.9 x 10 -10 cm 3 s -1 is about 8 times larger. These new reaction rates are derived using neutral densities, electron density, and solar EUV fluxes measured by Atmosphere Explorer C in 1974 during solar minimum. The new theoretical emission rates are in good agreement with the data for the two orbits studied by Rusch et al. and they are in reasonable agreement with data from five additional orbits that are used in this study. The authors have also examined the effect of uncertainties in the solar EUV flux on the derived reaction rates and found that 15% uncertainties in the solar flux could cause additional uncertainties of up to a factor of 1.5 in the O quenching rate. 19 refs., 4 figs., 8 tabs

2-16 Thermonuclear Reaction Rates in rp Process of sd

Institute of Scientific and Technical Information of China (English)

Lam; Yihua[1; Nadezda; A.; Smirnova[2; W.A.; Richter[3

2014-01-01

Recently, we have constructed a new set of isospin non-conserving (INC) shell-model Hamiltonians as a combinationof isospin conserving (IC) Hamiltonian, Coulomb interaction and effective isospin-symmetry breaking forcesof nuclear origin[1]. The advantage is that Coulomb effects are taken into account with great care, thus the new ap-Fig. 1 (color online) The comparison of resonant rates of23Al(p;)24Si calculated by IC and INC Hamiltonians. TheINC Hamiltonians of OB+USD, OB+USDA, OB+USDBwere constructed in Ref. [5]; whereas (cd-USD), (cd-USDA),(cd-USDB) are INC Hamiltonians in Ref. [1]. USD, USDA,USDB are IC Hamiltonians in Ref. [6].proach allows one to describe more accurately and topredict unknown nuclear level schemes and decay modes.Since the approximate isospin-symmetry becomes broken,a realistic amount of isospin-mixing in nuclearstates is thus introduced. Among numerous applicationsto the structure of proton-rich nuclei, we usedthe new Hamiltonian to calculate resonant reaction andnon-resonant reaction (direct capture) rates of radiativeproton-capture reactions important for astrophysical rpprocess.

Estimation of the Polymerization Rate of Liquid Propylene Using Adiabatic Reaction Calorimetry and Reaction Dilatometry

NARCIS (Netherlands)

Al-haj Ali, Mohammad; Betlem, Ben; Roffel, Brian; Weickert, Günter

2007-01-01

The use of pressure-drop and constant-pressure dilatometry for obtaining rate data for liquid propylene polymerization in filled batch reactors was examined. The first method uses reaction temperature and pressure as well as the compressibility of the reactor contents to calculate the polymerization

Superaerophobic Ultrathin Ni-Mo Alloy Nanosheet Array from In Situ Topotactic Reduction for Hydrogen Evolution Reaction.

Science.gov (United States)

Zhang, Qian; Li, Pengsong; Zhou, Daojin; Chang, Zheng; Kuang, Yun; Sun, Xiaoming

2017-11-01

Hydrogen evolution reaction (HER) has prospect to becoming clean and renewable technology for hydrogen production and Ni-Mo alloy is among the best HER catalysts in alkaline electrolytes. Here, an in situ topotactic reduction method to synthesize ultrathin 2D Ni-Mo alloy nanosheets for electrocatalytic hydrogen evolution is reported. Due to its ultrathin structure and tailored composition, the as-synthesized Ni-Mo alloy shows an overpotential of 35 mV to reach a current density of 10 mA cm -2 , along with a Tafel slope of 45 mV decade -1 , demonstrating a comparable intrinsic activity to state-of-art commercial Pt/C catalyst. Besides, the vertically aligned assemble structure of the 2D NiMo nanosheets on conductive substrate makes the electrode "superaerophobic," thus leading to much faster bubble releasing during HER process and therefore shows faster mass transfer behavior at high current density as compared with drop drying Pt/C catalyst on the same substrate. Such in situ topotactic conversion finds a way to design and fabricate low-cost, earth-abundant non-noble metal based ultrathin 2D nanostructures for electrocatalytic issues. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ fluorescence spectroscopy correlates ionomer degradation to reactive oxygen species generation in an operating fuel cell.

Science.gov (United States)

Prabhakaran, Venkateshkumar; Arges, Christopher G; Ramani, Vijay

2013-11-21

The rate of generation of reactive oxygen species (ROS) within the polymer electrolyte membrane (PEM) of an operating proton exchange member fuel cell (PEMFC) was monitored using in situ fluorescence spectroscopy. A modified barrier layer was introduced between the PEM and the electrocatalyst layer to eliminate metal-dye interactions and fluorescence resonance energy transfer (FRET) effects during measurements. Standard fuel cell operating parameters (temperature, relative humidity, and electrode potential) were systematically varied to evaluate their influence on the rate of ROS generation during PEMFC operation. Independently, the macroscopic rate of PEM degradation was measured by monitoring the fluoride ion emission rate (FER) in the effluent stream at each operating condition. The ROS generation reaction rate constant (estimated from the in situ fluorescence experiments) correlated perfectly with the measured FER across all conditions, demonstrating unequivocally for the first time that a direct correlation exists between in situ ROS generation and PEM macroscopic degradation. The activation energy for ROS generation within the PEM was estimated to be 12.5 kJ mol(-1).

Modeling thermal spike driven reactions at low temperature and application to zirconium carbide radiation damage

Science.gov (United States)

Ulmer, Christopher J.; Motta, Arthur T.

2017-11-01

The development of TEM-visible damage in materials under irradiation at cryogenic temperatures cannot be explained using classical rate theory modeling with thermally activated reactions since at low temperatures thermal reaction rates are too low. Although point defect mobility approaches zero at low temperature, the thermal spikes induced by displacement cascades enable some atom mobility as it cools. In this work a model is developed to calculate "athermal" reaction rates from the atomic mobility within the irradiation-induced thermal spikes, including both displacement cascades and electronic stopping. The athermal reaction rates are added to a simple rate theory cluster dynamics model to allow for the simulation of microstructure evolution during irradiation at cryogenic temperatures. The rate theory model is applied to in-situ irradiation of ZrC and compares well at cryogenic temperatures. The results show that the addition of the thermal spike model makes it possible to rationalize microstructure evolution in the low temperature regime.

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

International Nuclear Information System (INIS)

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

1979-05-01

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

Reevaluation of the O(+)(2P) reaction rate coefficients derived from Atmosphere Explorer C observations

Science.gov (United States)

Chang, T.; Torr, D. G.; Richards, P. G.; Solomon, S. C.

1993-01-01

O(+)(2P) is an important species for studies of the ionosphere and thermosphere: its emission at 7320 A can be used as a diagnostic of the thermospheric atomic oxygen density. Unfortunately, there are no laboratory measurements of the O and N2 reaction rates which are needed to determine the major sinks of (O+)(2p). We have recalculated the O and N2 reaction rates for O(+) (2P) using recent improvements in the solar EUV flux, cross sections, and photoelectron fluxes. For the standard solar EUV flux, the new N2 reaction rate of 3.4 +/- 1.5 x 10 exp -10 cu cm/s is close to the value obtained by Rusch et al. (1977), but the new O reaction rate of 4.0 +/- 1.9 x 10 exp -10 cu cm/sec is about 8 times larger. These new reaction rates are derived using neutral densities, electron density, and solar EUV fluxes measured by Atmosphere Explorer C in 1974 during solar minimum. The new theoretical emission rates are in good agreement with the data for the two orbits studied by Rusch et al.

SENSMG: First-Order Sensitivities of Neutron Reaction Rates, Reaction-Rate Ratios, Leakage, k_eff, and α Using PARTISN

Energy Technology Data Exchange (ETDEWEB)

Favorite, Jeffrey A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-11-21

SENSMG is a tool for computing first-order sensitivities of neutron reaction rates, reaction-rate ratios, leakage, k_eff, and α using the PARTISN multigroup discrete-ordinates code. SENSMG computes sensitivities to all of the transport cross sections and data (total, fission, nu, chi, and all scattering moments), two edit cross sections (absorption and capture), and the density for every isotope and energy group. It also computes sensitivities to the mass density for every material and derivatives with respect to all interface locations. The tool can be used for one-dimensional spherical (r) and two-dimensional cylindrical (r-z) geometries. The tool can be used for fixed-source and eigenvalue problems. The tool implements Generalized Perturbation Theory (GPT) as discussed by Williams and Stacey. Section II of this report describes the theory behind adjoint-based sensitivities, gives the equations that SENSMG solves, and defines the sensitivities that are output. Section III describes the user interface, including the input file and command line options. Section IV describes the output. Section V gives some notes about the coding that may be of interest. Section VI discusses verification, which is ongoing. Section VII lists needs and ideas for future work. Appendix A lists all of the input files whose results are presented in Sec. VI.

Estimating cumulative soil accumulation rates with in situ-produced cosmogenic nuclide depth profiles

International Nuclear Information System (INIS)

Phillips, William M.

2000-01-01

A numerical model relating spatially averaged rates of cumulative soil accumulation and hillslope erosion to cosmogenic nuclide distribution in depth profiles is presented. Model predictions are compared with cosmogenic 21 Ne and AMS radiocarbon data from soils of the Pajarito Plateau, New Mexico. Rates of soil accumulation and hillslope erosion estimated by cosmogenic 21 Ne are significantly lower than rates indicated by radiocarbon and regional soil-geomorphic studies. The low apparent cosmogenic erosion rates are artifacts of high nuclide inheritance in cumulative soil parent material produced from erosion of old soils on hillslopes. In addition, 21 Ne profiles produced under conditions of rapid accumulation (>0.1 cm/a) are difficult to distinguish from bioturbated soil profiles. Modeling indicates that while 10 Be profiles will share this problem, both bioturbation and anomalous inheritance can be identified with measurement of in situ-produced 14 C

Measurement of reaction rates of interest in stellar structure and evolution

International Nuclear Information System (INIS)

Terrasi, F.; D''Onofrio, A.; Campajola, L.; Imbriani, G.; Gialanella, L.; Greife, U.; Rolfs, C.; Strieder, F.; Trautvetter, H.P.; Roca, V.; Romano, M.; Straniero, O.

1998-01-01

Accurate determinations of reaction rates at astrophysical energies are very important in stellar structure and evolution studies. The cases of two key reactions, namely 7 Be(p,γ) 8 B and 12 C(α,γ) 16 O are discussed, both from the point of view of their astrophysical interest and of the experimental difficulties in the measurement of their cross section. (orig.)

Rate constant computation on some elementary reactions of Hg during combustion

Energy Technology Data Exchange (ETDEWEB)

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

2013-07-01

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

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

International Nuclear Information System (INIS)

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

1979-05-01

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

Computer investigations on the asymptotic behavior of the rate coefficient for the annihilation reaction A + A → product and the trapping reaction in three dimensions.

Science.gov (United States)

Litniewski, Marek; Gorecki, Jerzy

2011-06-28

We have performed intensive computer simulations of the irreversible annihilation reaction: A + A → C + C and of the trapping reaction: A + B → C + B for a variety of three-dimensional fluids composed of identical spherical particles. We have found a significant difference in the asymptotic behavior of the rate coefficients for these reactions. Both the rate coefficients converge to the same value with time t going to infinity but the convergence rate is different: the O(t(-1/2)) term for the annihilation reaction is higher than the corresponding term for the trapping reaction. The simulation results suggest that ratio of the terms is a universal quantity with the value equal to 2 or slightly above. A model for the annihilation reaction based on the superposition approximation predicts the difference in the O(t(-1/2)) terms, but overestimates the value for the annihilation reaction by about 30%. We have also performed simulations for the dimerization process: A + A → E, where E stands for a dimer. The dimerization decreases the reaction rate due to the decrease in the diffusion constant for A. The effect is successfully predicted by a simple model.

Development of Advanced In-Situ Techniques for Chemistry Monitoring and Corrosion Mitigation in SCWO Environments

International Nuclear Information System (INIS)

Macdonald, D. D.; Lvov, S. N.

2000-01-01

This project is developing sensing technologies and corrosion monitoring techniques for use in super critical water oxidation (SCWO) systems to reduce the volume of mixed low-level nuclear waste by oxidizing organic components in a closed cycle system where CO2 and other gaseous oxides are produced, leaving the radioactive elements concentrated in ash. The technique uses water at supercritical temperatures under highly oxidized conditions by maintaining a high fugacity of molecular oxygen in the system, which causes high corrosion rates of even the most corrosive resistant reactor materials. This project significantly addresses the high corrosion shortcoming through development of (a) advanced electrodes and sensors for in situ potentiometric monitoring of pH in high subcritical and supercritical aqueous solutions, (b) an approach for evaluating the association constants for 1-1 aqueous electrolytes using a flow-through electrochemical thermocell; (c) an electrochemical noise sensor for the in situ measurement of corrosion rate in subcritical and supercritical aqueous systems; (d) a model for estimating the effect of pressure on reaction rates, including corrosion reactions, in high subcritical and supercritical aqueous systems. The project achieved all objectives, except for installing some of the sensors into a fully operating SCWO system

Development of Advanced In-Situ Techniques for Chemistry Monitoring and Corrosion Mitigation in SCWO Environments

Energy Technology Data Exchange (ETDEWEB)

Macdonald, D. D.; Lvov, S. N.

2000-03-31

This project is developing sensing technologies and corrosion monitoring techniques for use in super critical water oxidation (SCWO) systems to reduce the volume of mixed low-level nuclear waste by oxidizing organic components in a closed cycle system where CO2 and other gaseous oxides are produced, leaving the radioactive elements concentrated in ash. The technique uses water at supercritical temperatures under highly oxidized conditions by maintaining a high fugacity of molecular oxygen in the system, which causes high corrosion rates of even the most corrosive resistant reactor materials. This project significantly addresses the high corrosion shortcoming through development of (a) advanced electrodes and sensors for in situ potentiometric monitoring of pH in high subcritical and supercritical aqueous solutions, (b) an approach for evaluating the association constants for 1-1 aqueous electrolytes using a flow-through electrochemical thermocell; (c) an electrochemical noise sensor for the in situ measurement of corrosion rate in subcritical and supercritical aqueous systems; (d) a model for estimating the effect of pressure on reaction rates, including corrosion reactions, in high subcritical and supercritical aqueous systems. The project achieved all objectives, except for installing some of the sensors into a fully operating SCWO system.

In Situ Measurement of Local Hydrogen Production Rate by Bubble-Evolved Recording

Directory of Open Access Journals (Sweden)

Xiaowei Hu

2013-01-01

Full Text Available Hydrogen visibly bubbles during photocatalytic water splitting under illumination with above-bandgap radiation, which provides a direct measurement of local gas-evolving reaction rate. In this paper, optical microscopy of superfield depth was used for recording the hydrogen bubble growth on Cd0.5Zn0.5S photocatalyst in reaction liquid and illuminated with purple light. By analyzing change of hydrogen bubble size as a function of time, we understood that hydrogen bubble growth experienced two periods, which were inertia effect dominated period and diffusion effect dominated period, respectively. The tendency of hydrogen bubble growth was similar to that of the gas bubble in boiling, while the difference in bubble diameter and growth time magnitude was great. Meanwhile, we obtained the local hydrogen production rate on photocatalyst active site by measuring hydrogen bubble growth variation characteristics. This method makes it possible to confirm local actual hydrogen evolution rate quantitatively during photocatalytic water splitting.

Effect of low and high heating rates on reaction path of Ni(V)/Al multilayer

Energy Technology Data Exchange (ETDEWEB)

Maj, Łukasz, E-mail: l.maj@imim.pl [Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 25 Reymonta St., 30-059 Kraków (Poland); Morgiel, Jerzy; Szlezynger, Maciej [Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 25 Reymonta St., 30-059 Kraków (Poland); Bała, Piotr; Cios, Grzegorz [AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, 30 Kawiory St., 30-055 Kraków (Poland)

2017-06-01

The effect of heating rates of Ni(V)/Al NanoFoils{sup ®} was investigated with transmission electron microscopy (TEM). The Ni(V)/Al were subjected to heating by using differential scanning calorimetry (DSC), in-situ TEM or electric pulse. Local chemical analysis was carried out using energy dispersive X-ray spectroscopy (EDS). Phase analysis was done with X-ray diffractions (XRD) and selected area electron diffractions (SAED). The experiments showed that slow heating in DSC results in development of separate exothermic effects at ∼230 °C, ∼280 °C and ∼390 °C, corresponding to precipitation of Al{sub 3}Ni, Al{sub 3}Ni{sub 2} and NiAl phases, respectively, i.e. like in vanadium free Ni/Al multilayers. Further heating to 700 °C allowed to obtain a single phase NiAl foil. The average grain size (g.s.) of NiAl phase produced in the DSC heat treated foil was comparable with the Ni(V)/Al multilayer period (∼50 nm), whereas in the case of reaction initiated with electric pulse the g.s. was in the micrometer range. Upon slow heating vanadium tends to segregate to zones parallel to the original multilayer internal interfaces, while in SHS process vanadium-rich phases precipitates at grain boundaries of the NiAl phase. - Highlights: • Peaks in DSC heating of Ni(V)/Al were explained by in-situ TEM observations. • Nucleation of Al{sub 3}Ni, Al{sub 3}Ni{sub 2} and NiAl at slow heating of Ni(V)/Al was documented. • Near surface NiAl obtained from NanoFoil show Ag precipitates at grain boundaries.

Directed ortho metalation-based methodology. Halo-, nitroso-, and boro-induced ipso-desilylation. Link to an in situ Suzuki reaction.

