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

The effect of reaction temperature on the room temperature ferromagnetic property of sol-gel derived tin oxide nanocrystal

Science.gov (United States)

Sakthiraj, K.; Hema, M.; Balachandra Kumar, K.

2018-06-01

In the present study, nanocrystalline tin oxide materials were prepared using sol-gel method with different reaction temperatures (25 °C, 50 °C, 75 °C & 90 °C) and the relation between the room temperature ferromagnetic property of the sample with processing temperature has been analysed. The X-ray diffraction pattern and infrared absorption spectra of the as-prepared samples confirm the purity of the samples. Transmission electron microscopy images visualize the particle size variation with respect to reaction temperature. The photoluminescence spectra of the samples demonstrate that luminescence process in materials is originated due to the electron transition mediated by defect centres. The room temperature ferromagnetic property is observed in all the samples with different amount, which was confirmed using vibrating sample magnetometer measurements. The saturation magnetization value of the as-prepared samples is increased with increasing the reaction temperature. From the photoluminescence & magnetic measurements we accomplished that, more amount of surface defects like oxygen vacancy and tin interstitial are created due to the increase in reaction temperature and it controls the ferromagnetic property of the samples.

Proceedings of the meeting on tunneling reaction and low temperature chemistry, 97 October. Tunneling reaction and quantum medium

Energy Technology Data Exchange (ETDEWEB)

Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru [eds.

1998-02-01

Present report is the proceedings of the 3rd Meeting on Tunneling Reaction and Low Temperature Chemistry held in Oct. 13 and 14, 1997. The main subject of the meeting is `Tunneling Reaction and Quantum Medium`. In the meeting, the physical and chemical phenomena in the liquid helium such as quantum nucleation, spectroscopy of atoms and molecules, and tunneling abstraction reaction of tritium atom were discussed as the main topics as well as the tunneling reactions in the solid hydrogen and organic compounds. Through the meetings held in 1995, 1996, and 1997, the tunneling phenomena proceeding at various temperatures (room temperature to mK) in the wide fields of chemistry, biology, and physics were discussed intensively and the importance of the tunneling phenomena in the science has been getting clear. The 12 of the presented papers are indexed individually. (J.P.N.)

Proceedings of the meeting on tunneling reaction and low temperature chemistry, 97 October. Tunneling reaction and quantum medium

International Nuclear Information System (INIS)

Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru

1998-02-01

Present report is the proceedings of the 3rd Meeting on Tunneling Reaction and Low Temperature Chemistry held in Oct. 13 and 14, 1997. The main subject of the meeting is 'Tunneling Reaction and Quantum Medium'. In the meeting, the physical and chemical phenomena in the liquid helium such as quantum nucleation, spectroscopy of atoms and molecules, and tunneling abstraction reaction of tritium atom were discussed as the main topics as well as the tunneling reactions in the solid hydrogen and organic compounds. Through the meetings held in 1995, 1996, and 1997, the tunneling phenomena proceeding at various temperatures (room temperature to mK) in the wide fields of chemistry, biology, and physics were discussed intensively and the importance of the tunneling phenomena in the science has been getting clear. The 12 of the presented papers are indexed individually. (J.P.N.)

Catalytic depolymerization of lignin and woody biomass in supercritical Ethanol: influence of reaction temperature and feedstock : Influence of reaction temperature and feedstock

NARCIS (Netherlands)

Huang, X.; Atay, C.; Zhu, J.; Palstra, S.W.L.; Korányi, T.I.; Boot, M.D.; Hensen, E.J.M.

2017-01-01

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while

Nasal reaction to changes in whole body temperature.

Science.gov (United States)

Lundqvist, G R; Pedersen, O F; Hilberg, O; Nielsen, B

1993-11-01

The changes in nasal patency following a 1.5 degrees C decrease or increase in whole body temperature were measured in 8 healthy young males, during and after 30 min of immersion in a 15 degrees C cold or a 40 degrees C warm bath, breathing air at the same temperature, in a cross-over experimental design. The nasal reactions were traced by consecutive measurements of changes in nasal cavity volumes by acoustic rhinometry. Swelling of the mucosa during cooling and an almost maximal shrinkage of the mucosa during heating were indicated by respectively a decrease and an increase in nasal cavity volumes. The reactions were determined predominantly by the whole body thermal balance, but were also influenced by the temperature of the inhaled air, either enhanced, reduced or temporarily reversed. The greatest change occurred in the nasal cavity, left or right, which differed most from the final state at the beginning of exposure due to the actual state of nasal cycle.

Characterization of Cu/CeO2/Al2O3 catalysts by temperature programmed reduction and activity for CO oxidation

International Nuclear Information System (INIS)

Cataluna, Renato; Baibich, Ione M.; Dallago, R.M.; Picinini, C.; Martinez-Arias, A.; Soria, J.

2001-01-01

The kinetic parameters for the CO oxidation reaction using copper/alumina-modified ceria as catalysts were determined. The catalysts with different concentrations of the metals were prepared using impregnation methods. In addition, the reduction-oxidation behaviour of the catalysts were investigated by temperature-programmed reduction. The activity results show that the mechanism for CO oxidation is bifunctional: oxygen is activated on the anionic vacancies of ceria surface, while carbon monoxide is adsorbed preferentially on the higher oxidation copper site. Therefore, the reaction occurs on the interfacial active centers. Temperatures-programmed Reduction patterns show a higher dispersion when cerium oxide is present. (author)

The reaction of hydrogen atoms with hydrogen peroxide as a function of temperature

DEFF Research Database (Denmark)

Lundström, T.; Christensen, H.; Sehested, K.