Science.gov (United States)

Zhao, Zhongdong; Snieckus, Victor

2005-06-23

[reaction: see text] Treatment of DoM-derived silylated aromatics 2-4 under standard electrophilic halogenation conditions cleanly affords ipso-desilyation products 5-7, while nitration of methoxy-substituted analogues 8, 9 leads to non-ipso isomers 10, 12 and 11, 13, controlled by a silicon steric effect. Sequential ipso-borodesilylation of 2a, 3a, and 20 followed by treatment with aryl halides under Pd-catalyzed conditions constitutes an in situ Suzuki-Miyaura cross-coupling protocol to biaryls and heterobiaryls 23.

In-situ buildup of cosmogenic isotopes at the earth's surface: measurement of erosion rates and exposure times

International Nuclear Information System (INIS)

Fifield, L.K.; Allan, G.L.; Stone, J.O.H.; Evans, J.M.; Cresswell, R.G.; Ophel, T.R.

1993-01-01

Cosmic rays produce a number of nuclides in rocks that can be used to determine the geomorphic history of surfaces. The most useful are the radioactive isotopes 10 Be (t 1/2 = 1.5Ma), 26 Al (0.7Ma) and 36 Cl (0.3Ma). Within the top 2m of the surface, these are produced principally by fast neutrons. At greater depths, production is dominated by the capture of negative muons. Measurements of a single nuclide produced in situ can be used to determine total exposure times or erosion rates. The use of multiple nuclides with different half-lives makes it possible to determine more complex histories, such as exposures interrupted by periods of burial. At the ANU, all three of the isotopes above are being used to study a variety of problems in geomorphology and paleoclimatology, although to date, most of the work has concentrated on 36 Cl. The accumulation of cosmogenic 36 Cl in calcite (CaCO 3 ) provides a means of measuring erosion rates on limestone surfaces. Sensitivity is achieved over a wide range of erosion rates due to the high production rate of 36 Cl in calcite (typically greater than 30 atoms/g/yr) and a detection limit of ca. 5000 atoms/g attainable with the ANU AMS system. The method is simplified by the predominance of Ca reactions (principally spallation) over other sources of 36 Cl in calcite, and the ease of sample preparation. This presentation discuss the results of measurements of 36 Cl in calcite from limestone samples from Australia and Papua New Guinea. Erosion rates derived from these measurements range from 3 microns per year (Australia) to over 200 microns per year in the New Guinea highlands. 3 refs

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

Science.gov (United States)

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

2017-12-21

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

Compositional Simulation of In-Situ Combustion EOR: A Study of Process Characteristics

DEFF Research Database (Denmark)

Jain, Priyanka; Stenby, Erling Halfdan; von Solms, Nicolas

2010-01-01

In order to facilitate the study of the influence of reservoir process characteristics in In-Situ combustion modeling and advance the work of Kristensen et al. in this domain; a fully compositional In-situ combustion (ISC) model of Virtual Kinetic Cell (VKC; single-cell model) for laboratory scale....... This incorporates fourteen pseudo components and fourteen reactions (distributed amongst thermal cracking, low temperature oxidation and high temperature oxidation). The paper presents a set of derivative plots indicating that reservoir process characterization in terms of thermal behavior of oil can be well...... construed in terms of thermo-oxidative sensitivity of SARA fractions. It can be interpreted from the results that operating parameters like air injection rate, oxygen feed concentration and activation energy have significant influence on oil recovery; an increase in air injection rate can lead to cooling...

Cross sections and reaction rates of d+{sup 8}Li reactions involved in Big Bang nucleosynthesis

Energy Technology Data Exchange (ETDEWEB)

Balbes, M.J. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Farrell, M.M. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Boyd, R.N. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics]|[Department of Astronomy, Ohio State University, Columbus, OH 43210 (United States); Gu, X. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Hencheck, M. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Kalen, J.D. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Mitchell, C.A. [Ohio State Univ., Columbus, OH (United States). Dept. of Physics; Kolata, J.J. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Lamkin, K. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); Smith, R. [Division of Nuclear Medicine, Department of Radiology, Hospital of the University of Pennsylvania, Philadelphia, PA 19104 (United States); Tighe, R. [Lawrence Berkeley Laboratory, Berkeley, CA 94720 (United States); Ashktorab, K. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Becchetti, F.D. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Brown, J. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Roberts, D. [Department of Physics, University of Michigan, Ann Arbor, MI 48109 (United States); Wang, T.F. [Lawrence Livermore National Laboratory, Livermore, CA 94550 (United States); Humphrey, D. [Department of Physics, University of Western Kentucky, Bowling Green, KY 42101 (United States); Vourvopoulos, G. [Department of Physics, University of Western Kentucky, Bowling Green, KY 42101 (United States); Islam, M.S. [Department of Physics, Ball State University, Muncie, IN 47306 (United States)

1995-02-20

We have measured angular distributions of the {sup 2}H({sup 8}Li, {sup 7}Li){sup 3}H and {sup 2}H({sup 8}Li, {sup 9}Be)n reactions at E{sub c.m.}=1.5 to 2.8 MeV using an {sup 8}Li-radioactive-beam technique. Astrophysical S-factors and reaction rates were calculated from the measured cross sections. Although the {sup 2}H({sup 8}Li, {sup 9}Be)n cross section is small, it can contribute to {sup 9}Be synthesis. The {sup 2}H({sup 8}Li, {sup 7}Li){sup 3}H reaction has a sufficiently large cross section to destroy {sup 8}Li, which may decrease the synthesis of heavier elements. No products from the {sup 2}H({sup 8}Li, {sup 9}Li)p reaction were detected. We also present the results of calculations using the inhomogeneous model of primordial nucleosynthesis in several regions of parameter space. ((orig.))

Calculation of multigroup reaction rates for the Ghana Research ...

African Journals Online (AJOL)

The discrete ordinate spatial model, which pro-vides solution to the differential form of the transport equation by the Carlson-SN (N=4) approach was adopted to solve the Ludwig-Boltzmann multigroup neutron transport equation for this analysis. The results show that for any fissile resonance absorber, the reaction rates ...

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.

Voltammetric, in-situ spectroelectrochemical and in-situ electrocolorimetric characterization of phthalocyanines

Energy Technology Data Exchange (ETDEWEB)

Koca, Atif [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey)], E-mail: akoca@eng.marmara.edu.tr; Bayar, Serife; Dincer, Hatice A. [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey); Gonca, Erguen [Department of Chemistry, Fatih University, TR34500 B.Cekmece, Istanbul (Turkey)

2009-04-01

In this work, electrochemical, and in-situ spectroelectrochemical characterization of the metallophthalocyanines bearing tetra-(1,1-(dicarbethoxy)-2-(2-methylbenzyl))-ethyl 3,10,17,24-tetra chloro groups were performed. Voltammetric and in-situ spectroelectrochemical measurements show that while cobalt phthalocyanine complex gives both metal-based and ring-based redox processes, zinc and copper phthalocyanines show only ring-based reduction and oxidation processes. The redox processes are generally diffusion-controlled, reversible and one-electron transfer processes. Differently lead phthalocyanine demetallized during second oxidation reaction while it was stable during reduction processes. An in-situ electrocolorimetric method, based on the 1931 CIE (Commission Internationale de l'Eclairage) system of colorimetry, has been applied to investigate the color of the electro-generated anionic and cationic forms of the complexes for the first time in this study.

Measurement of reaction rates of interest in stellar structure and evolution

Energy Technology Data Exchange (ETDEWEB)

Terrasi, F; D` Onofrio, A [Dipt. di Scienze Ambientali, Seconda Univ. di Napoli, Caserta (Italy); [INFN, Napoli (Italy); Campajola, L; Imbriani, G [INFN, Napoli (Italy); [Dipt. di Scienze Fisiche, Univ. Federico II, Napoli (Italy); Gialanella, L [INFN, Napoli (Italy); [Dipt. di Scienze Fisiche, Univ. Federico II, Napoli (Italy); [Inst. fuer Experimentalphysik III, Ruhr-Univ. Bochum, Bochum (Germany); Greife, U; Rolfs, C; Strieder, F; Trautvetter, H P [Inst. fuer Experimentalphysik III, Ruhr-Univ. Bochum, Bochum (Germany); Roca, V; Romano, M [INFN, Napoli (Italy); [Dipt. di Scienze Fisiche, Univ. Federico II, Napoli (Italy); Straniero, O [Osservatorio Astronomico di Collurania, Teramo (Italy)

1998-06-01

Accurate determinations of reaction rates at astrophysical energies are very important in stellar structure and evolution studies. The cases of two key reactions, namely {sup 7}Be(p,{gamma}){sup 8}B and {sup 12}C({alpha},{gamma}){sup 16}O are discussed, both from the point of view of their astrophysical interest and of the experimental difficulties in the measurement of their cross section. (orig.)

Hydration of swelling clay and bacteria interaction. An experimental in situ reaction study

International Nuclear Information System (INIS)

Berger, J.

2008-01-01

This study reports on the physical-chemical behaviour of swelling di-octahedral clays (smectites) and their interaction with aqueous solutions and bacteria (Shewanella putrefaciens). Experimental results are presented for compacted clays, hydrated under confined volume conditions, using a new type of reaction-cell (the 'wet-cell' of Warr and Hoffman, 2004) that was designed for in situ X-ray diffraction (XRD) measurement. For comparison, dispersed clay systems were studied using standard batch solutions subjected to varying degrees of agitation. The combination of time-dependent in situ XRD measurements with gravimetric measurements and calculated diffraction patterns using the CALCMIX software (Plancon and Drits, 1999) allowed to successful quantification of the dynamics of water uptake and storage. This analytical procedure combined with published water vapour adsorption data enabled determination of the abundance of structured water layers, developed in the interlayer space, and the amount of water contained in different storage sites (interlayers, surfaces and pore spaces). Qualitative information on surface area and textural organization was also estimated based on calculated changes in the average particle thickness and the organization of water layer structures (ordering). Abiotic smectite hydration experiments, using a range of natural and industrial bentonites (SWy-2, IBECO, MX80, TIXOTON), focused on defining the role of the interlayer cation, variable clay packing densities and the ionic strength of the infiltrating solution. The rate of smectite hydration, as expected, was seen to be highly dependent on the type of interlayer cation (enhanced for Ca as opposed to Na) and the ionic strength of solution (enhanced uptake rates with saline solutions, particularly as they infiltrate Na-smectite). A range of dynamic changes in micro textural state occurred as a function of packing density. These changes explain the differences in hydration behaviour observed

Optimized reaction mechanism rate rules for ignition of normal alkanes

KAUST Repository

Cai, Liming; Pitsch, Heinz; Mohamed, Samah; Raman, Venkat; Bugler, John; Curran, Henry; Sarathy, Mani

2016-01-01

fidelity reacting flow simulations capable of improving combustor design and operation. The development of such models for many new fuel components and/or surrogate molecules is greatly facilitated by the application of reaction classes and rate rules

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.

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.

Effect of crystallochemistry of starting materials on the rate of smectite to illite reaction

International Nuclear Information System (INIS)

Sato, Tsutomu; Isobe, Hiroshi; Ohnuki, Toshihiko; Murakami, Takashi

1995-01-01

A series of hydrothermal experiments was performed to determine the effect of layer charge of starting materials on the smectite to illite reaction rate that might be applied to nuclear-waste repository design. The experiments were conducted on K-saturated fractions of Wyoming smectite (SWy-1) and Tsukinuno smectite (SKu-F) in a closed system at temperatures of 95, 150, 200, 250, 300 C for run durations of up to 477 days with a 1:20 mass ratio of solid to deionized water. The mean layer charge and tetrahedral charge of SKu-F are larger than those of SWy-1. The proportion of smectite layers in illite/smectite interstratified minerals rapidly decreases, and then slowly decreases with increase in reaction time; a plot of ln (100/% smectite) vs. time produces two distinct straight lines in all experiments. These lines are suggestive of two first-order kinetic processes with different rates for this reaction; the first process has a greater rate than the second one. An Arrhenius plot of the reaction rates for each process produces a folding and straight lines for the first and second processes, respectively, suggesting that there are at least two parallel processes in the first process, and a dominant process is different between high- and low-temperature reactions. The activation energies of the first and second processes determined from the plots are the same for the two starting materials, meaning that the reaction mechanisms for the two starting materials are the same. However, the rate of the first process is different between the two starting materials, although that of the second process is similar. The difference in the rate of the first process results possibly from the difference in the amount of layer charge between the two starting smectites

Rate constant for reaction of hydroxyl radicals with bicarbonate ions

International Nuclear Information System (INIS)

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

1986-01-01

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

In situ Fourier transform infrared spectroscopy and on-line differential electrochemical mass spectrometry study of the NH3BH3 oxidation reaction on gold electrodes

International Nuclear Information System (INIS)

Belén Molina Concha, M.; Chatenet, Marian; Lima, Fabio H.B.; Ticianelli, Edson A.

2013-01-01

The ammonia borane (NH 3 BH 3 ) oxidation reaction (ABOR) was studied on gold electrodes using the rotating disk electrode (RDE) setup and coupled physical techniques: on-line differential electrochemical mass spectrometry (DEMS) and in situ Fourier transform infrared spectroscopy (FTIR). Non-negligible heterogeneous hydrolysis in the low-potential region was asserted via molecular H 2 detection. As a consequence, the number of electron exchanged per BH 3 OH − species is ca. 3 at low potential, and only reaches ca. 6 above 0.6 V vs. RHE. These figures were confirmed by Levich and Koutecki–Levich calculations using the RDE experiments data. The nature of the ABOR intermediates and products was determined using in situ FTIR. While BH 2 species were detected during the ABOR, it seems that its adsorption onto the Au electrode proceeds via the O atom, in opposition to what happens during the borohydride oxidation reaction (BOR). Therefore, it is likely that the mechanism of the ABOR differs from that of the BOR. From the whole set of data (RDE, DEMS, FTIR), a relevant reaction pathway was proposed, including competition between the BH 3 OH − heterogeneous hydrolysis and oxidation at low potential, and preponderant oxidation at higher potential. Finally, a simplified kinetic modeling accounting with this reaction pathway was proposed, which nicely fits the stationary (i vs. E) ABOR plot

In situ holographic measurements of the sizes and settling rates of oceanic particulates

Science.gov (United States)

Carder, Kendall L.; Steward, Robert G.; Betzer, Peter R.

1982-07-01

A free-floating sediment trap equipped with a holographic particle velocimeter (HPV) was deployed for 14.4 hours at a depth of 30 m in the western North Atlantic Ocean. The system recorded the in situ sizes, shapes, orientations, and settling rates of microscopic particles moving through the laser beam. The primary data reduction revealed particles from the system's lower limit of resolution, 15 micrometers in diameter, to 250 micrometers in diameter with settling velocities ranging from 0.0190 to 0.2302 cm/s (16-198 m/day). Individual particle densities, calculated from a modified Stokes equation, ranged from 1.37 to 5.10 g/ml. The presence of high density particles was independently corroborated through individual particle analysis of the trapped material with a computer-controlled, scanning electron microscope equipped with an energy dispersive X-ray analyzer. In the future, in situ holographic systems might be used to further our understanding of primary productivity, sediment erosion/deposition, and particle aggregation/disruption/dissolution.

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.

Calculation of rate coefficients of some proton-transfer ion-molecule reactions in weakly ionized gases

International Nuclear Information System (INIS)

Stiller, W.

1985-01-01

A classical collision theory is used to describe thermal bimolecular rate coefficeints for reaction between positive and negative ions and polar molecules in a carrier gas. Special attention is paid to ion-molecule reaction in which proton transfer occurs. These reactions play an important role in terrestrial plasma devices, in ionosphere, in planetary atmospheres and in interstellar matter. The equilibrium rate coefficients of the reactions are calculated based on a microscopic reactive cross section derived from a long distance polar molecule-ion potential. The results are compared with experimental values of afterglow measurements. (D.Gy.)

A study of the photocatalytic effects of aqueous suspensions of platinized semiconductor materials on the reaction rates of candidate redox reactions

Science.gov (United States)

Miles, A. M.

1982-01-01

The effectiveness of powdered semiconductor materials in photocatalyzing candidate redox reactions was investigated. The rate of the photocatalyzed oxidation of cyanide at platinized TiO2 was studied. The extent of the cyanide reaction was followed directly using an electroanalytical method (i.e. differential pulse polarography). Experiments were performed in natural or artificial light. A comparison was made of kinetic data obtained for photocatalysis at platinized powders with rate data for nonplatinized powders.

Recent developments in semiclassical mechanics: eigenvalues and reaction rate constants

International Nuclear Information System (INIS)

Miller, W.H.

1976-04-01

A semiclassical treatment of eigenvalues for a multidimensional non-separable potential function and of the rate constant for a chemical reaction with an activation barrier is presented. Both phenomena are seen to be described by essentially the same semiclassical formalism, which is based on a construction of the total Hamiltonian in terms of the complete set of ''good'' action variables (or adiabatic invariants) associated with the minimum in the potential energy surface for the eigenvalue case, or the saddle point in the potential energy surface for the case of chemical reaction

Micro-Membrane Electrode Assembly Design to Precisely Measure the in Situ Activity of Oxygen Reduction Reaction Electrocatalysts for PEMFC.