2001-01-01

The temperature dependence for the reaction of H atoms with H2O2 at pH 1 has been determined using pulse radiolysis technique. The reaction was studied in the temperature range 10-120 degreesC. The rate constant at 25 degreesC was found to be 5.1 +/- 0.5 x 10(7) dm(3) mol(-1) s(-1) and the activa......The temperature dependence for the reaction of H atoms with H2O2 at pH 1 has been determined using pulse radiolysis technique. The reaction was studied in the temperature range 10-120 degreesC. The rate constant at 25 degreesC was found to be 5.1 +/- 0.5 x 10(7) dm(3) mol(-1) s(-1...

Program BETA for simulation of particle decays and reactions

International Nuclear Information System (INIS)

Takhtamyshev, G.G.; Merkulova, T.A.

1997-01-01

Program BETA is designed for simulation of particle decays and reactions. The program also produces integration over the phase space and decay rate or the reaction cross section are calculated as a result of such integration. At the simulation process the adaptive random number generator SMART may be used, what is found to be useful for some difficult cases

Elementary reaction rate measurements at high temperatures by tunable-laser flash-absorption

Energy Technology Data Exchange (ETDEWEB)

Hessler, J.P. [Argonne National Laboratory, IL (United States)

1993-12-01

The major objective of this program is to measure thermal rate coefficients and branching ratios of elementary reactions. To perform these measurements, the authors constructed an ultrahigh-purity shock tube to generate temperatures between 1000 and 5500 K. The tunable-laser flash-absorption technique is used to measure the rate of change of the concentration of species which absorb below 50,000 cm{sup {minus}1} e.g.: OH, CH, and CH{sub 3}. This technique is being extended into the vacuum-ultraviolet spectral region where one can measure atomic species e.g.: H, D, C, O, and N; and diatomic species e.g.: O{sub 2}, CO, and OH.

Influence of transesterification reaction temperature on biodiesel production

Energy Technology Data Exchange (ETDEWEB)

Pighinelli, Anna Leticia Montenegro Turtelli; Zorzeto, Thais Queiroz; Park, Kil Jin [Universidade Estadual de Campinas (FEAGRI/UNICAMP), SP (Brazil). Fac. de Engenharia Agricola], E-mail: annalets@agr.unicamp.br; Bevilaqua, Gabriela [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

2008-07-01

Brazilian government policy has authorized the introduction of biodiesel into the national energy matrix, law no.11.097 of January 13th, 2005. It is necessary, like any new product, to invest in research which is able to cover its entire production chain (planting of oilseeds, vegetable oils extraction and chemical reactions), providing data and relevant information in order to optimize the process and solve critical issues. The objective of this work was to study the effects of temperature on crude sunflower transesterification reaction with ethanol. A central composite experimental design with five variation levels (25 deg, 32 deg, 47.5 deg, 64 deg and 70 deg C) was used and response surface methodology applied for the data analysis. The statistical analysis of the results showed that the production suffered the influence of temperature (linear and quadratic effects) and reaction time (linear and quadratic). The generated models did not show significant regression. The model generated was not well suited to the experimental data and the value of the coefficient of determination (R{sup 2}=0.52) was low. Consequently it was not possible to build the response surface. (author)

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).

High-temperature sensitivity and its acclimation for photosynthetic electron reactions of desert succulents

Energy Technology Data Exchange (ETDEWEB)

Chetti, M.B.; Nobel, P.S. (Univ. of California, Los Angeles (USA))

1987-08-01

Photosynthetic electron reactions of succulent plants from hot deserts are able to tolerate extremely high temperatures and to acclimate to seasonal increase in temperature. In this study, we report the influence of relatively long, in vivo, high-temperature treatments on electron transport reactions for two desert succulents, Agave deserti and Opuntia ficus-indica, species which can tolerate 60{degree}C. Whole chain electron transport averaged 3{degree}C more sensitive to a 1-hour high-temperature treatment than did PSII (Photosystem II) which in turn averaged 3{degree}C more sensitive than did PSI. For plants maintained at day/night air temperatures of 30{degree}C/20{degree}C, treatment at 50{degree}C cause these reactions to be inhibited an average of 39% during the first hour, an additional 31% during the next 4 hours, and 100% by 12 hours. Upon shifting the plants from 30{degree}C/20{degree}C to 45{degree}C/35{degree}C, the high temperatures where activity was inhibited 50% increased 3{degree}C to 8{degree}C for the three electron transport reactions, the half-times for acclimation averaging 5 days for A. deserti and 4 days for O. ficus-indica. For the 45{degree}C/35{degree}C plants treated at 60{degree}C for 1 hour, PSI activity was reduced by 54% for A. deserti and 36% for O. ficus-indica. Acclimation leads to a toleration of very high temperatures without substantial disruption of electron transport for these desert succulents, facilitating their survival in hot deserts. Indeed, the electron transport reactions of these species tolerate longer periods at higher temperatures than any other vascular plants so far reported.

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

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.

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.

Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

International Nuclear Information System (INIS)

Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

2015-01-01

Oxygen exchange reactions performed on PuO 2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO 2 . Previous CeO 2 surrogate studies exhibit similar behavior, confirming that CeO 2 is a good qualitative surrogate for PuO 2 , in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO 2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO 2 Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

CO2 as an Oxidant for High Temperature Reactions

Directory of Open Access Journals (Sweden)

Sibudjing eKawi

2015-03-01

Full Text Available This paper presents a review on the developments in catalyst technology for the reactions utilizing CO2 for high temperature applications. These include dehydrogenation of alkanes to olefins, the dehydrogenation of ethylbenzene to styrene and finally CO2 reforming of hydrocarbon feedstock (i.e. methane and alcohols. Aspects on the various reaction pathways are also highlighted. The literature on the role of promoters and catalyst development is critically evaluated. Most of the reactions discussed in this review are exploited in industries and related to on-going processes, thus providing extensive data from literature. However some reactions, such as CO2 reforming of ethanol and glycerol which have not reached industrial scale are also reviewed owing to their great potential in terms of sustainability which are essential as energy for the future. This review further illustrates the building-up of knowledge which shows the role of support and catalysts for each reaction and the underlying linkage between certain catalysts which can be adapted for the multiple CO2-related reactions.