Science.gov (United States)

Long, Zhi; Li, Yankai; Deng, Guangrong; Liu, Changpeng; Ge, Junjie; Ma, Shuhua; Xing, Wei

2017-06-20

An in situ micro-MEA technique, which could precisely measure the performance of ORR electrocatalyst using Nafion as electrolyte, was designed and compared with regular thin-film rotating-disk electrode (TFRDE) (0.1 M HClO 4 ) and normal in situ membrane electrode assembly (MEA) tests. Compared to the traditional TFRDE method, the micro-MEA technique makes the acquisition of catalysts' behavior at low potential values easily achieved without being limited by the solubility of O 2 in water. At the same time, it successfully mimics the structure of regular MEAs and obtains similar results to a regular MEA, thus providing a new technique to simply measure the electrode activity without being bothered by complicated fabrication of regular MEA. In order to further understand the importance of in situ measurement, Fe-N-C as a typical oxygen reduction reaction (ORR) free-Pt catalyst was evaluated by TFRDE and micro-MEA. The results show that the half wave potential of Fe-N-C only shifted negatively by -135 mV in comparison with state-of-the-art Pt/C catalysts from TFRDE tests. However, the active site density, mass transfer of O 2 , and the proton transfer conductivity are found to strongly influence the catalyst activity in the micro-MEA, thereby resulting in a much lower limiting current density than Pt/C (8.7 times lower). Hence, it is suggested that the micro-MEA is better in evaluating the in situ ORR performance, where the catalysts are characterized more thoroughly in terms of intrinsic activity, active site density, proton transfer, and mass transfer properties.

Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O

Science.gov (United States)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O

Science.gov (United States)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Evaporation rates and surface profiles on heterogeneous surfaces with mass transfer and surface reaction

Energy Technology Data Exchange (ETDEWEB)

Flytzani-Stephanopoulos, M; Schmidt, L D

1979-01-01

Simple models incorporating surface reaction and diffusion of volatile products through a boundary layer are developed to calculate effective rates of evaporation and local surface profiles on surfaces having active and inactive regions. The coupling between surface heterogeneities with respect to a particular reaction and external mass transfer may provide a mechanism for the surface rearrangement and metal loss encountered in several catalytic systems of practical interest. Calculated transport rates for the volatilization of platinum in oxidizing environments and the rearrangement of this metal during the ammonia oxidation reaction agree well with published experimental data.

Effect of directional solidification rate on the microstructure and properties of deformation-processed Cu–7Cr–0.1Ag in situ composites

Energy Technology Data Exchange (ETDEWEB)

Liu, Keming [Jiangxi Key Laboratory for Advanced Copper and Tungsten Materials, Jiangxi Academy of Sciences, Nanchang 330029 (China); School of Mechanical, Materials and Mechatronic Engineering, University of Wollongong, NSW 2522 (Australia); Jiang, Zhengyi; Zhao, Jingwei [School of Mechanical, Materials and Mechatronic Engineering, University of Wollongong, NSW 2522 (Australia); Zou, Jin; Chen, Zhibao [Jiangxi Key Laboratory for Advanced Copper and Tungsten Materials, Jiangxi Academy of Sciences, Nanchang 330029 (China); Lu, Deping, E-mail: llludp@163.com [Jiangxi Key Laboratory for Advanced Copper and Tungsten Materials, Jiangxi Academy of Sciences, Nanchang 330029 (China)

2014-11-05

Highlights: • Effect of directional solidification (DS) rate on a Cu–Cr–Ag in situ composite. • The microstructure and properties of the DS in situ composite were investigated. • The second-phase Cr grains were parallel to drawing direction, and were finer. • The tensile strength was higher and the combination of properties was better. - Abstract: The influence of directional solidification rate on the microstructure, mechanical properties and conductivity of deformation-processed Cu–7Cr–0.1Ag in situ composites produced by thermo-mechanical processing was systematically investigated. The microstructure was analyzed by optical microscopy and scanning electronic microscopy. The mechanical properties and conductivity were evaluated by tensile-testing machine and micro-ohmmeter, respectively. The results indicate that the size, shape and distribution of second-phase Cr grains are significantly different in the Cu–7Cr–0.1Ag alloys with different growth rates. At a growth rate of 200 μm s{sup −1}, the Cr grains transform into fine Cr fiber-like grains parallel to the pulling direction from the Cr dendrites. The tensile strength of the Cu–7Cr–0.1Ag in situ composites from the directional solidification (DS) alloys is significantly higher than that from the as-cast alloy, while the conductivity of the in situ composites from the DS alloys is slightly lower than that from the as-cast alloy. The following combinations of tensile strength, elongation to fracture and conductivity of the Cu–7Cr–0.1Ag in situ composites from the DS alloy with a growth rate of 200 μm s{sup −1} and a cumulative cold deformation strain of 8 after isochronic aging treatment for 1 h can be obtained respectively as: (i) 1067 MPa, 2.9% and 74.9% IACS; or (ii) 1018 MPa, 3.0%, and 76.0% IACS or (iii) 906 MPa, 3.3% and 77.6% IACS.

Interfacial reactions in intermetallic matrix composites

International Nuclear Information System (INIS)

Cantrell, L.B.; Clevenger, E.M.; Perepezko, J.H.

1993-01-01

The thermal stability of advanced composites is dominated by the behavior of internal interfaces. Analysis of these internal interfaces often involves consideration of at least ternary order phase equilibria. Limited thermodynamic data exists for ternary and higher order systems. However, a combined approach based upon the use of binary data to estimate ternary phase equilibria and experimentally determined reaction pathways is effective in the analysis of interface reactions in composite systems. In blended powder samples, thermal analysis was used to find possible reaction temperatures, while X-ray analysis, EDS, and EPMA of diffusion couples were used to assess interdiffusion reaction pathways. The approach is illustrated by compatibility studies between TiAl and TiSi 2 at 1,100 C, and in-situ reactions between B 4 C and TiAl at 1300 C where multiple reaction sequences have been analyzed to provide guidance for the design of in-situ reaction processing of composites

In-situ degradation of sulphur mustard using (1R)-(-)-(camphorylsulphonyl) oxaziridine impregnated adsorbents

Energy Technology Data Exchange (ETDEWEB)

Sharma, Abha, E-mail: abha_052002@yahoo.co.in [Industrial Toxicology Research Centre, Mahatam Gandhi Marg, Lucknow, UP (India); Saxena, Amit; Singh, Beer [Defence Research and Development Establishment, Jhansi Road, Gwalior, MP (India)

2009-12-30

Bis-2-chloroethyl sulphide (sulphur mustard or HD) is an extremely toxic and persistent chemical warfare agent. For in-situ degradation of HD and its analogues (simulants), i.e., dibutyl sulphide (DBS) and ethyl 2-hydroxyethyl sulphide (HEES), different adsorbents systems loaded with (1R)-(-)-(camphorylsulphonyl) oxaziridine were prepared. Solution of sulphur mustard and its simulants was prepared in carbon tetrachloride and taken for uniform adsorption on the impregnated systems using incipient volume. Degradation kinetics monitored by GC/FID were found to be first-order. The half-life of degradation reactions for simulants was obtained in less than 30 and for HD in 120 min. From the studied kinetics it was observed that reaction was very rapid with simulants and decreased rate was found for HD. The order of reactivity of MgO/Oxa system for HD and simulants was found to be DBS > HEES > HD. Reaction products of the oxidation reaction of simulants and HD on adsorbents were extracted in dichloromethane and analysed by GC-MS. The products were found to be non-toxic sulphoxide. The objective of the study is to develop a reactive adsorbent for in-situ degradation of sulphur mustard which could be used in nuclear biological and chemical (NBC) filtration systems.

Determination of the enzyme reaction rate in a differential fixed-bed reactor: a case study

Directory of Open Access Journals (Sweden)

Baruque Filho E.A.

2001-01-01

Full Text Available The reaction rate of starch hydrolysis catalyzed by a glucoamylase covalently bound to chitin particles was measured in a Differential Fixed-Bed Reactor (DFBR. Under selected test conditions the initial reaction rate may represent biocatalyst activity. Some aspects which influence measurement of the initial reaction rate of an immobilized enzyme were studied: the amount of desorbed enzyme and its hydrolytic activity, the extent of pore blockage of the biocatalyst caused by substrate solution impurities and the internal and external diffusional mass transfer effects. The results showed that the enzyme glucoamylase was firmly bound to the support, as indicated by the very low amount of desorbed protein found in the recirculating liquid. Although this protein was very active, its contribution to the overall reaction rate was negligible. It was observed that the biocatalyst pores were susceptible to being blocked by the impurities of the starch solution. This latter effect was accumulative, increasing with the number of sequential experiments carried out. When the substrate solution was filtered before use, very reliable determinations of immobilized enzyme reaction rates could be performed in the DFBR. External and internal diffusional resistences usually play a significant role in fixed-bed reactors. However, for the experimental system studied, internal mass transfer effects were not significant, and it was possible to select an operational condition (recirculation flow rate value that minimized the external diffusional limitations.

The study of redox mechanism of dobutamine at different pH media by electrochemical and in situ spectroelectrochemical methods

International Nuclear Information System (INIS)

Yang Gongjun; Xu Jingjuan; Chen Hongyuan

2004-01-01

Based on the comprehensive analyses of the experimental results of the electrochemical methods, in situ UV-Vis absorption spectra, in situ electron spin resonance (ESR), and attenuated total-internal reflection (ATR) as well as the calculation of UV-Vis absorption data by PM3 Semi-Empirical method, a reaction mechanism for the redox processes of dobutamine was presented. When the anodic sweep is carried out, dobutamine firstly undergoes a free radical reaction with one-electron and one-proton to form semi-quinone free radicals, which will continuously convert to its corresponding quinone form by further electrochemical oxidation reaction. The formed quinone cannot only undergo a cyclization process by chemical reaction to produce a new compound, which can be reduced at more negative potential, but also be reduced to form dobutamine again when subsequent cathodic sweep is followed. The cyclization rate is depended upon pH values, and it increases with the increase of pH. In neutral medium, the corresponding oxidation form of the cyclization reaction product is easy to convert to melanin

Relationship between reaction layer thickness and leach rate for nuclear waste glasses

International Nuclear Information System (INIS)

Chick, L.A.; Pederson, L.R.

1984-02-01

Three leaching tests, devised to distinguish among several proposed nuclear waste glass leaching mechanisms, were carried out for four different waste glasses. In the first test, the influence of a pre-formed reaction layer on elemental release was evaluated. In the second test, glass specimens were replaced with fresh samples halfway through the leaching experiment, to evaluate the influence of the concentration of glass components in leaching. Finally, regular replacement of the leachant at fixed time intervals essentially removed the variable changing solution concentration, and allowed an assessment of the influence of reaction layer thickness on the leaching rate. Results for all glasses tested indicated that the reaction layer presented little or no barrier to leaching, and that most of the retardation on leaching rates generally observed are attributable to saturation effects. 20 references, 6 figures, 1 table

Understanding and Improvement of an Experiment Measuring Chemical Reaction Rates by Monitoring Volume Change of a Gas: On the Reaction between HCl(aq) and Mg(s)

International Nuclear Information System (INIS)

Bang, Jeong Ah; Yoon, Hee Sook; Jeong, Dae Hong; Choi, Won Ho

2006-01-01

In this study we analyzed and improved an experiment measuring chemical reaction rates introduced in the high school science textbooks through an understanding of the phenomena observed in carrying out the experiment. For this purpose, the contents of textbooks related to the experiment were analyzed, and the problems observed in carrying out the experiment were addressed through experimental analysis. When the experiment was carried out by the method of aquatic transposition presented in textbooks, the observed volume change of H 2 gas was delayed and chemical reaction rate was increased in the early stage of reaction period. To resolve these problems, an improved method for measuring the reaction rates was suggested. In the improved experiment the reaction rate was measured to be constant on time, which was interpreted in terms of the concentration of H + and the surface area of magnesium

A simple recipe for modeling reaction-rate in flows with turbulent-combustion

Science.gov (United States)

Girimaji, Sharath S.

1991-01-01

A computationally viable scheme to account for chemical reaction in turbulent flows is presented. The multivariate beta-pdf model for multiple scalar mixing forms the basis of this scheme. Using the model scalar joint pdf and a general form of the instantaneous reaction-rate, the unclosed chemical reaction terms are expressed as simple functions of scalar means and the turbulent scalar energy. The calculation procedure requires that the mean scalar equations and only one other transport equation - for the turbulent scalar energy - be solved.

Primordial lithium: New reaction rates, new abundances, new constraints

International Nuclear Information System (INIS)

Kawano, L.; Schramm, D.; Steigman, G.

1986-12-01

Newly measured nuclear reaction rates for 3 H(α,γ) 7 Li (higher than previous values) and 7 Li(p,α) 4 He (lower than previous values) are shown to increase the 7 Li yield from big bang nucleosynthesis for lower baryon to photon ratio (eta ≤ 4 x 10 -10 ); the yield for higher eta is not affected. New, independent determinations of Li abundances in extreme Pop II stars are in excellent agreement with the earlier work of the Spites and give continued confidence in the use of 7 Li in big bang baryon density determinations. The new 7 Li constraints imply a lower limit on eta of 2 x 10 -10 and an upper limit of 5 x 10 -10 . This lower limit to eta is concordant with that obtained from considerations of D + 3 He. The upper limit is consistent with, but even more restrictive than, the D bound. With the new rates, any observed primordial Li/H ratio below 10 -10 would be inexplicable by the standard big bang nucleosynthesis. A review is made of the strengths and possible weaknesses of utilizing conclusions drawn from big bang lithium considerations. An appendix discusses the null effect of a factor of 32 increase in the experimental rate for the D(d,γ) 4 He reaction. 28 refs., 1 fig

In-situ buildup of cosmogenic isotopes at the earth`s surface: measurement of erosion rates and exposure times

Energy Technology Data Exchange (ETDEWEB)

Fifield, L K; Allan, G L; Stone, J O.H.; Evans, J M; Cresswell, R G; Ophel, T R [Australian National Univ., Canberra, ACT (Australia)

1994-12-31

Cosmic rays produce a number of nuclides in rocks that can be used to determine the geomorphic history of surfaces. The most useful are the radioactive isotopes {sup 10}Be (t{sub 1/2} = 1.5Ma), {sup 26}Al (0.7Ma) and {sup 36}Cl (0.3Ma). Within the top 2m of the surface, these are produced principally by fast neutrons. At greater depths, production is dominated by the capture of negative muons. Measurements of a single nuclide produced in situ can be used to determine total exposure times or erosion rates. The use of multiple nuclides with different half-lives makes it possible to determine more complex histories, such as exposures interrupted by periods of burial. At the ANU, all three of the isotopes above are being used to study a variety of problems in geomorphology and paleoclimatology, although to date, most of the work has concentrated on {sup 36}Cl. The accumulation of cosmogenic {sup 36}Cl in calcite (CaCO{sub 3}) provides a means of measuring erosion rates on limestone surfaces. Sensitivity is achieved over a wide range of erosion rates due to the high production rate of {sup 36}Cl in calcite (typically greater than 30 atoms/g/yr) and a detection limit of ca. 5000 atoms/g attainable with the ANU AMS system. The method is simplified by the predominance of Ca reactions (principally spallation) over other sources of {sup 36}Cl in calcite, and the ease of sample preparation. This presentation discuss the results of measurements of {sup 36}Cl in calcite from limestone samples from Australia and Papua New Guinea. Erosion rates derived from these measurements range from 3 microns per year (Australia) to over 200 microns per year in the New Guinea highlands. 3 refs.

In-situ buildup of cosmogenic isotopes at the earth`s surface: measurement of erosion rates and exposure times

Energy Technology Data Exchange (ETDEWEB)

Fifield, L.K.; Allan, G.L.; Stone, J.O.H.; Evans, J.M.; Cresswell, R.G.; Ophel, T.R. [Australian National Univ., Canberra, ACT (Australia)

1993-12-31

Cosmic rays produce a number of nuclides in rocks that can be used to determine the geomorphic history of surfaces. The most useful are the radioactive isotopes {sup 10}Be (t{sub 1/2} = 1.5Ma), {sup 26}Al (0.7Ma) and {sup 36}Cl (0.3Ma). Within the top 2m of the surface, these are produced principally by fast neutrons. At greater depths, production is dominated by the capture of negative muons. Measurements of a single nuclide produced in situ can be used to determine total exposure times or erosion rates. The use of multiple nuclides with different half-lives makes it possible to determine more complex histories, such as exposures interrupted by periods of burial. At the ANU, all three of the isotopes above are being used to study a variety of problems in geomorphology and paleoclimatology, although to date, most of the work has concentrated on {sup 36}Cl. The accumulation of cosmogenic {sup 36}Cl in calcite (CaCO{sub 3}) provides a means of measuring erosion rates on limestone surfaces. Sensitivity is achieved over a wide range of erosion rates due to the high production rate of {sup 36}Cl in calcite (typically greater than 30 atoms/g/yr) and a detection limit of ca. 5000 atoms/g attainable with the ANU AMS system. The method is simplified by the predominance of Ca reactions (principally spallation) over other sources of {sup 36}Cl in calcite, and the ease of sample preparation. This presentation discuss the results of measurements of {sup 36}Cl in calcite from limestone samples from Australia and Papua New Guinea. Erosion rates derived from these measurements range from 3 microns per year (Australia) to over 200 microns per year in the New Guinea highlands. 3 refs.

Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.

Science.gov (United States)

Habershon, Scott

2016-04-12

In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.