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.

Effect of Temperature Profile on Reaction Violence in Heated, Self-Ignited, PBX-9501

Science.gov (United States)

Asay, Blaine; Dickson, Peter; Henson, Bryan; Smilowitz, Laura; Tellier, Larry

2001-06-01

Historically, the location of ignition in heated explosives has been implicated in the violence of subsequent reactions. This is based on the observation that typically, when an explosive is heated quickly, ignition occurs at the surface, leading to premature failure of confinement, a precipitous drop in pressure, and failure of the reaction. During slow heating, reaction usually occurs near the center of the charge, and more violent reactions are observed. Many safety protocols use these global results in determining safety envelopes and procedures. We have conducted instrumented experiments with cylindrical symmetry and precise thermal boundary conditions which have shown that the temperature profile in the explosive, along with the time spent at critical temperatures, and not the location of ignition, are responsible for the level of violence observed. Microwave interferometry was used to measure case expansion velocities and reaction violence. We are using the data in a companion study to develop better kinetic models for HMX and PBX 9501. Additionally, the spatially- and temporally-resolved temperature data are being made available for those who would like to use them.

Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

Energy Technology Data Exchange (ETDEWEB)

Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

2009-12-23

Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

Self-sustained high-temperature reactions : Initiation, propagation and synthesis

NARCIS (Netherlands)

Martinez Pacheco, M.

2007-01-01

Self-Propagating High-Temperature Synthesis (SHS), also called combustion synthesis is an exothermic and self-sustained reaction between the constituents, which has assumed significance for the production of ceramics and ceramic-metallic materials (cermets), because it is a very rapid processing

Reaction of hydroxyl radicals with ammonia in liquid water at elevated temperatures

DEFF Research Database (Denmark)

Hickel, B.; Sehested, K.

1992-01-01

The reaction of hydroxyl radical with ammonia in aqueous solutions has been studied by pulse radiolysis in the temperature range 20-200-degrees-C. The rate constant of the reaction was determined by monitoring the decay of the OH radical absorption at 260 nm for different concentrations of ammonia....... At room temperature the rate constant is (9.7 +/- 1) x 10(7) dm3 mol-1 s-1. In the whole range of temperatures the Tate constant follows Arrhenius law with an activation energy of (5.7 +/- 1) kJ mol-1. The protective effect of dissolved hydrogen on the radiolytic decomposition of ammon a is discussed....

Computer simulation for sodium-concrete reactions

International Nuclear Information System (INIS)

Zhang Bin; Zhu Jizhou

2006-01-01

In the liquid metal cooled fast breeder reactors (LMFBRs), direct contacts between sodium and concrete is unavoidable. Due to sodium's high chemical reactivity, sodium would react with concrete violently. Lots of hydrogen gas and heat would be released then. This would harm the ignorantly of the containment. This paper developed a program to simualte sodium-conrete reactions across-the-board. It could give the reaction zone temperature, pool temperature, penetration depth, penetration rate, hydrogen flux and reaction heat and so on. Concrete was considered to be composed of silica and water only in this paper. The variable, the quitient of sodium hydroxide, was introduced in the continuity equation to simulate the chemical reactions more realistically. The product of the net gas flux and boundary depth was ably transformed to that of penetration rate and boundary depth. The complex chemical kinetics equations was simplified under some hypothesises. All the technique applied above simplified the computer simulation consumedly. In other words, they made the computer simulation feasible. Theoretics models that applied in the program and the calculation procedure were expatiated in detail. Good agreements of an overall transient behavior were obtained in the series of sodium-concrete reaction experiment analysis. The comparison between the analytical and experimental results showed the program presented in this paper was creditable and reasonable for simulating the sodium-concrete reactions. This program could be used for nuclear safety judgement. (authors)

Temperature dependence of third order ion molecule reactions. The reaction H+3 + 2H2 = H+5 + H2

International Nuclear Information System (INIS)

Hiraoka, K.; Kebarle, P.

1975-01-01

The rate constants k 1 for Reaction (1): H + 3 +2H 2 = H + 5 +H 2 were measured in the temperature range 100--300 degreeK. The temperature dependence of k 1 has the form k 1 proportionalT - /subn/, where n=2.3. Pierce and Porter have reported a much stronger negative temperature dependence with n=4.6. The difference arises from a determination of k 1 at 300 degreeK obtained by Arifov and used by Porter. The present k 1 (300 degreeK) =9times10 -30 (cm 6 molecules -2 center-dotsec -1 ). This is more than an order of magnitude larger than the Arifov value. The temperature dependence of third body dependent association reactions like (1) is examined on the basis of the energy transfer theory and the recently proposed trimolecular complex transition state theory by Meot-Ner, Solomon, Field, and Gershinowitz. The temperature dependence of the rate constant for the reverse reaction (-1) is obtained from k 1 and the previously determined temperature dependence of the equilibria (1). k/sub -//sub 1/ gives a good straight line Arrhenius plot leading to k/sub -//sub 1/ =8.7times10 -6 exp(-8.4/RT) cm 3 molecules -1 center-dotsec -1 . The activation energy is in kcal/mole. The preexponential factor is much larger than the rate constant for Langevin collisions. This is typical for pyrolysis of ions involving second order activation

Rate coefficients for the reactions of ions with polar molecules at interstellar temperatures

International Nuclear Information System (INIS)

Adams, N.G.; Smith, D.; Clary, D.C.