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

Energy Technology Data Exchange (ETDEWEB)

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

1979-05-15

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

Measurement from sun-synchronous orbit of a reaction rate controlling the diurnal NOx cycle in the stratosphere

Directory of Open Access Journals (Sweden)

A. Dudhia

2011-05-01

Full Text Available A reaction rate associated with the nighttime formation of an important diurnally varying species, N2O5, is determined from MIPAS-ENVISAT. During the day, photolysis of N2O5 in the stratosphere contributes to nitrogen-catalysed ozone destruction. However, at night concentrations of N2O5 increase, temporarily sequestering reactive NOx NO and NO2 in a natural cycle which regulates the majority of stratospheric ozone. In this paper, the reaction rate controlling the formation of N2O5 is determined from this instrument for the first time. The observed reaction rate is compared to the currently accepted rate determined from laboratory measurements. Good agreement is obtained between the observed and accepted experimental reaction rates within the error bars.

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

International Nuclear Information System (INIS)

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

1983-01-01

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

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

NARCIS (Netherlands)

Juraszek, J.; Bolhuis, P.G.

2008-01-01

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

In situ observation of the reaction of scandium and carbon by neutron diffraction

Energy Technology Data Exchange (ETDEWEB)

Juarez-Arellano, Erick A., E-mail: eajuarez@unpa.edu.m [Institut fuer Geowissenschaften, Universitaet Frankfurt, Altenhoeferallee 1, 60438 Frankfurt a.M. (Germany); Universidad del Papaloapan, Circuito Central 200, Parque Industrial, Tuxtepec 68301 (Mexico); Winkler, Bjorn [Institut fuer Geowissenschaften, Universitaet Frankfurt, Altenhoeferallee 1, 60438 Frankfurt a.M. (Germany); Vogel, Sven C. [Los Alamos National Laboratory, Lujan Center. Mail Stop H805, Los Alamos, NM 87545 (United States); Senyshyn, Anatoliy [Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universitaet Muenchen, Lichtenbergstr. 1, D-85747 Garching (Germany); Materialwissenschaft, TU Darmstadt, Petersensstr. 23, D-64287 Darmstadt (Germany); Kammler, Daniel R. [Sandia National Laboratories, Albuquerque, NM 87185 (United States); Avalos-Borja, Miguel [CNyN, UNAM, A. Postal 2681, Ensenada, B.C. (Mexico)

2011-01-05

Research highlights: {yields} Exist two ScC cubic phases with B1-structure type differing in site occupancy of C. {yields} A new orthorhombic scandium carbide phase is formed at 1473(50) K. {yields} The recrystallization of alpha-Sc occurs between 1000 and 1223 K. - Abstract: The formation of scandium carbides by reaction of the elements has been investigated by in situ neutron diffraction up to 1823 K. On heating, the recrystallization of {alpha}-Sc occurs between 1000 and 1223 K. The formation of Sc{sub 2}C and ScC (NaCl-B1 type structure) phases has been detected at 1323 and 1373 K, respectively. The formation of a new orthorhombic scandium carbide phase was observed at 1473(50) K. Once the scandium carbides are formed they are stable upon heating or cooling. No other phases were detected in the present study, in which the system was always carbon saturated. The thermal expansion coefficients of all phases have been determined, they are constant throughout the temperature interval studied.

A numerical evaluation of prediction accuracy of CO2 absorber model for various reaction rate coefficients

Directory of Open Access Journals (Sweden)

Shim S.M.

2012-01-01

Full Text Available The performance of the CO2 absorber column using mono-ethanolamine (MEA solution as chemical solvent are predicted by a One-Dimensional (1-D rate based model in the present study. 1-D Mass and heat balance equations of vapor and liquid phase are coupled with interfacial mass transfer model and vapor-liquid equilibrium model. The two-film theory is used to estimate the mass transfer between the vapor and liquid film. Chemical reactions in MEA-CO2-H2O system are considered to predict the equilibrium pressure of CO2 in the MEA solution. The mathematical and reaction kinetics models used in this work are calculated by using in-house code. The numerical results are validated in the comparison of simulation results with experimental and simulation data given in the literature. The performance of CO2 absorber column is evaluated by the 1-D rate based model using various reaction rate coefficients suggested by various researchers. When the rate of liquid to gas mass flow rate is about 8.3, 6.6, 4.5 and 3.1, the error of CO2 loading and the CO2 removal efficiency using the reaction rate coefficients of Aboudheir et al. is within about 4.9 % and 5.2 %, respectively. Therefore, the reaction rate coefficient suggested by Aboudheir et al. among the various reaction rate coefficients used in this study is appropriate to predict the performance of CO2 absorber column using MEA solution. [Acknowledgement. This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF, funded by the Ministry of Education, Science and Technology (2011-0017220].

Rate coefficients from quantum and quasi-classical cumulative reaction probabilities for the S(1D) + H2 reaction

Science.gov (United States)

Jambrina, P. G.; Lara, Manuel; Menéndez, M.; Launay, J.-M.; Aoiz, F. J.

2012-10-01

Cumulative reaction probabilities (CRPs) at various total angular momenta have been calculated for the barrierless reaction S(1D) + H2 → SH + H at total energies up to 1.2 eV using three different theoretical approaches: time-independent quantum mechanics (QM), quasiclassical trajectories (QCT), and statistical quasiclassical trajectories (SQCT). The calculations have been carried out on the widely used potential energy surface (PES) by Ho et al. [J. Chem. Phys. 116, 4124 (2002), 10.1063/1.1431280] as well as on the recent PES developed by Song et al. [J. Phys. Chem. A 113, 9213 (2009), 10.1021/jp903790h]. The results show that the differences between these two PES are relatively minor and mostly related to the different topologies of the well. In addition, the agreement between the three theoretical methodologies is good, even for the highest total angular momenta and energies. In particular, the good accordance between the CRPs obtained with dynamical methods (QM and QCT) and the statistical model (SQCT) indicates that the reaction can be considered statistical in the whole range of energies in contrast with the findings for other prototypical barrierless reactions. In addition, total CRPs and rate coefficients in the range of 20-1000 K have been calculated using the QCT and SQCT methods and have been found somewhat smaller than the experimental total removal rates of S(1D).

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.

Actinide complexation kinetics: rate and mechanism of dioxoneptunium (V) reaction with chlorophosphonazo III

International Nuclear Information System (INIS)

Fugate, G.; Feil-Jenkins, J.F.; Sullivan, J.C.; Nash, K.L.

1996-12-01

Rates of complex formation and dissociation in NpO 2 + - Chlorophosphonazo III (2,7-bis(4-chloro-2-phosphonobenzeneazo)-1,8- dihydroxynapthalene-3,6-disulfonic acid)(CLIII) were investigated by stopped-flow spectrophotometry. Also, limited studies were made of the rates of reaction of La 3+ , Eu 3+ , Dy 3+ , and Fe 3+ with CLIII. Rate determining step in each system is an intramolecular process, the NpO 2 + -CLIII reaction proceeding by a first order approach to equilibrium in the acid range from 0.1 to 1.0 M. Complex formation occurs independent of acidity, while both acid dependent and independent dissociation pathways are observed. Activation parameters for the complex formation reaction are ΔH=46.2±0.3 kJ/m and ΔS=7± J/mK (I=1.0 M); these for the acid dependent and independent dissociation pathways are ΔH=38.8±0.6 kJ/m, ΔS=-96±18 J/mK, ΔH=70.0± kJ/m, and ΔS=17±1 J/mK, respectively. An isokinetic relationship is observed between the activation parameters for CLIII complex formation with NpO 2 + , UO 2 2+ , Th 4+ , and Zr 4+ . Rates of CLIII complex formation reactions for Fe 3+ , Zr 4+ , NpO 2 + , UO 2 2+ , Th 4+ , La 3+ , Eu 3+ , and Dy 3+ correlate with cation radius rather than charge/radius ratio

Reaction rate of a composite core-shell nanoreactor with multiple nanocatalysts.

Science.gov (United States)

Galanti, Marta; Fanelli, Duccio; Angioletti-Uberti, Stefano; Ballauff, Matthias; Dzubiella, Joachim; Piazza, Francesco

2016-07-27

We present a detailed theory for the total reaction rate constant of a composite core-shell nanoreactor, consisting of a central solid core surrounded by a hydrogel layer of variable thickness, where a given number of small catalytic nanoparticles are embedded at prescribed positions and are endowed with a prescribed surface reaction rate constant. Besides the precise geometry of the assembly, our theory accounts explicitly for the diffusion coefficients of the reactants in the hydrogel and in the bulk as well as for their transfer free energy jump upon entering the hydrogel shell. Moreover, we work out an approximate analytical formula for the overall rate constant, which is valid in the physically relevant range of geometrical and chemical parameters. We discuss in depth how the diffusion-controlled part of the rate depends on the essential variables, including the size of the central core. In particular, we derive some simple rules for estimating the number of nanocatalysts per nanoreactor for an efficient catalytic performance in the case of small to intermediate core sizes. Our theoretical treatment promises to provide a very useful and flexible tool for the design of superior performing nanoreactor geometries with optimized nanoparticle load.

Gas sensing properties and in situ diffuse reflectance infrared Fourier transform spectroscopy study of trichloroethylene adsorption and reactions on SnO2 films

Science.gov (United States)

Zhang, Zhenxin; Huang, Kaijin; Yuan, Fangli; Xie, Changsheng

2014-05-01

The detection of trichloroethylene has attracted much attention because it has an important effect on human health. The sensitivity of the SnO2 flat-type coplanar gas sensor arrays to 100 ppm trichloroethylene in air was investigated. The adsorption and surface reactions of trichloroethylene were investigated at 100-200 °C by in-situ diffuse reflection Fourier transform infrared spectroscopy (DIRFTS) on SnO2 films. Molecularly adsorbed trichloroethylene, dichloroacetyl chloride (DCAC), phosgene, HCl, CO, H2O, CHCl3, Cl2 and CO2 surface species are formed during trichloroethylene adsorption at 100-200 °C. A possible mechanism of the reaction process is discussed.

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

International Nuclear Information System (INIS)

Damunir

2007-01-01

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

EFFECTS OF PORE STRUCTURE CHANGE AND MULTI-SCALE HETEROGENEITY ON CONTAMINANT TRANSPORT AND REACTION RATE UPSCALING

Energy Technology Data Exchange (ETDEWEB)

Peters, Catherine A [Princeton University

2013-05-15

This project addressed the scaling of geochemical reactions to core and field scales, and the interrelationship between reaction rates and flow in porous media. We targeted reactive transport problems relevant to the Hanford site specifically the reaction of highly caustic, radioactive waste solutions with subsurface sediments, and the immobilization of 90Sr and 129I through mineral incorporation and passive flow blockage, respectively. We addressed the correlation of results for pore-scale fluid-soil interaction with field-scale fluid flow, with the specific goals of (i) predicting attenuation of radionuclide concentration; (ii) estimating changes in flow rates through changes of soil permeabilities; and (iii) estimating effective reaction rates. In supplemental work, we also simulated reactive transport systems relevant to geologic carbon sequestration. As a whole, this research generated a better understanding of reactive transport in porous media, and resulted in more accurate methods for reaction rate upscaling and improved prediction of permeability evolution. These scientific advancements will ultimately lead to better tools for management and remediation of DOE legacy waste problems.

Effects of Processing Parameters on the Fabrication of in-situ Al/TiC Composites by Thermally Activated Combustion Reaction Process in an Aluminium Melt using Al-TiO_2-C Powder Mixtures

International Nuclear Information System (INIS)

Kim, Hwa-Jung; Lee, Jung-Moo; Cho, Young-Hee; Kim, Jong-Jin; Kim, Su-Hyeon; Lee, Jae-Chul

2012-01-01

A feasible way to fabricate in-situ Al/TiC composites was investigated. An elemental mixture of Al-TiO_2-C pellet was directly added into an Al melt at 800-920°C to form TiC by self-combustion reaction. The addition of CuO initiates the self-combustion reaction to form TiC in 1-2 um at the melt temperature above 850°C. Besides the CuO addition, a diluent element of excess Al plays a significant role in the TiC formation by forming a precursor phase, Al_3Ti. Processing parameters such as CuO content, the amount of excess Al and the melt temperature, have affected the combustion reaction and formation of TiC, and their influences on the microstructures of in-situ Al/TiC composites are examined.

Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Copper

CERN Document Server

American Society for Testing and Materials. Philadelphia

2011-01-01

1.1 This test method covers procedures for measuring reaction rates by the activation reaction 63Cu(n,α)60Co. The cross section for 60Co produced in this reaction increases rapidly with neutrons having energies greater than about 5 MeV. 60Co decays with a half-life of 1925.27 days (±0.29 days)(1) and emits two gamma rays having energies of 1.1732278 and 1.332492 MeV (1). The isotopic content of natural copper is 69.17 % 63Cu and 30.83 % 65Cu (2). The neutron reaction, 63Cu(n,γ)64Cu, produces a radioactive product that emits gamma rays which might interfere with the counting of the 60Co gamma rays. 1.2 With suitable techniques, fission-neutron fluence rates above 109 cm−2·s−1 can be determined. The 63Cu(n,α)60Co reaction can be used to determine fast-neutron fluences for irradiation times up to about 15 years (for longer irradiations, see Practice E261). 1.3 Detailed procedures for other fast-neutron detectors are referenced in Practice E261. 1.4 This standard does not purport to address all of the...

Standard Test Method for Measuring Reaction Rates by Radioactivation of Uranium-238

CERN Document Server

American Society for Testing and Materials. Philadelphia

2008-01-01

1.1 This test method covers procedures for measuring reaction rates by assaying a fission product (F.P.) from the fission reaction 238U(n,f)F.P. 1.2 The reaction is useful for measuring neutrons with energies from approximately 1.5 to 7 MeV and for irradiation times up to 30 to 40 years. 1.3 Equivalent fission neutron fluence rates as defined in Practice E 261 can be determined. 1.4 Detailed procedures for other fast-neutron detectors are referenced in Practice E 261. 1.5 The values stated in SI units are to be regarded as standard. No other unites of measurement are included in this standard. 1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

Standard Test Method for Measuring Reaction Rates by Radioactivation of Neptunium-237

CERN Document Server

American Society for Testing and Materials. Philadelphia

2008-01-01

1.1 This test method covers procedures for measuring reaction rates by assaying a fission product (F.P.) from the fission reaction 237Np(n,f)F.P. 1.2 The reaction is useful for measuring neutrons with energies from approximately 0.7 to 6 MeV and for irradiation times up to 30 to 40 years. 1.3 Equivalent fission neutron fluence rates as defined in Practice E 261 can be determined. 1.4 Detailed procedures for other fast-neutron detectors are referenced in Practice E 261. 1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard. 1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

Large area isotopic silicon targets for astrophysical reaction rate studies in Si-26

NARCIS (Netherlands)

Greene, JP; Berg, GPA

2005-01-01

For measurements of stellar reaction rates of proton rich nuclei involving resonance levels just above threshold, targets of Si-28 were used in studies of the Si-21(He-4, He-6)Si-26 reaction using the Research Center for Nuclear Physics (RCNP) Ring Cyclotron at Osaka University. Resonance structure

Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Aluminum

CERN Document Server

American Society for Testing and Materials. Philadelphia

2011-01-01

1.1 This test method covers procedures measuring reaction rates by the activation reaction 27Al(n,α)24Na. 1.2 This activation reaction is useful for measuring neutrons with energies above approximately 6.5 MeV and for irradiation times up to about 2 days (for longer irradiations, see Practice E261). 1.3 With suitable techniques, fission-neutron fluence rates above 106 cm−2·s−1 can be determined. 1.4 Detailed procedures for other fast neutron detectors are referenced in Practice E261. 1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

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

International Nuclear Information System (INIS)

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

1976-01-01

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

A new approach to estimate the in situ fractional degradation rate of organic matter and nitrogen in wheat yeast concentrates

NARCIS (Netherlands)

De Jonge, L. H.; Van Laar, H.; Hendriks, W. H.; Dijkstra, J.

2015-01-01

In the classic in situ method, small particles are removed during rinsing and hence their fractional degradation rate cannot be determined. A new approach was developed to estimate the fractional degradation rate of nutrients in small particles. This approach was based on an alternative rinsing

Rates of ionic reactions with charged nanoparticles in aqueous media

NARCIS (Netherlands)

Duval, J.F.L.; Leeuwen, van H.P.

2012-01-01

A theory is developed to evaluate the electrostatic correction for the rate of reaction between a small ion and a charged ligand nanoparticle. The particle is assumed to generally consist of an impermeable core and a shell permeable to water and ions. A derivation is proposed for the ion diffusion

Lithium iron phosphate with high-rate capability synthesized through hydrothermal reaction in glucose solution

Energy Technology Data Exchange (ETDEWEB)

Liang, Guangchuan; Wang, Li; Ou, Xiuqin; Zhao, Xia; Xu, Shengzhao [Institute of Power Source and Ecomaterials Science, Box 1055, Hebei University of Technology, 300130 Tianjin (China)

2008-10-01

Carbon-coated lithium iron phosphate (LiFePO{sub 4}/C) was hydrothermally synthesized from commercial LiOH, FeSO{sub 4} and H{sub 3}PO{sub 4} as raw materials and glucose as carbon precursor in aqueous solution at 180 C for 6 h followed by being fired at 750 C for 6 h. The samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and constant current charge-discharge cycling test. The results show that the synthesized powders are in situ coated with carbon precursor produced from glucose. At ambient temperature (25{+-}2 C), the specific discharge capacities are 154 mAh g{sup -1} at 0.2C and 136 mAh g{sup -1} at 5 C rate, and the cycling capacity retention rate reaches 98% over 90 cycles. The excellent electrochemical performance can be correlated with the in situ formation of carbon precursor/carbon, thus leading to the even distribution of carbon and the enhancement of conductibility of individual grains. (author)

Expedient construction of small molecule macroarrays via sequential palladium- and copper-mediated reactions and their ex situ biological testing.

Science.gov (United States)

Frei, Reto; Breitbach, Anthony S; Blackwell, Helen E

2012-05-01

We report the highly efficient syntheses of a series of focused libraries in the small molecule macroarray format using Suzuki-Miyaura and copper-catalyzed azide-alkyne cycloaddition (or "click") reactions. The libraries were based on stilbene and triazole scaffolds, which are known to have a broad range of biological activities, including quorum-sensing (QS) modulation in bacteria. The library products were generated in parallel on the macroarray in extremely short reaction times (~10-20 min) and isolated in excellent purities. Biological testing of one macroarray library post-cleavage (ex situ) revealed several potent agonists of the QS receptor, LuxR, in Vibrio fischeri. These synthetic agonists, in contrast to others that we have reported, were only active in the presence of the native QS signal in V. fischeri, which is suggestive of a different mode of activity. Notably, the results presented herein showcase the ready compatibility of the macroarray platform with chemical reactions that are commonly utilized in small molecule probe and drug discovery today. As such, this work serves to expand the utility of the small molecule macroarray as a rapid and operationally straightforward approach toward the synthesis and screening of bioactive agents.

In situ growth rate measurements during plasma-enhanced chemical vapour deposition of vertically aligned multiwall carbon nanotube films

International Nuclear Information System (INIS)

Joensson, M; Nerushev, O A; Campbell, E E B

2007-01-01

In situ laser reflectivity measurements are used to monitor the growth of multiwalled carbon nanotube (MWCNT) films grown by DC plasma-enhanced chemical vapour deposition (PECVD) from an iron catalyst film deposited on a silicon wafer. In contrast to thermal CVD growth, there is no initial increase in the growth rate; instead, the initial growth rate is high (as much as 10 μm min -1 ) and then drops off rapidly to reach a steady level (2 μm min -1 ) for times beyond 1 min. We show that a limiting factor for growing thick films of multiwalled nanotubes (MWNTs) using PECVD can be the formation of an amorphous carbon layer at the top of the growing nanotubes. In situ reflectivity measurements provide a convenient technique for detecting the onset of the growth of this layer

In situ DRIFTS investigation of NH3-SCR reaction over CeO2/zirconium phosphate catalyst

Science.gov (United States)

Zhang, Qiulin; Fan, Jie; Ning, Ping; Song, Zhongxian; Liu, Xin; Wang, Lanying; Wang, Jing; Wang, Huimin; Long, Kaixian

2018-03-01

A series of ceria modified zirconium phosphate catalysts were synthesized for selective catalytic reduction of NO with ammonia (NH3-SCR). Over 98% NOx conversion and 98% N2 selectivity were obtained by the CeO2/ZrP catalyst with 20 wt.% CeO2 loading at 250-425 °C. The interaction between CeO2 and zirconium phosphate enhanced the redox abilities and surface acidities of the catalysts, resulting in the improvement of NH3-SCR activity. The in situ DRIFTS results indicated that the NH3-SCR reaction over the catalysts followed both Eley-Rideal and Langmuir-Hinshelwood mechanisms. The amide (sbnd NH2) groups and the NH4+ bonded to Brønsted acid sites were the important intermediates of Eley-Rideal mechanism.

The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients.

Science.gov (United States)

Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

2017-09-07

A theoretical study, involving the calculation of reaction enthalpies, activation energies, mechanisms, and rate coefficients, was made of the reaction of hydroxyl radicals with methyl nitrate, an important process for methyl nitrate removal in the earth's atmosphere. Four reaction channels were considered: formation of H 2 O + CH 2 ONO 2 , CH 3 OOH + NO 2 , CH 3 OH + NO 3 , and CH 3 O + HNO 3 . For all channels, geometry optimization and frequency calculations were performed at the M06-2X/6-31+G** level, while relative energies were improved at the UCCSD(T*)-F12/CBS level. The major channel is found to be the H abstraction channel, to give the products H 2 O + CH 2 ONO 2 . The reaction enthalpy (ΔH 298 K RX ) of this channel is computed as -17.90 kcal mol -1 . Although the other reaction channels are also exothermic, their reaction barriers are high (>24 kcal mol -1 ), and therefore these reactions do not contribute to the overall rate coefficient in the temperature range considered (200-400 K). Pathways via three transition states were identified for the H abstraction channel. Rate coefficients were calculated for these pathways at various levels of variational transition state theory including tunneling. The results obtained are used to distinguish between two sets of experimental rate coefficients, measured in the temperature range of 200-400 K, one of which is approximately an order of magnitude greater than the other. This comparison, as well as the temperature dependence of the computed rate coefficients, shows that the lower experimental values are favored. The implications of the results to atmospheric chemistry are discussed.

Combining nanocalorimetry and dynamic transmission electron microscopy for in situ characterization of materials processes under rapid heating and cooling

Energy Technology Data Exchange (ETDEWEB)

Grapes, Michael D., E-mail: mgrapes1@jhu.edu [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Materials Measurement Science Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); LaGrange, Thomas; Reed, Bryan W.; Campbell, Geoffrey H. [Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Friedman, Lawrence H.; LaVan, David A., E-mail: david.lavan@nist.gov [Materials Measurement Science Division, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (United States); Weihs, Timothy P., E-mail: weihs@jhu.edu [Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States)

2014-08-15

Nanocalorimetry is a chip-based thermal analysis technique capable of analyzing endothermic and exothermic reactions at very high heating and cooling rates. Here, we couple a nanocalorimeter with an extremely fast in situ microstructural characterization tool to identify the physical origin of rapid enthalpic signals. More specifically, we describe the development of a system to enable in situ nanocalorimetry experiments in the dynamic transmission electron microscope (DTEM), a time-resolved TEM capable of generating images and electron diffraction patterns with exposure times of 30 ns–500 ns. The full experimental system consists of a modified nanocalorimeter sensor, a custom-built in situ nanocalorimetry holder, a data acquisition system, and the DTEM itself, and is capable of thermodynamic and microstructural characterization of reactions over a range of heating rates (10{sup 2} K/s–10{sup 5} K/s) accessible by conventional (DC) nanocalorimetry. To establish its ability to capture synchronized calorimetric and microstructural data during rapid transformations, this work describes measurements on the melting of an aluminum thin film. We were able to identify the phase transformation in both the nanocalorimetry traces and in electron diffraction patterns taken by the DTEM. Potential applications for the newly developed system are described and future system improvements are discussed.

Control rod effects on reaction rate distributions in tight pitched PuO2-UO2 fuel assembly

International Nuclear Information System (INIS)

Gil, Choong-Sup; Okumura, Keisuke; Ishiguro, Yukio

1991-11-01

Investigations were made for the heterogeneity effects caused by insertion or withdrawal of a B 4 C control rod on fine structure of reaction rates distributions in a tight pitched PuO 2 -UO 2 fuel assembly. Analysis was carried out by using the VIM and SRAC codes with the libraries based on JENDL-2 for the hexagonal fuel assembly basically corresponding to the PROTEUS-LWHCR experimental core. The reaction rates are affected more remarkably by the withdrawal of the control rod rather than its insertion. The changes of the reaction rates were decomposed into three terms of spectrum shifts, the changes of effective cross sections with fine groups, and their higher order components. From the analysis, it is concluded that most changes of reaction rates are caused by spectral shifts. The SRAC code with fine group constants can predict the distribution of reaction rates and their ratios with the accuracy of about 5 % except for the values related to Pu-242 capture rate, as compared with the VIM results. To increase the accuracy, it is necessary to generate the effective cross sections of the fuel near control rods with consideration of the heterogeneities in the fuel assembly. (author)

Temperature dependence of electrocatalytic and photocatalytic oxygen evolution reaction rates using NiFe oxide

KAUST Repository

Nurlaela, Ela

2016-01-25

The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER kinetics were investigated. For electrocatalysis, a NiFeOx catalyst was hydrothermally decorated on Ni foam. In 1 M KOH solution, the NiFeOx electrocatalyst achieved 10 mA cm-2 at an overpotential of 260 mV. The same catalyst was decorated on the surface of Ta3N5 photocatalyst powder. The reaction was conducted in the presence of 0.1 M Na2S2O8 as a strong electron scavenger, thus likely leading to the OER being kinetically relevant. When compared with the bare Ta3N5, NiFeOx/Ta3N5 demonstrated a 5-fold improvement in photocatalytic activity in the OER under visible light irradiation, achieving a quantum efficiency of 24 % at 480 nm. Under the conditions investigated, a strong correlation between the electrocatalytic and photocatalytic performances was identified: an improvement in electrocatalysis corresponded with an improvement in photocatalysis without altering the identity of the materials. The rate change at different pH was likely associated with electrocatalytic kinetics that accordingly influenced the photocatalytic rates. The sensitivity of the reaction rates with respective to the reaction temperature resulted in an apparent activation energy of 25 kJ mol-1 in electrocatalysis, whereas that in photocatalysis was 16 kJ mol-1. The origin of the difference in these activation energy values is likely attributed to the possible effects of temperature on the individual thermodynamic and kinetic parameters of the reaction process. The work described herein demonstrates a method of “transferring the knowledge of electrocatalysis to photocatalysis” as a strong tool to rationally and quantitatively understand the complex reaction schemes involved in photocatalytic reactions.

Kinetics of isotope exchange reactions involving intra- and intermolecular reactions: 1. Rate law for a system with two chemical compounds and three exchangeable atoms

International Nuclear Information System (INIS)

Xuelei Chu; Ohmoto, Hiroshi

1991-01-01

For an isotopic exchange reaction between two compounds (X and AB) in a homogeneous system, such as a gaseous or aqueous system, where one (AB) of them possesses two exchangeable atoms in non-equivalent positions and where one intramolecular isotope exchange (A ↔ B) and two intermolecular isotope exchange reactions (X ↔ A and X ↔ B) may occur, its rate law no longer obeys a pseudo-first order rate equation described for simple two-component systems by many previous investigators. The change with time of the δ value of each of the three components (X, A, and B) in a closed and homogeneous system is a complicated function of the initial δ values of the three components, the chemical concentrations of the two compounds, and the overall rate constants of the forward and reverse reactions involving the two intermolecular and one intramolecular reactions of isotope exchanges. Also, for some one of the three components, the change of its δ value with time may not be monotonic, and the relationship of 1n (1 - F) with time may be non-linear in a plot of 1n (1 - F) vs. t. In addition, the rate law of the isotope exchange reaction in this system also provides a quantitative method to estimate the overall rate constants for the one-intra-and two intermolecular isotope exchanges and the equilibrium isotopic fractionation factors among the three components

Up-Scaling Geochemical Reaction Rates for Carbon Dioxide (CO2) in Deep Saline Aquifers

Energy Technology Data Exchange (ETDEWEB)

Peters, Catherine A

2013-02-28

Geochemical reactions in deep subsurface environments are complicated by the consolidated nature and mineralogical complexity of sedimentary rocks. Understanding the kinetics of these reactions is critical to our ability to make long-term predictions about subsurface processes such as pH buffering, alteration in rock structure, permeability changes, and formation of secondary precipitates. In this project, we used a combination of experiments and numerical simulation to bridge the gap between our knowledge of these reactions at the lab scale and rates that are meaningful for modeling reactive transport at core scales. The focus is on acid-driven mineral dissolution, which is specifically relevant in the context of CO2-water-rock interactions in geological sequestration of carbon dioxide. The project led to major findings in three areas. First, we modeled reactive transport in pore-network systems to investigate scaling effects in geochemical reaction rates. We found significant scaling effects when CO2 concentrations are high and reaction rates are fast. These findings indicate that the increased acidity associated with geological sequestration can generate conditions for which proper scaling tools are yet to be developed. Second, we used mathematical modeling to investigate the extent to which SO2, if co-injected with CO2, would acidify formation brines. We found that there exist realistic conditions in which the impact on brine acidity will be limited due to diffusion rate-limited SO2 dissolution from the CO2 phase, and the subsequent pH shift may also be limited by the lack of availability of oxidants to produce sulfuric acid. Third, for three Viking sandstones (Alberta sedimentary basin, Canada), we employed backscattered electron microscopy and energy dispersive X-ray spectroscopy to statistically characterize mineral contact with pore space. We determined that for reactive minerals in sedimentary consolidated rocks, abundance alone is not a good predictor of

Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Nickel

CERN Document Server

American Society for Testing and Materials. Philadelphia

2008-01-01

1.1 This test method covers procedures for measuring reaction rates by the activation reaction 58Ni(n,p)58Co. 1.2 This activation reaction is useful for measuring neutrons with energies above approximately 2.1 MeV and for irradiation times up to about 200 days in the absence of high thermal neutron fluence rates (for longer irradiations, see Practice E 261). 1.3 With suitable techniques fission-neutron fluence rates densities above 107 cm−2·s−1 can be determined. 1.4 Detailed procedures for other fast-neutron detectors are referenced in Practice E 261. 1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard. 1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Note—The burnup corrections were com...

Thermonuclear F-19(p,alpha(0))O-16 reaction rate

Czech Academy of Sciences Publication Activity Database

He, J. J.; Lombardo, I.; Dell'Aquila, D.; Xu, Yi; Zang, L. Y.; Liu, W. P.

2018-01-01

Roč. 42, č. 1 (2018), č. článku 015001. ISSN 1674-1137 Institutional support: RVO:61389005 Keywords : asymptotic giant branch (AGB) star * nucleosynthesis * astrophysical S factor * cross section * reaction rate Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics OBOR OECD: Astronomy (including astrophysics,space science) Impact factor: 5.084, year: 2016

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):

In situ synthesis of TiB2-TiC particulates locally reinforced medium carbon steel-matrix composites via the SHS reaction of Ni-Ti-B4C system during casting

International Nuclear Information System (INIS)

Wang, H.Y.; Huang, L.; Jiang, Q.C.

2005-01-01

The fabrication of medium carbon steel-matrix composites locally reinforced with in situ TiB 2 -TiC particulates using self-propagating high-temperature synthesis (SHS) reaction of Ni-Ti-B 4 C system during casting was investigated. X-ray diffraction (XRD) results reveal that the exotherm of 1042 deg. C initiated by heat release of the solid state reaction in the differential thermal analysis (DTA) curve is an incomplete reaction in Ni-Ti-B 4 C system. As-cast microstructures of the in situ processed composites reveal a relatively uniform distribution of TiB 2 -TiC particulates in the locally reinforced regions. Furthermore, the particulate size and micro-porosity in the locally reinforced regions are significantly decreased with the increasing of the Ni content in the preforms. For a Ni content of 30 and 40 wt.%, near fully dense composites locally reinforced with in situ TiB 2 and TiC particulates can be fabricated. Although most of fine TiB 2 and TiC particulates which form by the reaction-precipitation mechanism during SHS reaction are present in the locally reinforced region, some large particulates which form by the nucleation-growth mechanism during solidification are entrapped inside the Fe-rich region located in the reinforcing region or inside the matrix region nearby the interface between matrix and reinforcing region. The hardness of the reinforcing region in the composite is significantly higher than that of the unreinforced medium carbon steel. Furthermore, the hardness values of the composites synthesized from 30 to 40 wt.% Ni-Ti-B 4 C systems are higher than those of the composites synthesized from 10 to 20 wt.% Ni-Ti-B 4 C systems

Kinetic aspects of the embedded clusters: Reaction - Rate Theory

International Nuclear Information System (INIS)

Despa, F.; Apostol, M.

1995-07-01

The main stages of the cluster growth process are reviewed using Reaction - Rate Theory. The precipitation stage is shown as a relaxation of the solute towards a cluster state characterized by a higher stability. The kinetic of the late stage of phase separation, the coarsening process, is analyzed by an off-centre diffusion mechanism. The theoretical results are compared to the experimental ones. (author). 37 refs, 6 figs

Nonequilibrium Contribution to the Rate of Reaction. III. Isothermal Multicomponent Systems

Science.gov (United States)

Shizgal, B.; Karplus, M.

1970-10-01

The nonequilibrium contribution to the reaction rate of an isothermal multicomponent system is obtained by solution of the appropriate Chapman-Enskog equation; the system is composed of reactive species in contact with a heat bath of inert atoms M.

Determining Role of the Chain Mechanism in the Temperature Dependence of the Gas-Phase Rate of Combustion Reactions

Science.gov (United States)

Azatyan, V. V.; Bolod'yan, I. A.; Kopylov, N. P.; Kopylov, S. N.; Prokopenko, V. M.; Shebeko, Yu. N.

2018-05-01

It is shown that the strong dependence of the rate of gas-phase combustion reactions on temperature is determined by the high values of the reaction rate constants of free atoms and radicals. It is established that with a branched chain mechanism, a special role in the reaction rate temperature dependence is played by positive feedback between the concentrations of active intermediate species and the rate of their change. The role of the chemical mechanism in the temperature dependence of the process rate with and without inhibitors is considered.

Possibility of increasing the average rate of heterogeneous catalytic reactions by operating in the self-oscillating regime

Energy Technology Data Exchange (ETDEWEB)

Chumakov, G A; Slinko, M G

1979-05-01

The possibility of increasing the average rate of heterogeneous catalytic reactions by operating in the self-oscillating regime was demonstrated by analyzing a kinetic model of hydrogen interaction with oxygen over a metallic catalyst. Within a certain interval of partial pressures of oxygen, the average reaction rate over a period of oscillation may be over five times that of the steady-state reaction.

Decomposition reaction rate of BCl3-C3H6(propene)-H2 in the gas phase.