1985-01-01

A theory has been developed recently which predicts that the rate coefficients, k, for the reactions of ions with polar molecules at low temperatures will be much greater than the canonical value of 10 -9 cm 3 s -1 . The new theory indicates that k is greatest for low-lying rotational sates and increases rapidly with decreasing temperature. We refer to recent laboratory measurements which validate the theory, present calculated values of k for the reactions of H + 3 ions with several polar molecules, and discuss their significance to interstellar chemistry. For the reactions of ions with molecules having large dipole moments, we recommend that k values as large as 10 -7 cm 3 s -1 should be used in ion-chemical models of low-temperature interstellar clouds

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.

Localized temperature and chemical reaction control in nanoscale space by nanowire array.

Science.gov (United States)

Jin, C Yan; Li, Zhiyong; Williams, R Stanley; Lee, K-Cheol; Park, Inkyu

2011-11-09

We introduce a novel method for chemical reaction control with nanoscale spatial resolution based on localized heating by using a well-aligned nanowire array. Numerical and experimental analysis shows that each individual nanowire could be selectively and rapidly Joule heated for local and ultrafast temperature modulation in nanoscale space (e.g., maximum temperature gradient 2.2 K/nm at the nanowire edge; heating/cooling time chemical reactions such as polymer decomposition/cross-linking and direct and localized hydrothermal synthesis of metal oxide nanowires were demonstrated.

Carbon-13 Labeling Used to Probe Cure and Degradation Reactions of High- Temperature Polymers

Science.gov (United States)

Meador, Mary Ann B.; Johnston, J. Christopher

1998-01-01

High-temperature, crosslinked polyimides are typically insoluble, intractible materials. Consequently, in these systems it has been difficult to follow high-temperature curing or long-term degradation reactions on a molecular level. Selective labeling of the polymers with carbon-13, coupled with solid nuclear magnetic resonance spectrometry (NMR), enables these reactions to be followed. We successfully employed this technique to provide insight into both curing and degradation reactions of PMR-15, a polymer matrix resin used extensively in aircraft engine applications.

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.

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

Science.gov (United States)

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

2017-11-30

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

The effects of reactants ratios, reaction temperatures and times on Maillard reaction products of the L-ascorbic acid/L-glutamic acid system

Directory of Open Access Journals (Sweden)

Yong-Yan ZHOU

2016-01-01

Full Text Available Abstract The transformation law of the Maillard reaction products with three different reactants ratios - equimolar reactants, excess L-glutamic acid and excess L-ascorbic acid reaction respectively, five different temperatures, and different time conditions for the L-ascorbic acid / L-glutamic acid system were investigated. Results showed that, the increase of the reaction time and temperature led to the increase of the browning products, uncoloured intermediate products, as well as aroma compounds. Compared with the equimolar reaction system, the excess L-ascorbic acid reaction system produced more browning products and uncoloured intermediate products, while the aroma compounds production remained the same. In the excess L-glutamic acid system, the uncoloured intermediate products increased slightly, the browning products remained the same, while the aroma compounds increased.

An optics-based variable-temperature assay system for characterizing thermodynamics of biomolecular reactions on solid support

Energy Technology Data Exchange (ETDEWEB)

Fei, Yiyan; Landry, James P.; Zhu, X. D., E-mail: xdzhu@physics.ucdavis.edu [Department of Physics, University of California, One Shields Avenue, Davis, California 95616 (United States); Li, Yanhong; Yu, Hai; Lau, Kam; Huang, Shengshu; Chokhawala, Harshal A.; Chen, Xi [Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616 (United States)

2013-11-15

A biological state is equilibrium of multiple concurrent biomolecular reactions. The relative importance of these reactions depends on physiological temperature typically between 10 °C and 50 °C. Experimentally the temperature dependence of binding reaction constants reveals thermodynamics and thus details of these biomolecular processes. We developed a variable-temperature opto-fluidic system for real-time measurement of multiple (400–10 000) biomolecular binding reactions on solid supports from 10 °C to 60 °C within ±0.1 °C. We illustrate the performance of this system with investigation of binding reactions of plant lectins (carbohydrate-binding proteins) with 24 synthetic glycans (i.e., carbohydrates). We found that the lectin-glycan reactions in general can be enthalpy-driven, entropy-driven, or both, and water molecules play critical roles in the thermodynamics of these reactions.

Proceedings of the meeting on tunneling reaction and low temperature chemistry, 98 August. Tunneling reaction and its theory

Energy Technology Data Exchange (ETDEWEB)

Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru [eds.

1998-10-01

Present report is the proceedings of the 4th Meeting on Tunneling Reaction and Low Temperature Chemistry held in August 3 and 4, 1998. The main subject of the meeting is `Tunneling Reaction and Its Theory`. In the present meeting the theoretical aspects of tunneling phenomena in the chemical reaction were discussed intensively as the main topics. Ten reports were presented on the quantum diffusion of muon and proton in the metal and H{sub 2}{sup -} anion in the solid para-hydrogen, the theory of tunnel effect in the nuclear reaction and the tunneling reaction in the organic compounds. One special lecture was presented by Prof. J. Kondo on `Proton Tunneling in Solids`. The 11 of the presented papers are indexed individually. (J.P.N.)