Science.gov (United States)

Xiao, Jun; Su, Kehe; Liu, Yan; Ren, Hongjiang; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong

2012-07-05

The decomposition reaction rate in the BCl(3)-C(3)H(6)-H(2) gas phase reaction system in preparing boron carbides was investigated based on the most favorable reaction pathways proposed by Jiang et al. [Theor. Chem. Accs. 2010, 127, 519] and Yang et al. [J. Theor. Comput. Chem. 2012, 11, 53]. The rate constants of all the elementary reactions were evaluated with the variational transition state theory. The vibrational frequencies for the stationary points as well as the selected points along the minimum energy paths (MEPs) were calculated with density functional theory at the B3PW91/6-311G(d,p) level and the energies were refined with the accurate model chemistry method G3(MP2). For the elementary reaction associated with a transition state, the MEP was obtained with the intrinsic reaction coordinates, while for the elementary reaction without transition state, the relaxed potential energy surface scan was employed to obtain the MEP. The rate constants were calculated for temperatures within 200-2000 K and fitted into three-parameter Arrhenius expressions. The reaction rates were investigated by using the COMSOL software to solve numerically the coupled differential rate equations. The results show that the reactions are, consistent with the experiments, appropriate at 1100-1500 K with the reaction time of 30 s for 1100 K, 1.5 s for 1200 K, 0.12 s for 1300 K, 0.011 s for 1400 K, or 0.001 s for 1500 K, for propene being almost completely consumed. The completely dissociated species, boron carbides C(3)B, C(2)B, and CB, have very low concentrations, and C(3)B is the main product at higher temperatures, while C(2)B is the main product at lower temperatures. For the reaction time 1 s, all these concentrations approach into a nearly constant. The maximum value (in mol/m(3)) is for the highest temperature 1500 K with the orders of -13, -17, and -23 for C(3)B, C(2)B, and CB, respectively. It was also found that the logarithm of the overall reaction rate and reciprocal

Examining the reaction of monetary policy to exchange rate changes: A nonlinear ARDL approach

Science.gov (United States)

Manogaran, Lavaneesvari; Sek, Siok Kun

2017-04-01

Previous studies showed the exchange rate changes can have significant impacts on macroeconomic performance. Over fluctuation of exchange rate may lead to economic instability. Hence, monetary policy rule tends to react to exchange rate changes. Especially, in emerging economies where the policy-maker tends to limit the exchange rate movement through interventions. In this study, we seek to investigate how the monetary policy rule reacts to exchange rate changes. The nonlinear autoregressive distributed lag (NARDL) model is applied to capture the asymmetric effect of exchange rate changes on monetary policy reaction function (interest rate). We focus the study in ASEAN5 countries (Indonesia, Malaysia, Philippines, Thailand and Singapore). The results indicated the existence of asymmetric effect of exchange rates changes on the monetary reaction function for all ASEAN5 countries in the long-run. Where, in majority of the cases the monetary policy is reacting to the appreciation and depreciation of exchange rate by raising the policy rate. This affirms the intervention of policymakers with the `fear of floating' behavior.

Mixing effects on apparent reaction rates and isotope fractionation during denitrification in a heterogeneous aquifer

Science.gov (United States)

Green, Christopher T.; Böhlke, John Karl; Bekins, Barbara A.; Phillips, Steven P.

2010-01-01

Gradients in contaminant concentrations and isotopic compositions commonly are used to derive reaction parameters for natural attenuation in aquifers. Differences between field‐scale (apparent) estimated reaction rates and isotopic fractionations and local‐scale (intrinsic) effects are poorly understood for complex natural systems. For a heterogeneous alluvial fan aquifer, numerical models and field observations were used to study the effects of physical heterogeneity on reaction parameter estimates. Field measurements included major ions, age tracers, stable isotopes, and dissolved gases. Parameters were estimated for the O2 reduction rate, denitrification rate, O2 threshold for denitrification, and stable N isotope fractionation during denitrification. For multiple geostatistical realizations of the aquifer, inverse modeling was used to establish reactive transport simulations that were consistent with field observations and served as a basis for numerical experiments to compare sample‐based estimates of “apparent” parameters with “true“ (intrinsic) values. For this aquifer, non‐Gaussian dispersion reduced the magnitudes of apparent reaction rates and isotope fractionations to a greater extent than Gaussian mixing alone. Apparent and true rate constants and fractionation parameters can differ by an order of magnitude or more, especially for samples subject to slow transport, long travel times, or rapid reactions. The effect of mixing on apparent N isotope fractionation potentially explains differences between previous laboratory and field estimates. Similarly, predicted effects on apparent O2threshold values for denitrification are consistent with previous reports of higher values in aquifers than in the laboratory. These results show that hydrogeological complexity substantially influences the interpretation and prediction of reactive transport.

Phenomenon of quantum low temperature limit of chemical reaction rates

International Nuclear Information System (INIS)

Gol'danskij, V.I.

1975-01-01

The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerisation, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerisation reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau 0 ) required to add one new link to the polymer chain of formaldehyde during its polymerisation by radiation and during postpolymerisation and to establish that below 80K the increase of tau 0 slows down and that at T approximately equal to 10-4K the time tau 0 reaches a plateau (tau 0 approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life)

Phenomenon of quantum low temperature limit of chemical reaction rates

Energy Technology Data Exchange (ETDEWEB)

Gol' danskii, V I [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1975-12-01

The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius Law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerization, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerization reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau/sub 0/) required to add one new link to the polymer chain of formaldehyde during its polymerization by radiation and during postpolymerization and to establish that below 80K the increase of tau/sub 0/ slows down and that at T approximately equal to 10-4K the time tau/sub 0/ reaches a plateau (tau/sub 0/ approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life).

Nickel group cluster anion reactions with carbon monoxide: Rate coefficients and chemisorption efficiency

Science.gov (United States)

Hintz, Paul A.; Ervin, Kent M.

1994-04-01

Reactions of Ni-n(n=3-10), Pd-n(n=3-8), and Pt-n(n=3-7) with CO are studied in a flow tube reactor. Bimolecular rate coefficients are measured for the association reaction of CO adsorbing on the cluster surface. The rate coefficients range from about 10% of the collision rate for the trimer anions to near the collision rate for clusters larger than four atoms. The maximum number of CO molecules that bind to each cluster is determined. Whereas the saturation limits for nickel are typical for an 18 electron transition metal, the limits for platinum are lower, reflecting the electron deficient structures observed in condensed phase chemistry. The CO saturated palladium clusters represent the first examples of saturated binary palladium carbonyl compounds. Comparisons are made to similar studies on metal cation and neutral clusters and also to surface scattering studies of nickel group metals.

Influence of the medium on the reaction rate of the t-butoxyl radical with iron(II)

International Nuclear Information System (INIS)

Mihaljevic, B.; Razem, D.

2002-01-01

Complete text of publication follows. Tert-butoxyl radicals (t-BuO.) were generated by homolytic photodecomposition of di-tert-butylperoxide using ruby laser flashes at 347 nm. The reaction of t-BuO. radicals with Fe 2+ was studied under pseudo-first order conditions. The quantum yield Φ(Fe 3+ ) was determined by measuring the absorbance of Fe 3+ ion as [FeCl] 2+ complex at 360 nm 2 μs after the flash. According to the equation derived from the reaction scheme, the rate constant k 3 was obtained from the relative rate constant k r (k r =k 0 /k 3 ) and the value of k 0 ; the latter refers to the overall rate of the competing disappearance of t-BuO. radicals from the system (reaction 2), including the highest contribution of β-cleavage. The rate constant k 0 was determined using diphenylmethanol instead of Fe 2+ . The known rate constant of the reaction of t-BuO. radical with diphenylmethanol giving ketyl radicals (6.9 x 10 6 dm 3 mol -1 s -1 ) was applied. The quantum yield of ketyl radicals was determined by measuring the maximum of absorbance at 535 nm. At acid concentration of 0.023 mol dm -3 HCl the rate constant k 3 = 3.4 x 10 8 dm 3 mol -1 s -1 was determined. The relative rate constant increased with an increase of the hydrochloric acid concentration which has been ascribed to the lower stability of t-BuO. radical at higher acidity of the medium. The effect of polarity of the medium on the reaction rate was also determined. Decreasing k 3 in media of increasing polarity were explained by increasing of the β-scission rate of t-BuO. radical with increasing polarity of the medium

Novel concept of recycling sludge and dust to BOF converter through dispersed in-situ phase induced by composite ball explosive reaction

Science.gov (United States)

Tang, Fu-ping; Yu, Shu-juan; Fei, Peng; Hou, Hou-yu; Qian, Feng; Wang, Xiao-feng

2017-08-01

Recycling of iron and steelmaking dusts is a key issue in environmental protection efforts and to ensure efficient utilization. In this investigation, we developed a novel recovery process that uses a dispersed in-situ phase induced by an explosive reaction of composite balls of iron and steelmaking dusts. We designed and prepared composite balls for this function using a laboratory model batch-type balling disc (at 12 r/min) and optimized the feeding modes in 180-t and 260-t basic oxygen furnace (BOF) converters. The results indicate that feeding composite balls into BOF converters is an effective novel technology for recovering iron and steelmaking dusts. The period after hot metal charging and prior to the oxygen-blowing process is the most reasonable time to feed composite balls. Composite ball treatment is not appropriate for steel production with sulfur requirements lower than 80 ppm. The maximum composite ball feeding amount is 40 kg/t and the iron yield rate is better than 95%. Compared with the conventional recycling process of sludge and dust, this novel technology is more convenient and efficient, saving up to 309 RMB per ton of steel. Further investigation of this novel recycling technology is merited.

Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

International Nuclear Information System (INIS)

Janev, R.K.; Kato, T.; Wang, J.G.

2001-05-01

The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C x H y charge exchange reactions from thermal energies up to several hundreds keV for all C x H y molecules with x=1, 2, 3 and 1 ≤ y ≤ 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

In situ infrared spectroscopic study of the electrochromic reactions of tungsten trioxide films

International Nuclear Information System (INIS)

Habib, M.A.; Maheswari, S.P.

1991-01-01

This paper reports on thin WO 3 films which are transparent in the oxidized state and colored in the reduced state. These changes in optical properties are associated with compositional variations of the material. Changes in vibrational intensities of W double-bond O, W emdash O, and W double-bond O emdash H bonds in the electrochromic WO 3 film were detected by an in situ FTIR technique at various stages of reduction (coloration). The absorbance due to O emdash H stretching and bending vibrations was found to increase during the electrochemical reduction of the film, indicating the incorporation of water into the film along with the formation of H x WO 3 bronze during coloration. The absorbance due to W double-bond O vibration decreased while that due to W emdash O vibration increased during reduction. These observations suggest that during the coloration process W double-bond O bonds break and new W emdash O bonds form in the film, and thus, provide direct evidence for the electrochromic reaction. O 2 W double-bond O + xH + + xe - ↔ O 2 W emdash O emdash H x

The TDF System for Thermonuclear Plasma Reaction Rates, Mean Energies and Two-Body Final State Particle Spectra

International Nuclear Information System (INIS)

Warshaw, S I

2001-01-01

The rate of thermonuclear reactions in hot plasmas as a function of local plasma temperature determines the way in which thermonuclear ignition and burning proceeds in the plasma. The conventional model approach to calculating these rates is to assume that the reacting nuclei in the plasma are in Maxwellian equilibrium at some well-defined plasma temperature, over which the statistical average of the reaction rate quantity σv is calculated, where σ is the cross-section for the reaction to proceed at the relative velocity v between the reacting particles. This approach is well-understood and is the basis for much nuclear fusion and astrophysical nuclear reaction rate data. The Thermonuclear Data File (TDF) system developed at the Lawrence Livermore National Laboratory (Warshaw 1991), which is the topic of this report, contains data on the Maxwellian-averaged thermonuclear reaction rates for various light nuclear reactions and the correspondingly Maxwellian-averaged energy spectra of the particles in the final state of those reactions as well. This spectral information closely models the output particle and energy distributions in a burning plasma, and therefore leads to more accurate computational treatments of thermonuclear burn, output particle energy deposition and diagnostics, in various contexts. In this report we review and derive the theoretical basis for calculating Maxwellian-averaged thermonuclear reaction rates, mean particle energies, and output particle spectral energy distributions for these reactions in the TDF system. The treatment of the kinematics is non-relativistic. The current version of the TDF system provides exit particle energy spectrum distributions for two-body final state reactions only. In a future report we will discuss and describe how output particle energy spectra for three- and four-body final states can be developed for the TDF system. We also include in this report a description of the algorithmic implementation of the TDF

In-situ characterization of heterogeneous catalysts

CERN Document Server

Rodriguez, Jose A; Chupas, Peter J

2013-01-01

Helps researchers develop new catalysts for sustainable fuel and chemical production Reviewing the latest developments in the field, this book explores the in-situ characterization of heterogeneous catalysts, enabling readers to take full advantage of the sophisticated techniques used to study heterogeneous catalysts and reaction mechanisms. In using these techniques, readers can learn to improve the selectivity and the performance of catalysts and how to prepare catalysts as efficiently as possible, with minimum waste. In-situ Characterization of Heterogeneous Catalysts feat

Investigating phase behavior and structural changes in NiO/Ni-YSZ composite with monochromatic in-situ 2D and static 3D neutron imaging

DEFF Research Database (Denmark)

Makowska, Malgorzata G.; Strobl, Markus; Kardjilov, Nikolay

2017-01-01

oxide fuel cells, and for cathodes in solid oxide electrolysis cells). Results of in-situ 2D and ex-situ 3D measurements are presented. In-situ observation of phase transition between NiO and Ni were performed at the test Beamline for neutron Optics and other Applications (BOA) at the continuous neutron...... and post mortem tomography provides complementary information about the reduction/oxidation degree and e.g. crack evolution in the investigated system and it is therefore possible to acquire information about the rate of chemical reactions and spatial evolution of phases and morphological features....

Verification of dosimetry cross sections above 10 MeV based on measurement of activation reaction rates in fission neutron field

International Nuclear Information System (INIS)

Odano, Naoteru; Miura, Toshimasa; Yamaji, Akio.

1996-01-01

To validate the dosimetry cross sections in fast neutron energy range, activation reaction rates were measured for 5 types of dosimetry cross sections which have sensitivity in the energy rage above 10 MeV utilizing JRR-4 reactor of JAERI. The measured reaction rates were compared with the calculations reaction rates by a continuous energy monte carlo code MVP. The calculated reaction rates were based on two dosimetry files, JENDL Dosimetry File and IRDF-90.2. (author)

Comparison of measured and calculated reaction rate distributions in an scwr-like test lattice

Energy Technology Data Exchange (ETDEWEB)

Raetz, Dominik, E-mail: dominik.raetz@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Jordan, Kelly A., E-mail: kelly.jordan@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Murphy, Michael F., E-mail: mike.murphy@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Perret, Gregory, E-mail: gregory.perret@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Chawla, Rakesh, E-mail: rakesh.chawla@psi.ch [Paul Scherrer Institut, CH-5232 Villigen PSI (Switzerland); Ecole Polytechnique Federale de Lausanne (EPFL), CH-1015 Lausanne, EPFL (Switzerland)

2011-04-15

High resolution gamma-ray spectroscopy measurements were performed on 61 rods of an SCWR-like fuel lattice, after irradiation in the central test zone of the PROTEUS zero-power research reactor at the Paul Scherrer Institute in Switzerland. The derived reaction rates are the capture rate in {sup 238}U (C{sub 8}) and the total fission rate (F{sub tot}), and also the reaction rate ratio C{sub 8}/F{sub tot}. Each of these has been mapped rod-wise on the lattice and compared to calculated results from whole-reactor Monte Carlo simulations with MCNPX. Ratios of calculated to experimental values (C/E's) have been assessed for the C{sub 8}, F{sub tot} and C{sub 8}/F{sub tot} distributions across the lattice. These C/E's show excellent agreement between the calculations and the measurements. For the {sup 238}U capture rate distribution, the 1{sigma} level in the comparisons corresponds to an uncertainty of {+-}0.8%, while for the total fission rate the corresponding value is {+-}0.4%. The uncertainty for C{sub 8}/F{sub tot}, assessed as a reaction rate ratio characterizing each individual rod position in the test lattice, is significantly higher at {+-}2.2%. To determine the reproducibility of these results, the measurements were performed twice, once in 2006 and again in 2009. The agreement between these two measurement sets is within the respective statistical uncertainties.

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

International Nuclear Information System (INIS)

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

1991-01-01

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

Chemical reaction rates and non-equilibrium pressure of reacting gas mixtures in the state-to-state approach

International Nuclear Information System (INIS)

Kustova, Elena V.; Kremer, Gilberto M.

2014-01-01

Highlights: • State-to-state approach for coupled vibrational relaxation and chemical reactions. • Self-consistent model for rates of non-equilibrium reactions and energy transitions. • In viscous flows mass action law is violated. • Cross coupling between reaction rates and non-equilibrium pressure in viscous flow. • Results allow implementing the state-to-state approach for viscous flow simulations. - Abstract: Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman–Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N 2 flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure

Chemical reaction rates and non-equilibrium pressure of reacting gas mixtures in the state-to-state approach

Energy Technology Data Exchange (ETDEWEB)

Kustova, Elena V., E-mail: e.kustova@spbu.ru [Department of Mathematics and Mechanics, Saint Petersburg State University, 198504 Universitetskiy pr. 28, Saint Petersburg (Russian Federation); Kremer, Gilberto M., E-mail: kremer@fisica.ufpr.br [Departamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, 81531-980 Curitiba (Brazil)

2014-12-05

Highlights: • State-to-state approach for coupled vibrational relaxation and chemical reactions. • Self-consistent model for rates of non-equilibrium reactions and energy transitions. • In viscous flows mass action law is violated. • Cross coupling between reaction rates and non-equilibrium pressure in viscous flow. • Results allow implementing the state-to-state approach for viscous flow simulations. - Abstract: Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman–Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N{sub 2} flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure.