CO{sub 2} as an Oxidant for High-Temperature Reactions

Energy Technology Data Exchange (ETDEWEB)

Kawi, Sibudjing, E-mail: chekawis@nus.edu.sg; Kathiraser, Yasotha [Department of Chemical and Biomolecular Engineering, Faculty of Engineering, National University of Singapore, Singapore (Singapore)

2015-03-18

This paper presents a review on the developments in catalyst technology for the reactions utilizing CO{sub 2} for high-temperature applications. These include dehydrogenation of alkanes to olefins, the dehydrogenation of ethylbenzene to styrene, and finally CO{sub 2} reforming of hydrocarbon feedstock (i.e., methane) and alcohols. Aspects on the various reaction pathways are also highlighted. The literature on the role of promoters and catalyst development is critically evaluated. Most of the reactions discussed in this review are exploited in industries and related to on-going processes, thus providing extensive data from literature. However, some reactions, such as CO{sub 2} reforming of ethanol and glycerol, which have not reached industrial scale, are also reviewed owing to their great potential in terms of sustainability, which is essential as energy for the future. This review further illustrates the building-up of knowledge that shows the role of support and catalysts for each reaction and the underlying linkage between certain catalysts, which can be adapted for the multiple CO{sub 2}-related reactions.

The Influence of Mixing in High Temperature Gas Phase Reactions

DEFF Research Database (Denmark)

Østberg, Martin

1996-01-01

by injection of NH3 with carrier gas into the flue gas. NH3 can react with NO and form N2, but a competing reaction path is the oxidation of NH3 to NO.The SNR process is briefly described and it is shown by chemical kinetic modelling that OH radicals under the present conditions will initiate the reaction......The objective of this thesis is to describe the mixing in high temperature gas phase reactions.The Selective Non-Catalytic Reduction of NOx (referred as the SNR process) using NH3 as reductant was chosen as reaction system. This in-furnace denitrification process is made at around 1200 - 1300 K...... diffusion. The SNR process is simulated using the mixing model and an empirical kinetic model based on laboratory experiments.A bench scale reactor set-up has been built using a natural gas burner to provide the main reaction gas. The set-up has been used to perform an experimental investigation...

Kinetics of the high temperature oxygen exchange reaction on {sup 238}PuO{sub 2} powder

Energy Technology Data Exchange (ETDEWEB)

Whiting, Christofer E., E-mail: chris.whiting@udri.udayton.edu [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States); Du, Miting; Felker, L. Kevin; Wham, Robert M. [Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN 37831 (United States); Barklay, Chadwick D.; Kramer, Daniel P. [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States)

2015-12-15

Oxygen exchange reactions performed on PuO{sub 2} suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO{sub 2}. Previous CeO{sub 2} surrogate studies exhibit similar behavior, confirming that CeO{sub 2} is a good qualitative surrogate for PuO{sub 2}, in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO{sub 2} oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO{sub 2} Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol: Influence of Reaction Temperature and Feedstock.

Science.gov (United States)

Huang, Xiaoming; Atay, Ceylanpinar; Zhu, Jiadong; Palstra, Sanne W L; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

2017-11-06

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while char-forming reactions become significant at high reaction temperature (>380 °C). At preferred intermediate temperatures (300-340 °C), char-forming reactions are effectively suppressed by alkylation and Guerbet and esterification reactions. This shifts the reaction toward depolymerization, explaining high monomeric aromatics yield. Carbon-14 dating analysis of the lignin residue revealed that a substantial amount of the carbon in the lignin residue originates from reactions of lignin with ethanol. Recycling tests show that the activity of the regenerated catalyst was strongly decreased due to a loss of basic sites due to hydrolysis of the MgO function and a loss of surface area due to spinel oxide formation of the Cu and Al components. The utility of this one-step approach for upgrading woody biomass was also demonstrated. An important observation is that conversion of the native lignin contained in the lignocellulosic matrix is much easier than the conversion of technical lignin.

Effect of reaction temperature on biodiesel production from waste cooking oil using lipase as biocatalyst

Science.gov (United States)

Istiningrum, Reni Banowati; Aprianto, Toni; Pamungkas, Febria Lutfi Udin

2017-12-01

This study aims to determine the effect of temperature on conversion of biodiesel from waste cooking oil enzymatically using lipase extracted from rice bran. The feedstock was simulated waste cooking oil and lipase enzyme was extracted with buffer pH variation. The enzyme activity was titrimetrically determined and the optimum pH buffer was used to study the effect of temperature on the transesterification reaction. Temperature effects were assessed in the range of 45-60 °C and the content of methyl esters in biodiesel was determined by GC-MS. The reaction temperature significantly influences the transesterification reaction with optimum biodiesel conversion occurred at 55 °C with methyl ester content of 81.19%. The methyl ester composition in the resulting biodiesel is methyl palmitate, methyl oleate and methyl stearate.

Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions

Energy Technology Data Exchange (ETDEWEB)

Burke, Michael P.; Goldsmith, C. Franklin; Klippenstein, Stephen J.; Welz, Oliver; Huang, Haifeng; Antonov, Ivan O.; Savee, John D.; Osborn, David L.; Zádor, Judit; Taatjes, Craig A.; Sheps, Leonid

2015-07-16

We have developed a multi-scale approach (Burke, M. P.; Klippenstein, S. J.; Harding, L. B. Proc. Combust. Inst. 2013, 34, 547–555.) to kinetic model formulation that directly incorporates elementary kinetic theories as a means to provide reliable, physics-based extrapolation to unexplored conditions. Here, we extend and generalize the multi-scale modeling strategy to treat systems of considerable complexity – involving multi-well reactions, potentially missing reactions, non-statistical product branching ratios, and non-Boltzmann (i.e. non-thermal) reactant distributions. The methodology is demonstrated here for a subsystem of low-temperature propane oxidation, as a representative system for low-temperature fuel oxidation. A multi-scale model is assembled and informed by a wide variety of targets that include ab initio calculations of molecular properties, rate constant measurements of isolated reactions, and complex systems measurements. Active model parameters are chosen to accommodate both “parametric” and “structural” uncertainties. Theoretical parameters (e.g. barrier heights) are included as active model parameters to account for parametric uncertainties in the theoretical treatment; experimental parameters (e.g. initial temperatures) are included to account for parametric uncertainties in the physical models of the experiments. RMG software is used to assess potential structural uncertainties due to missing reactions. Additionally, branching ratios among product channels are included as active model parameters to account for structural uncertainties related to difficulties in modeling sequences of multiple chemically activated steps. The approach is demonstrated here for interpreting time-resolved measurements of OH, HO2, n-propyl, i-propyl, propene, oxetane, and methyloxirane from photolysis-initiated low-temperature oxidation of propane at pressures from 4 to 60 Torr and temperatures from 300 to 700 K. In particular, the multi-scale informed

Effect of Temperature Profile on Reaction Violence in Heated and Self-Ignited PBX 9501

Science.gov (United States)

Asay, Blaine; Dickson, Peter; Henson, Bryan; Smilowitz, Laura; Tellier, Larry

2002-07-01

Historically, the location of ignition in heated explosives has been implicated in the violence of subsequent reactions. This is based on the observation that typically, when an explosive is heated quickly, ignition occurs at the surface, leading to premature failure of confinement, a precipitous drop in pressure, and failure of the reaction. During slow heating, reaction usually occurs near the center of the charge, and more violent reactions are observed. Many safety protocols use these global results in determining safety envelopes and procedures. We are conducting instrumented experiments with cylindrical symmetry and precise thermal boundary conditions which are beginning to show that the temperature profile in the explosive, along with the time spent at critical temperatures, and not the location of ignition, are responsible for the level of violence observed. Microwave interferometry was used to measure case expansion velocities which can be considered a measure of reaction violence. We are using the data in a companion study to develop better kinetic models for HMX and PBX 9501. Additionally, the spatially- and temporally-resolved temperature data are being made available for those who would like to use them.

An improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions

CERN Document Server

Kraft, M

2003-01-01

We propose an improved stochastic algorithm for temperature-dependent homogeneous gas phase reactions. By combining forward and reverse reaction rates, a significant gain in computational efficiency is achieved. Two modifications of modelling the temperature dependence (with and without conservation of enthalpy) are introduced and studied quantitatively. The algorithm is tested for the combustion of n-heptane, which is a reference fuel component for internal combustion engines. The convergence of the algorithm is studied by a series of numerical experiments and the computational cost of the stochastic algorithm is compared with the DAE code DASSL. If less accuracy is needed the stochastic algorithm is faster on short simulation time intervals. The new stochastic algorithm is significantly faster than the original direct simulation algorithm in all cases considered.

Electrodeless, multi-megawatt reactor for room-temperature, lithium-6/deuterium nuclear reactions

International Nuclear Information System (INIS)

Drexler, J.

1993-01-01

This paper describes a reactor design to facilitate a room-temperature nuclear fusion/fission reaction to generate heat without generating unwanted neutrons, gamma rays, tritium, or other radioactive products. The room-temperature fusion/fission reaction involves the sequential triggering of billions of single-molecule, 6 LiD 'fusion energy pellets' distributed in lattices of a palladium ion accumulator that also acts as a catalyst to produce the molecules of 6 LiD from a solution comprising D 2 O, 6 LiOD with D 2 gas bubbling through it. The D 2 gas is the source of the negative deuterium ions in the 6 LiD molecules. The next step is to trigger a first nuclear fusion/fission reaction of some of the 6 LiD molecules, according to the well-known nuclear reaction: 6 Li + D → 2 4 He + 22.4 MeV. The highly energetic alpha particles ( 4 He nuclei) generated by this nuclear reaction within the palladium will cause shock and vibrations in the palladium lattices, leading to compression of other 6 LiD molecules and thereby triggering a second series of similar fusion/fission reactions, leading to a third series, and so on. The absorption of the kinetic energy in the palladium will, in turn, generate a continuous flow of heat into the heavy water carrier, which would be removed with a heat exchanger. (author)

Development of a Temperature Programmed Identification Technique to Characterize the Organic Sulphur Functional Groups in Coal

Directory of Open Access Journals (Sweden)

Moinuddin Ghauri

2017-06-01

Full Text Available The Temperature Programmed Reduction (TPR technique is employed for the characterisation of various organic sulphur functional groups in coal. The TPR technique is modified into the Temperature Programmed Identification technique to investigate whether this method can detect various functional groups corresponding to their reduction temperatures. Ollerton, Harworth, Silverdale, Prince of Wales coal and Mequinenza lignite were chosen for this study. High pressure oxydesulphurisation of the coal samples was also done. The characterization of various organic sulphur functional groups present in untreated and treated coal by the TPR method and later by the TPI method confirmed that these methods can identify the organic sulphur groups in coal and that the results based on total sulphur are comparable with those provided by standard analytical techniques. The analysis of the untreated and treated coal samples showed that the structural changes in the organic sulphur matrix due to a reaction can be determined.

Theoretical estimation of adiabatic temperature rise from the heat flow data obtained from a reaction calorimeter

International Nuclear Information System (INIS)

Das, Parichay K.

2012-01-01

Highlights: ► This method for estimating ΔT ad (t) against time in a semi-batch reactor is distinctively pioneer and novel. ► It has established uniquely a direct correspondence between the evolution of ΔT ad (t) in RC and C A (t) in a semi-batch reactor. ► Through a unique reaction scheme, the independent effects of heat of mixing and reaction on ΔT ad (t) has been demonstrated quantitatively. ► This work will help to build a thermally safe corridor of a thermally hazard reaction. ► This manuscript, the author believes will open a new vista for further research in Adiabatic Calorimetry. - Abstract: A novel method for estimating the transient profile of adiabatic rise in temperature has been developed from the heat flow data for exothermic chemical reactions that are conducted in reaction calorimeter (RC). It has also been mathematically demonstrated by the present design that there exists a direct qualitative equivalence between the temporal evolution of the adiabatic temperature rise and the concentration of the limiting reactant for an exothermic chemical reaction, carried out in semi batch mode. The proposed procedure shows that the adiabatic temperature rise will always be less than that of the reaction executed at batch mode thereby affording a thermally safe corridor. Moreover, a unique reaction scheme has been designed to establish the independent heat effect of dissolution and reaction quantitatively. It is hoped that the testimony of the transient adiabatic temperature rise that can be prepared by the proposed method, may provide ample scope for further research.

The Effect of Temperature on the Enzyme-Catalyzed Reaction: Insights from Thermodynamics

Science.gov (United States)

Aledo, Juan Carlos; Jimenez-Riveres, Susana; Tena, Manuel

2010-01-01

When teaching the effect of temperature on biochemical reactions, the problem is usually oversimplified by confining the thermal effect to the catalytic constant, which is identified with the rate constant of the elementary limiting step. Therefore, only positive values for activation energies and values greater than 1 for temperature coefficients…

OH+ Formation in the Low-temperature O+(4S) + H2 Reaction

Science.gov (United States)

Kovalenko, Artem; Dung Tran, Thuy; Rednyk, Serhiy; Roučka, Štěpán; Dohnal, Petr; Plašil, Radek; Gerlich, Dieter; Glosík, Juraj

2018-04-01

Formation of OH+ in collisions of ground-state O+(4S) ions with normal H2 has been studied using a variable temperature 22-pole RF ion trap. From 300 to 30 K the measured reaction rate coefficient is temperature-independent, with a small decrease toward 15 K. The recent wave packet calculation predicts a slightly steeper temperature dependence. The rate coefficients at 300 and 15 K are almost the same, (1.4 ± 0.3) × 10‑9 cm3 s‑1 and (1.3 ± 0.3) × 10‑9 cm3 s‑1, respectively. The influence of traces of the two metastable ions, O+(2D) and O+(2P), has been examined by monitoring the H+ products of their reactions with H2, as well as by chemically probing them with N2 reactant gas.

Gravitropic reaction of primary seminal roots of Zea mays L. influenced by temperature and soil water potential.

Science.gov (United States)

Nakamoto, T

1995-03-01

The growth of the primary seminal root of maize (Zea mays L.) is characterized by an initial negative gravitropic reaction and a later positive one that attains a plagiotropic liminal angle. The effects of temperature and water potential of the surrounding soil on these gravitropic reactions were studied. Temperatures of 32, 25, and 18C and soil water potentials of -5, -38, and -67 kPa were imposed and the direction of growth was measured for every 1 cm length of the root. The initial negative gravitropic reaction extended to a distance of about 10 cm from the grain. Higher temperatures reduced the initial negative gravitropic reaction. Lower soil water potential induced a downward growth at root emergence. A mathematical model, in which it was assumed that the rate of the directional change of root growth was a sum of a time-dependent negative gravitropic reaction and an establishment of the liminal angle, adequately fitted the distance-angle relations. It was suggested that higher temperatures and/or a lower water potential accelerated the diminution of the initial negative gravitropic reaction.

The ecology and evolution of temperature-dependent reaction norms for sex determination in reptiles: a mechanistic conceptual model.

Science.gov (United States)

Pezaro, Nadav; Doody, J Sean; Thompson, Michael B

2017-08-01

Sex-determining mechanisms are broadly categorised as being based on either genetic or environmental factors. Vertebrate sex determination exhibits remarkable diversity but displays distinct phylogenetic patterns. While all eutherian mammals possess XY male heterogamety and female heterogamety (ZW) is ubiquitous in birds, poikilothermic vertebrates (fish, amphibians and reptiles) exhibit multiple genetic sex-determination (GSD) systems as well as environmental sex determination (ESD). Temperature is the factor controlling ESD in reptiles and temperature-dependent sex determination (TSD) in reptiles has become a focal point in the study of this phenomenon. Current patterns of climate change may cause detrimental skews in the population sex ratios of reptiles exhibiting TSD. Understanding the patterns of variation, both within and among populations and linking such patterns with the selection processes they are associated with, is the central challenge of research aimed at predicting the capacity of populations to adapt to novel conditions. Here we present a conceptual model that innovates by defining an individual reaction norm for sex determination as a range of incubation temperatures. By deconstructing individual reaction norms for TSD and revealing their underlying interacting elements, we offer a conceptual solution that explains how variation among individual reaction norms can be inferred from the pattern of population reaction norms. The model also links environmental variation with the different patterns of TSD and describes the processes from which they may arise. Specific climate scenarios are singled out as eco-evolutionary traps that may lead to demographic extinction or a transition to either male or female heterogametic GSD. We describe how the conceptual principles can be applied to interpret TSD data and to explain the adaptive capacity of TSD to climate change as well as its limits and the potential applications for conservation and management

Ab initio molecular dynamics study of thermite reaction at Al and CuO nano-interfaces at different temperatures

Science.gov (United States)

Tang, Cui-Ming; Chen, Xiao-Xu; Cheng, Xin-Lu; Zhang, Chao-Yang; Lu, Zhi-Peng

2018-05-01

The thermite reaction at Al/CuO nano-interfaces is investigated with ab initio molecular dynamics calculations in canonical ensemble at 500 K, 800 K, 1200 K and 1500 K, respectively. The reaction process and reaction products are analyzed in terms of chemical bonds, average charge, time constants and total potential energy. The activity of the reactants enhances with increasing temperature, which induces a faster thermite reaction. The alloy reaction obviously expands outward at Cu-rich interface of Al/CuO system, and the reaction between Al and O atoms obviously expands outward at O-rich interface as temperature increases. Different reaction products are found at the outermost layer of different interfaces in the Al/CuO system. In generally, the average charge of the outer layer aluminum atoms (i.e., Al1, Al2, Al5 and Al6) increases with temperature. The potential energy of Al/CuO system decreases significantly, which indicates that drastic exothermic reaction occurs at the Al/CuO system. This research enhances fundamental understanding in temperature effect on the thermite reaction at atomic level, which can potentially open new possibilities for its industrial application.