Measurements of 14C in ancient ice from Taylor Glacier, Antarctica constrain in situ cosmogenic 14CH4 and 14CO production rates

Science.gov (United States)

Petrenko, Vasilii V.; Severinghaus, Jeffrey P.; Schaefer, Hinrich; Smith, Andrew M.; Kuhl, Tanner; Baggenstos, Daniel; Hua, Quan; Brook, Edward J.; Rose, Paul; Kulin, Robb; Bauska, Thomas; Harth, Christina; Buizert, Christo; Orsi, Anais; Emanuele, Guy; Lee, James E.; Brailsford, Gordon; Keeling, Ralph; Weiss, Ray F.

2016-03-01

Carbon-14 (14C) is incorporated into glacial ice by trapping of atmospheric gases as well as direct near-surface in situ cosmogenic production. 14C of trapped methane (14CH4) is a powerful tracer for past CH4 emissions from ;old; carbon sources such as permafrost and marine CH4 clathrates. 14C in trapped carbon dioxide (14CO2) can be used for absolute dating of ice cores. In situ produced cosmogenic 14C in carbon monoxide (14CO) can potentially be used to reconstruct the past cosmic ray flux and past solar activity. Unfortunately, the trapped atmospheric and in situ cosmogenic components of 14C in glacial ice are difficult to disentangle and a thorough understanding of the in situ cosmogenic component is needed in order to extract useful information from ice core 14C. We analyzed very large (≈1000 kg) ice samples in the 2.26-19.53 m depth range from the ablation zone of Taylor Glacier, Antarctica, to study in situ cosmogenic production of 14CH4 and 14CO. All sampled ice is >50 ka in age, allowing for the assumption that most of the measured 14C originates from recent in situ cosmogenic production as ancient ice is brought to the surface via ablation. Our results place the first constraints on cosmogenic 14CH4 production rates and improve on prior estimates of 14CO production rates in ice. We find a constant 14CH4/14CO production ratio (0.0076 ± 0.0003) for samples deeper than 3 m, which allows the use of 14CO for correcting the 14CH4 signals for the in situ cosmogenic component. Our results also provide the first unambiguous confirmation of 14C production by fast muons in a natural setting (ice or rock) and suggest that the 14C production rates in ice commonly used in the literature may be too high.

Metal-silicon reaction rates - The effects of capping

Science.gov (United States)

Weizer, Victor G.; Fatemi, Navid S.

1989-01-01

Evidence is presented showing that the presence of the commonly used anti-reflection coating material Ta2O5 on the free surface of contact metallization can either suppress or enhance, depending on the system, the interaction that takes place at elevated temperatures between the metallization and the underlying Si. The cap layer is shown to suppress both the generation and annihilation of vacancies at the free surface of the metal which are necessary to support metal-Si interactons. Evidence is also presented indicating that the mechanical condition of the free metal surface has a significant effect on the metal-silicon reaction rate.

In situ observation of lithium hydride hydrolysis by DRIFT spectroscopy

International Nuclear Information System (INIS)

Awbery, Roy P.; Broughton, Duncan A.; Tsang, S.C.

2008-01-01

Polycrystalline LiH was studied in situ using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy to investigate the effect water vapour has on the rate of production of the corrosion products, particularly LiOH. The reaction rate of the formation of surface LiOH was monitored by measurement of the hydroxyl (OH) band at 3676 cm -1 . The initial hydrolysis rate of LiH exposed to water vapour at 50% relative humidity was found to be almost two times faster than LiH exposed to water vapour at 2% relative humidity. The hydrolysis rate was shown to be initially very rapid followed by a much slower, almost linear rate. The change in hydrolysis rate was attributed to the formation of a coherent layer of LiOH on the LiH surface. Exposure to lower levels of water vapour appeared to result in the formation of a more coherent corrosion product, resulting in effective passivation of the surface to further attack from water

FT-IR spectroscopic imaging of reactions in multiphase flow in microfluidic channels.

Science.gov (United States)

Chan, K L Andrew; Kazarian, Sergei G

2012-05-01

Rapid, in situ, and label-free chemical analysis in microfluidic devices is highly desirable. FT-IR spectroscopic imaging has previously been shown to be a powerful tool to visualize the distribution of different chemicals in flows in a microfluidic device at near video rate imaging speed without tracers or dyes. This paper demonstrates the possibility of using this imaging technology to capture the chemical information of all reactants and products at different points in time and space in a two-phase system. Differences in the rates of chemical reactions in laminar flow and segmented flow systems are also compared. Neutralization of benzoic acid in decanol with disodium phosphate in water has been used as the model reaction. Quantitative information, such as concentration profiles of reactant and products, can be extracted from the imaging data. The same feed flow rate was used in both the laminar flow and segmented flow systems. The laminar flow pattern was achieved using a plain wide T-junction, whereas the segmented flow was achieved by introducing a narrowed section and a nozzle at the T-junction. The results show that the reaction rate is limited by diffusion and is much slower with the laminar flow pattern, whereas the reaction is completed more quickly in the segmented flow due to better mixing.

Ultrasonication aided in-situ transesterification of microbial lipids to biodiesel.

Science.gov (United States)

Zhang, Xiaolei; Yan, Song; Tyagi, Rajeshwar Dayal; Surampalli, Rao Y; Valéro, Jose R

2014-10-01

In-situ transesterification of microbial lipid to biodiesel has been paid substantial attention due to the fact that the lipid extraction and transesterification can be conducted in one-stage process. To improve the feasibility of in-situ transesterification, ultrasonication was employed to reduce methanol requirement and reaction time. The results showed that the use of ultrasonication could achieve high conversion of lipid to FAMEs (92.1% w lipid conversion/w total lipids) with methanol to lipid molar ratio 60:1 and NaOH addition 1% w/w lipid in 20 min, while methanol to lipid molar ratio 360:1, NaOH addition 1% w/w lipid, and reaction time 12h was required to obtain similar yield in in-situ transesterification without ultrasonication. The compositions of FAMEs obtained in case of ultrasonication aided in-situ transesterification were similar as that of two-stage extraction followed by transesterification processes. Copyright © 2014. Published by Elsevier Ltd.

A method for in situ estimation of prey selectivity and predation rate in large plankton, exemplified with the jellyfish Aurelia aurita (L.)

DEFF Research Database (Denmark)

Hansson, L.J.

2006-01-01

, predation rate can be calculated as increase in gut content over time. Clearance rates for different prey can be calculated from predation rates and prey concentrations in the water, allowing accurate estimates of prey selectivity. Thus, the problem of unknown feeding history and feeding environment, which...... of a specific individual plankton predator in situ.After prey has been evacuated from the gut of an individual predator, the predator is incubated in situ, and observed by SCUBA-divers who recapture the individual after a defined time. Given that this incubation time is shorter than prey digestion time...... among individual jellyfish and among the various oral arms and gastric pouches within individuals. Clearance rates varied strongly with prey type. The medusae selected large crustacean prey (cladocerans and copepods/copepodites) over echinoderm larvae and copepod nauplii. Prey distribution within...

An effective rate equation approach to reaction kinetics in small volumes: theory and application to biochemical reactions in nonequilibrium steady-state conditions.

Science.gov (United States)

Grima, R

2010-07-21

Chemical master equations provide a mathematical description of stochastic reaction kinetics in well-mixed conditions. They are a valid description over length scales that are larger than the reactive mean free path and thus describe kinetics in compartments of mesoscopic and macroscopic dimensions. The trajectories of the stochastic chemical processes described by the master equation can be ensemble-averaged to obtain the average number density of chemical species, i.e., the true concentration, at any spatial scale of interest. For macroscopic volumes, the true concentration is very well approximated by the solution of the corresponding deterministic and macroscopic rate equations, i.e., the macroscopic concentration. However, this equivalence breaks down for mesoscopic volumes. These deviations are particularly significant for open systems and cannot be calculated via the Fokker-Planck or linear-noise approximations of the master equation. We utilize the system-size expansion including terms of the order of Omega(-1/2) to derive a set of differential equations whose solution approximates the true concentration as given by the master equation. These equations are valid in any open or closed chemical reaction network and at both the mesoscopic and macroscopic scales. In the limit of large volumes, the effective mesoscopic rate equations become precisely equal to the conventional macroscopic rate equations. We compare the three formalisms of effective mesoscopic rate equations, conventional rate equations, and chemical master equations by applying them to several biochemical reaction systems (homodimeric and heterodimeric protein-protein interactions, series of sequential enzyme reactions, and positive feedback loops) in nonequilibrium steady-state conditions. In all cases, we find that the effective mesoscopic rate equations can predict very well the true concentration of a chemical species. This provides a useful method by which one can quickly determine the

Electron capture rates in stars studied with heavy ion charge exchange reactions

Science.gov (United States)

Bertulani, C. A.

2018-01-01

Indirect methods using nucleus-nucleus reactions at high energies (here, high energies mean ~ 50 MeV/nucleon and higher) are now routinely used to extract information of interest for nuclear astrophysics. This is of extreme relevance as many of the nuclei involved in stellar evolution are short-lived. Therefore, indirect methods became the focus of recent studies carried out in major nuclear physics facilities. Among such methods, heavy ion charge exchange is thought to be a useful tool to infer Gamow-Teller matrix elements needed to describe electron capture rates in stars and also double beta-decay experiments. In this short review, I provide a theoretical guidance based on a simple reaction model for charge exchange reactions.

Combined effect of whole-body vibration and ambient lighting on human discomfort, heart rate, and reaction time.

Science.gov (United States)

Monazzam, Mohammad Reza; Shoja, Esmaeil; Zakerian, Seyed Abolfazl; Foroushani, Abbas Rahimi; Shoja, Mohsen; Gharaee, Masoumeh; Asgari, Amin

2018-03-12

This study aimed to investigate the effect of whole-body vibration and ambient lighting, as well as their combined effect on human discomfort, heart rate, and reaction time in laboratory conditions. 44 men were recruited with an average age of 25.4 ± 1.9 years. Each participant was subjected to 12 experimental steps, each step lasting five minutes for four different vibration accelerations in X, Y, and Z axes at a fixed frequency; three different lighting intensities of 50, 500, and 1000 lx were also considered. At each step, a visual computerized reaction test was taken from subjects and their heart rate recorded by pulse oximeter. In addition, the discomfort rate of subjects was measured using Borg scale. Increasing vibration acceleration significantly increased the discomfort rate and heart beat but not the reaction time. Lack of lighting caused more discomfort in the subjects, but there was no significant correlation between lighting intensity with heart rate and reaction time. The results also showed that the combined effect of vibration and lighting had no significant effect on any of the discomfort, heart rate, and reaction time variables. Whole-body vibration is an important factor in the development of human subjective and physiological reactions compared to lighting. Therefore, consideration of the level of vibration to which an individual is exposed in workplaces subject to vibration plays an important role in reducing the level of human discomfort, but its interaction with ambient lighting does not have a significant effect on human subjective and physiological responses.

Efficient solvothermal wet in situ transesterification of Nannochloropsis gaditana for biodiesel production.

Science.gov (United States)

Kim, Bora; Chang, Yong Keun; Lee, Jae W

2017-05-01

In situ transesterification of wet microalgae is a promising, simplified alternative biodiesel production process that replaces multiple operations of cell drying, extraction, and transesterification reaction. This study addresses enhanced biodiesel production from Nannochloropsis gaditana at elevated temperatures. Compared with the previously reported in situ transesterification process of conducting the reaction at a temperature ranging from 95 to 125 °C, the present work employs higher temperatures of at least 150 °C. This relatively harsh condition allows much less acid catalyst with or without co-solvent to be used during this single extraction-conversion process. Without any co-solvent, 0.58% (v/v) of H 2 SO 4 in the reaction medium can achieve 90 wt% of the total lipid conversion to biodiesel at 170 °C when the moisture content of wet algal paste is 80 wt%. Here, the effects of temperature, acid catalyst, and co-solvent on the FAEE yield and specification were scrutinized, and the reaction kinetic was investigated to understand the solvothermal in situ transesterification reaction at the high temperature. Having a biphasic system (water/chloroform) during the reaction also helped to meet biodiesel quality standard EN 14214, as Na + , K + , Ca 2+ , Mg 2+ cations and phosphorus were detected only below 5 ppm. With highlights on the economic feasibility, wet in situ transesterification at the high temperature can contribute to sustainable production of biodiesel from microalgae by reducing the chemical input and relieve the burden of extensive post purification process, therefore a step towards green process.

Partial oxidation of jet fuels over Rh/Al_2O_3. Design and reaction kinetics of sulfur-containing surrogates

International Nuclear Information System (INIS)

Baer, Julian Nicolaas

2016-01-01

The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al_2O_3 at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e.g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al_2O_3, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product distribution. An

Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

Energy Technology Data Exchange (ETDEWEB)

Janev, R.K.; Kato, T. [National Inst. for Fusion Science, Toki, Gifu (Japan); Wang, J.G. [Department of Physics and Astronomy, University of Georgia, Athens (United States)

2001-05-01

The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C{sub x}H{sub y} charge exchange reactions from thermal energies up to several hundreds keV for all C{sub x}H{sub y} molecules with x=1, 2, 3 and 1 {<=} y {<=} 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

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.

The rate of the reaction between CN and C2H2 at interstellar temperatures

Science.gov (United States)

Woon, D. E.; Herbst, E.

1997-01-01

The rate coefficient for the important interstellar reaction between CN and C2H2 has been calculated as a function of temperature between 10 and 300 K. The potential surface for this reaction has been determined through ab initio quantum chemical techniques; the potential exhibits no barrier in the entrance channel but does show a small exit channel barrier, which lies below the energy of reactants. Phase-space calculations for the reaction dynamics, which take the exit channel barrier into account, show the same unusual temperature dependence as determined by experiment, in which the rate coefficient at first increases as the temperature is reduced below room temperature and then starts to decrease as the temperature drops below 50-100 K. The agreement between theory and experiment provides strong confirmation that the reaction occurs appreciably at cool interstellar temperatures.

The rate of the reaction between C2H and C2H2 at interstellar temperatures

Science.gov (United States)

Herbst, E.; Woon, D. E.

1997-01-01

The reaction between the radical C2H and the stable hydrocarbon C2H2 is one of the simplest neutral-neutral hydrocarbon reactions in chemical models of dense interstellar clouds and carbon-rich circumstellar shells. Although known to be rapid at temperatures > or = 300 K, the reaction has yet to be studied at lower temperatures. We present here ab initio calculations of the potential surface for this reaction and dynamical calculations to determine its rate at low temperature. Despite a small potential barrier in the exit channel, the calculated rate is large, showing that this reaction and, most probably, more complex analogs contribute to the formation of complex organic molecules in low-temperature sources.

A comprehensive model to determine the effects of temperature and species fluctuations on reaction rates in turbulent reaction flows

Science.gov (United States)

Magnotti, F.; Diskin, G.; Matulaitis, J.; Chinitz, W.

1984-01-01

The use of silane (SiH4) as an effective ignitor and flame stabilizing pilot fuel is well documented. A reliable chemical kinetic mechanism for prediction of its behavior at the conditions encountered in the combustor of a SCRAMJET engine was calculated. The effects of hydrogen addition on hydrocarbon ignition and flame stabilization as a means for reduction of lengthy ignition delays and reaction times were studied. The ranges of applicability of chemical kinetic models of hydrogen-air combustors were also investigated. The CHARNAL computer code was applied to the turbulent reaction rate modeling.

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.

A chiral Brønsted acid-catalyzed highly enantioselective Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines.

Science.gov (United States)

Unhale, Rajshekhar A; Sadhu, Milon M; Ray, Sumit K; Biswas, Rayhan G; Singh, Vinod K

2018-04-03

A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-hydroxyisoindolinones has been demonstrated in this communication. A variety of isoindolinone-based α-amino diazo esters bearing a quaternary stereogenic center were afforded in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the products has been depicted by the hydrogenation of the diazo moiety of adducts.

Rate coefficients of exchange reactions accounting for vibrational excitation of reagents and products

Science.gov (United States)

Kustova, E. V.; Savelev, A. S.; Kunova, O. V.

2018-05-01

Theoretical models for the vibrational state-resolved Zeldovich reaction are assessed by comparison with the results of quasi-classical trajectory (QCT) calculations. An error in the model of Aliat is corrected; the model is generalized taking into account NO vibrational states. The proposed model is fairly simple and can be easily implemented to the software for non-equilibrium flow modeling. It provides a good agreement with the QCT rate coefficients in the whole range of temperatures and reagent/product vibrational states. The developed models are tested in simulations of vibrational and chemical relaxation of air mixture behind a shock wave. The importance of accounting for excitated NO vibrational states and accurate prediction of Zeldovich reactions rates is shown.