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

KAUST Repository

Nurlaela, Ela; Shinagawa, Tatsuya; Qureshi, Muhammad; Dhawale, Dattatray Sadashiv; Takanabe, Kazuhiro

2016-01-01

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

Initiation Temperature for Runaway Tri-n-Butyl Phosphate/Nitric Acid Reaction

Energy Technology Data Exchange (ETDEWEB)

Rudisill, T.S.

2000-11-28

During a review of the H-Canyon authorization basis, Defense Nuclear Facility Safety Board (DNFSB) staff members questioned the margin of safety associated with a postulated tri-n-butyl phosphate (TBP)/nitric acid runaway reaction due to the inadvertent heating of a canyon tank containing greater than 3000 lbs (1362 kg) of TBP. The margin of safety was partially based on experiments and calculations performed by the Actinide Technology Section (ATS) to support deletion of indication of tank agitation as a Safety Class System. In the technical basis for deletion of this system, ATS personnel conservatively calculated the equilibrium temperature distribution of a canyon tank containing TBP and nitric acid layers which were inadvertently heated by a steam jet left on following a transfer. The maximum calculated temperature (128 degrees C) was compared to the minimum initiation temperature for a runaway reaction (greater than 130 degrees C) documented by experimental work in the mid 195 0s. In this work, the initiation temperature as a function of nitric acid concentration was measured for 0 and 20 wt percent dissolved solids. The DNFSB staff members were concerned that data for 0 wt percent dissolved solids were not conservative given the facts that data for 20 wt percent dissolved solids show initiation temperatures at or below 130 degrees C and H-Canyon solutions normally contained a small amount of dissolved solids.

Fundamental study on temperature estimation of steam generator tubes at sodium-water reaction

International Nuclear Information System (INIS)

Furukawa, Tomohiro; Yoshida, Eiichi

2008-11-01

In case of the tube failure in the steam generator of the sodium cooled fast breeder reactor, its adjoined tubes are rapidly heated up by the chemical reaction between sodium and water/steam. And it is known that the tubes have the damage called 'wastage' by the disclosure steam jet. This research is a fundamental study based on the metallography about temperature estimation of the damaged tubes at the sodium-water reaction for the establishment of mechanism analysis technique of the behavior. In the examination, the material which gave the rapid thermal history which imitated sodium-water reaction was produced. And it was investigated whether the thermal history (i.e. maximum temperature and the holding time) of the samples could be presumed from the metallurgical examination of the samples. The major results are as follows: (1) The microstructure of the sample which was given the rapid thermal heating has reserved the influence of the maximum temperature and the time, and the structure can explain by referring to the equilibrium diagram and the continuous cooling transformation diagram. (2) Results of the electrolytic extraction of the samples, the ratio of the remained volume to the electrolyzed volume degreased with the increase of the maximum temperature and the time. Furthermore, it was observed the correlation between the remained volume of each element (Cr, Mo, Fe, V and Nb) and the thermal history. (3) It was obtained that the thermal history of the tubes damaged by sodium-water reaction might be able to be estimated from the metallurgical examinations. (author)

A computer program incorporating Pitzer's equations for calculation of geochemical reactions in brines

Science.gov (United States)

Plummer, Niel; Parkhurst, D.L.; Fleming, G.W.; Dunkle, S.A.

1988-01-01

The program named PHRQPITZ is a computer code capable of making geochemical calculations in brines and other electrolyte solutions to high concentrations using the Pitzer virial-coefficient approach for activity-coefficient corrections. Reaction-modeling capabilities include calculation of (1) aqueous speciation and mineral-saturation index, (2) mineral solubility, (3) mixing and titration of aqueous solutions, (4) irreversible reactions and mineral water mass transfer, and (5) reaction path. The computed results for each aqueous solution include the osmotic coefficient, water activity , mineral saturation indices, mean activity coefficients, total activity coefficients, and scale-dependent values of pH, individual-ion activities and individual-ion activity coeffients , and scale-dependent values of pH, individual-ion activities and individual-ion activity coefficients. A data base of Pitzer interaction parameters is provided at 25 C for the system: Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O, and extended to include largely untested literature data for Fe(II), Mn(II), Sr, Ba, Li, and Br with provision for calculations at temperatures other than 25C. An extensive literature review of published Pitzer interaction parameters for many inorganic salts is given. Also described is an interactive input code for PHRQPITZ called PITZINPT. (USGS)

Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

Science.gov (United States)

Li, Zenghua; Kong, Biao; Wei, Aizhu; Yang, Yongliang; Zhou, Yinbo; Zhang, Lanzhun

2016-12-01

Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.

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.

The effect of irradiation temperature on the non-enzymatic browning reaction in cooked rice

Energy Technology Data Exchange (ETDEWEB)

Lee, Ju-Woon [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Oh, Sang-Hee [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Kim, Jae-Hun [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Byun, Eui-Hong [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of); Ree Kim, Mee [Department of Food and Nutrition, Chungnam National University, Gung-Dong 220, Yuseong, Daejeon 305-764 (Korea, Republic of); Baek, Min [Atomic Energy Policy Division