In-situ Measurements of the Effect of Au Doping in Ni Catalysts on the Yield of Tubular Carbon Nanostructures

DEFF Research Database (Denmark)

Sharma, Renu; Chee, S.; Rez, P.

characterization of as-deposited films, the samples were heated in vacuum up to reaction temperatures (500-650 °C). Acetylene was introduced in the sample region and pressures were kept constant during each experiment but varied between 1-3 mTorr for each individual experiment. Digital videos (15 frames/s) at low....... Formation of different structures depended upon the rate of growth, which was in turn controlled by pressure and temperature. Both in-situ and ex-situ analysis of the composition of the catalyst particles, effect of temperature and pressure on the morphology and structural mechanism for the formation...

A review of the rates of reaction of unirradiated uranium in gaseous atmospheres

International Nuclear Information System (INIS)

Pearce, R.J.

1989-10-01

The review collates available quantitative rate data for the reaction of unirradiated uranium in dry and moist air, steam and carbon dioxide based atmospheres at temperatures ranging from room temperature to above the melting point of uranium. Reactions in nitrogen and carbon monoxide are also considered. The aim of the review is to provide a compilation of base data for the hazard analysis of fault conditions relating to Magnox fuel. (author)

Air kerma rate estimation by means of in-situ gamma spectrometry: A Bayesian approach

International Nuclear Information System (INIS)

Cabal, Gonzalo; Kluson, Jaroslav

2008-01-01

Full text: Bayesian inference is used to determine the Air Kerma Rate based on a set of in situ environmental gamma spectra measurements performed with a NaI(Tl) scintillation detector. A natural advantage of such approach is the possibility to quantify uncertainty not only in the Air Kerma Rate estimation but also for the gamma spectra which is unfolded within the procedure. The measurements were performed using a 3'' x 3'' NaI(Tl) scintillation detector. The response matrices of such detection system were calculated using a Monte Carlo code. For the calculations of the spectra as well as the Air Kerma Rate the WinBugs program was used. WinBugs is a dedicated software for Bayesian inference using Monte Carlo Markov chain methods (MCMC). The results of such calculations are shown and compared with other non-Bayesian approachs such as the Scofield-Gold iterative method and the Maximum Entropy Method

Transcriptional dynamics with time-dependent reaction rates

Science.gov (United States)

Nandi, Shubhendu; Ghosh, Anandamohan

2015-02-01

Transcription is the first step in the process of gene regulation that controls cell response to varying environmental conditions. Transcription is a stochastic process, involving synthesis and degradation of mRNAs, that can be modeled as a birth-death process. We consider a generic stochastic model, where the fluctuating environment is encoded in the time-dependent reaction rates. We obtain an exact analytical expression for the mRNA probability distribution and are able to analyze the response for arbitrary time-dependent protocols. Our analytical results and stochastic simulations confirm that the transcriptional machinery primarily act as a low-pass filter. We also show that depending on the system parameters, the mRNA levels in a cell population can show synchronous/asynchronous fluctuations and can deviate from Poisson statistics.

Transcriptional dynamics with time-dependent reaction rates

International Nuclear Information System (INIS)

Nandi, Shubhendu; Ghosh, Anandamohan

2015-01-01

Transcription is the first step in the process of gene regulation that controls cell response to varying environmental conditions. Transcription is a stochastic process, involving synthesis and degradation of mRNAs, that can be modeled as a birth–death process. We consider a generic stochastic model, where the fluctuating environment is encoded in the time-dependent reaction rates. We obtain an exact analytical expression for the mRNA probability distribution and are able to analyze the response for arbitrary time-dependent protocols. Our analytical results and stochastic simulations confirm that the transcriptional machinery primarily act as a low-pass filter. We also show that depending on the system parameters, the mRNA levels in a cell population can show synchronous/asynchronous fluctuations and can deviate from Poisson statistics. (paper)

Monitoring biodegradation of diesel fuel in bioventing processes using in situ respiration rate.

Science.gov (United States)

Lee, T H; Byun, I G; Kim, Y O; Hwang, I S; Park, T J

2006-01-01

An in situ measuring system of respiration rate was applied for monitoring biodegradation of diesel fuel in a bioventing process for bioremediation of diesel contaminated soil. Two laboratory-scale soil columns were packed with 5 kg of soil that was artificially contaminated by diesel fuel as final TPH (total petroleum hydrocarbon) concentration of 8,000 mg/kg soil. Nutrient was added to make a relative concentration of C:N:P = 100:10:1. One soil column was operated with continuous venting mode, and the other one with intermittent (6 h venting/6 h rest) venting mode. On-line O2 and CO2 gas measuring system was applied to measure O2 utilisation and CO2 production during biodegradation of diesel for 5 months. Biodegradation rate of TPH was calculated from respiration rate measured by the on-line gas measuring system. There were no apparent differences between calculated biodegradation rates from two columns with different venting modes. The variation of biodegradation rates corresponded well with trend of the remaining TPH concentrations comparing other biodegradation indicators, such as C17/pristane and C18/phytane ratio, dehydrogenase activity, and the ratio of hydrocarbon utilising bacteria to total heterotrophic bacteria. These results suggested that the on-line measuring system of respiration rate would be applied to monitoring biodegradation rate and to determine the potential applicability of bioventing process for bioremediation of oil contaminated soil.

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

Polypropylene/graphite nanocomposites by in situ polymerization

International Nuclear Information System (INIS)

Milani, Marceo A.; Galland, Giselda B.; Quijada, Raul

2011-01-01

This work presents the synthesis of nanocomposites of polypropylene/graphite by in situ polymerization using metallocene catalyst and graphene nanosheets. Initially was analyzed which of the metallocene catalysts rac-Et(Ind) 2 ZrCl 2 or rac-Me 2 Si(Ind) 2 ZrCl 2 produces polypropylene with mechanical properties more relevant. Then it were performed the in situ polymerization reactions to obtain the nanocomposites. The polymeric materials were characterized by XRD, DSC, GPC and DMTA. (author)

Fathead minnow whole-mount in situ hybridization (WISH)

Data.gov (United States)

U.S. Environmental Protection Agency — This study demonstrates the potential of whole-mount in situ hybridization (WISH), in conjunction with quantitative real-time polymerase chain reaction (QPCR)...

Experimental determination of nuclear reaction rates (n,γ) by the gamma-rays capture spectrometry technique

International Nuclear Information System (INIS)

Lucatero, M.A.

1976-01-01

The technique of the gamma-rays capture spectrometry was used in the experimental determination of nuclear reaction rates of the type (n,γ). This technique consists in the incidence of a thermal neutrons collimated beam upon a sample, detecting the capture spectrum of gamma rays emitted at a solid fixed angle. In the determination of the efficiency curve intrinsic to the detection electronic system the reactions 199 Hg(n,γ) 200 Hg, 56 Fe(n,γ) 57 Fe and 63 Cu(n,γ) 64 Cu were used with the energy of the gamma rays capture of 5.976, 7.635 and 7.915 Mev respectively, through the irradiation of standard samples of Hg(175.3g), Fe(110.4g) and Cu(108.5g) of cylindrical geometry the two former and parallelepiped the latter. The problem concerning the corrections due to the thermal neutrons flux depression, the gammas auto-attenuation, and the geometric factor due to the cylindrical and parallelepiped geometry are involved in the data process. The experimental determination of the reaction 35 Cl(n,γ) 36 Cl rate was made through the observation of the gamma caputre of 6.111 Mev when a sample of CaCl 2 of cylindrical geometry was irradiated. This rate can be favorably compared with the reaction rate determined theoretically. (author)

Astrophysical reaction rate for the neutron-generator reaction 13C(alpha,n)16O in asymptotic giant branch stars.

Science.gov (United States)

Johnson, E D; Rogachev, G V; Mukhamedzhanov, A M; Baby, L T; Brown, S; Cluff, W T; Crisp, A M; Diffenderfer, E; Goldberg, V Z; Green, B W; Hinners, T; Hoffman, C R; Kemper, K W; Momotyuk, O; Peplowski, P; Pipidis, A; Reynolds, R; Roeder, B T

2006-11-10

The reaction 13C(alpha,n) is considered to be the main source of neutrons for the s process in asymptotic giant branch stars. At low energies, the cross section is dominated by the 1/2+ 6.356 MeV subthreshold resonance in (17)O whose contribution at stellar temperatures is uncertain by a factor of 10. In this work, we performed the most precise determination of the low-energy astrophysical S factor using the indirect asymptotic normalization (ANC) technique. The alpha-particle ANC for the subthreshold state has been measured using the sub-Coulomb alpha-transfer reaction ((6)Li,d). Using the determined ANC, we calculated S(0), which turns out to be an order of magnitude smaller than in the nuclear astrophysics compilation of reaction rates.

Calculation of astrophysical S-factor and reaction rate in 12C(p, γ)13N reaction

Science.gov (United States)

Moghadasi, A.; Sadeghi, H.; Pourimani, R.

2018-02-01

The 12C(p, γ)13N reaction is the first process in the CNO cycle. Also it is a source of low-energy solar neutrinos in various neutrino experiments. Therefore, it is of high interest to gain data of the astrophysical S-factor in low energies. By applying Faddeev's method, we calculated wave functions for the bound state of 13N. Then the cross sections for resonance and non-resonance were calculated through using Breit-Wigner and direct capture cross section formulae, respectively. After that, we calculated the total S-factor and compared it with previous experimental data, revealing a good agreement altogether. Then, we extrapolated the S-factor in zero energy and the result was 1.32 ± 0.19 (keV.b). In the end, we calculated reaction rate and compared it with NACRE data.

Rate Coefficient Measurements and Theoretical Analysis of the OH + ( E) CF3CH=CHCF3 Reaction.

Science.gov (United States)

Baasandorj, Munkhbayar; Marshall, Paul; Waterland, Robert L; Ravishankara, Akkihebbal R; Burkholder, James B

2018-04-25

Rate coefficients, k, for the gas-phase reaction of the OH radical with (E) CF3CH=CHCF3 ((E)-1,1,14,4,4-hexafluoro-2-butene, HFO-1336mzz(E)) were measured over a range of temperature (211-374 K) and bath gas pressure (20-300 Torr; He, N2) using a pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique. k1(T) was independent of pressure over this range of conditions with k1(296 K) = (1.31 ± 0.15) × 10 13 cm3 molecule 1 s 1 and k1(T) = (6.94 ± 0.80) × 10 13 exp[ (496 ± 10)/T] cm3 molecule 1 s 1, where the uncertainties are 2 and the pre-exponential term includes estimated systematic error. Rate coefficients for the OD reaction were also determined over a range of temperature (262-374 K) at 100 Torr (He). The OD rate coefficients were ~15% greater than the OH values and showed similar temperature dependent behavior with k2(T) = (7.52 ± 0.44) × 10 13 exp[ (476 ± 20)/T] and k2(296 K) = (1.53 ± 0.15) × 10 13 cm3 molecule 1 s 1. The rate coefficients for reaction 1 were also measured using a relative rate technique between 296 and 375 K with k1(296 K) measured to be (1.22 ± 0.1) × 10 13 cm3 molecule 1 s 1 in agreement with the PLP-LIF results. In addition, the 296 K rate coefficient for the O3 + (E) CF3CH=CHCF3 reaction was determined to be reaction and the significant decrease in OH reactivity compared to the (Z) CF3CH=CHCF3 stereoisomer reaction. The estimated atmospheric lifetime of (E) CF3CH=CHCF3, due to loss by reaction with OH, is estimated to be ~90 days, while the actual lifetime will depend on the location and season of its emission. Infrared absorption spectra of (E) CF3CH=CHCF3 were measured and used to estimate the 100-year time horizon global warming potentials (GWP) of 32 (atmospherically well-mixed) and 14 (lifetime-adjusted).

In situ growth rates and biofilm development of Pseudomonas aeruginosa populations in chronic lung infections

DEFF Research Database (Denmark)

Yang, L.; Haagensen, J.A.; Jelsbak, L.

2008-01-01

matrix, whereas nonmucoid variants were present mainly as dispersed cells. To obtain estimates of the growth rates of P. aeruginosa in CF lungs, we used quantitative FISH to indirectly measure growth rates of bacteria in sputum samples (reflecting the in vivo lung conditions). The concentration of r......The growth dynamics of bacterial pathogens within infected hosts are a fundamental but poorly understood feature of most infections. We have focused on the in situ distribution and growth characteristics of two prevailing and transmissible Pseudomonas aeruginosa clones that have caused chronic lung......RNA in bacteria isolated from sputa was measured and correlated with the rRNA contents of the same bacteria growing in vitro at defined rates. The results showed that most cells were actively growing with doubling times of between 100 and 200 min, with some growing even faster. Only a small stationary...

Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

Science.gov (United States)

Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

2018-05-01

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

Substrate-Coated Illumination Droplet Spray Ionization: Real-Time Monitoring of Photocatalytic Reactions

Science.gov (United States)

Zhang, Hong; Li, Na; Zhao, Dandan; Jiang, Jie; You, Hong

2017-09-01

Real-time monitoring of photocatalytic reactions facilitates the elucidation of the mechanisms of the reactions. However, suitable tools for real-time monitoring are lacking. Herein, a novel method based on droplet spray ionization named substrate-coated illumination droplet spray ionization (SCI-DSI) for direct analysis of photocatalytic reaction solution is reported. SCI-DSI addresses many of the analytical limitations of electrospray ionization (ESI) for analysis of photocatalytic-reaction intermediates, and has potential for both in situ analysis and real-time monitoring of photocatalytic reactions. In SCI-DSI-mass spectrometry (MS), a photocatalytic reaction occurs by loading sample solutions onto the substrate-coated cover slip and by applying UV light above the modified slip; one corner of this slip adjacent to the inlet of a mass spectrometer is the high-electric-field location for launching a charged-droplet spray. After both testing and optimizing the performance of SCI-DSI, the value of this method for in situ analysis and real-time monitoring of photocatalytic reactions was demonstrated by the removal of cyclophosphamide (CP) in TiO2/UV. Reaction times ranged from seconds to minutes, and the proposed reaction intermediates were captured and identified by tandem mass spectrometry. Moreover, the free hydroxyl radical (·OH) was identified as the main radicals for CP removal. These results show that SCI-DSI is suitable for in situ analysis and real-time monitoring of CP removal under TiO2-based photocatalytic reactions. SCI-DSI is also a potential tool for in situ analysis and real-time assessment of the roles of radicals during CP removal under TiO2-based photocatalytic reactions. Graphical Abstract[Figure not available: see fulltext.

A mathematical analysis of Prx2-STAT3 disulfide exchange rate constants for a bimolecular reaction mechanism.

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Langford, Troy F; Deen, William M; Sikes, Hadley D

2018-03-22

Appreciation of peroxiredoxins as the major regulators of H 2 O 2 concentrations in human cells has led to a new understanding of redox signaling. In addition to their status as the primary reducers of H 2 O 2 to water, the oxidized peroxiredoxin byproduct of this reaction has recently been shown capable of participation in H 2 O 2 -mediated signaling pathways through disulfide exchange reactions with the transcription factor STAT3. The dynamics of peroxidase-transcription factor disulfide exchange reactions have not yet been considered in detail with respect to how these reactions fit into the larger network of competing reactions in human cells. In this study, we used a kinetic model of oxidation and reduction reactions related to H 2 O 2 metabolism in the cytosol of human cells to study the dynamics of peroxiredoxin-2 mediated oxidation of the redox-regulated transcription factor STAT3. In combination with previously reported experimental data, the model was used to estimate the rate coefficient of a biomolecular reaction between Prx2 and STAT3 for two sets of assumptions that constitute lower and upper bound cases. Using these estimates, we calculated the relative rates of the reaction of oxidized peroxiredoxin-2 and STAT3 and other competing reactions in the cytosol. These calculations revealed that peroxiredoxin-2-mediated oxidation of STAT3 likely occurs at a much slower rate than competing reactions in the cytosol. This analysis suggests the existence of more complex mechanisms, potentially involving currently unknown protein-protein recognition partners, which facilitate disulfide exchange reactions between peroxiredoxin-2 and STAT3. Copyright © 2018 Elsevier Inc. All rights reserved.

Generalization of the Activated Complex Theory of Reaction Rates. I. Quantum Mechanical Treatment

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Marcus, R. A.

1964-01-01

In its usual form activated complex theory assumes a quasi-equilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced.

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

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DeMore, W.; Bayes, K.

1998-01-01

Relative rate experiements were used to measure rate constants and temperature denpendencies of the reactions of OH with propane, n-butane, n-pentane, n-hexane, cyclopropane, cyclobutane, cyclopentane, and dimethyl ether.

Correlation between discrete probability and reaction front propagation rate in heterogeneous mixtures

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Naine, Tarun Bharath; Gundawar, Manoj Kumar

2017-09-01

We demonstrate a very powerful correlation between the discrete probability of distances of neighboring cells and thermal wave propagation rate, for a system of cells spread on a one-dimensional chain. A gamma distribution is employed to model the distances of neighboring cells. In the absence of an analytical solution and the differences in ignition times of adjacent reaction cells following non-Markovian statistics, invariably the solution for thermal wave propagation rate for a one-dimensional system with randomly distributed cells is obtained by numerical simulations. However, such simulations which are based on Monte-Carlo methods require several iterations of calculations for different realizations of distribution of adjacent cells. For several one-dimensional systems, differing in the value of shaping parameter of the gamma distribution, we show that the average reaction front propagation rates obtained by a discrete probability between two limits, shows excellent agreement with those obtained numerically. With the upper limit at 1.3, the lower limit depends on the non-dimensional ignition temperature. Additionally, this approach also facilitates the prediction of burning limits of heterogeneous thermal mixtures. The proposed method completely eliminates the need for laborious, time intensive numerical calculations where the thermal wave propagation rates can now be calculated based only on macroscopic entity of discrete probability.

Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation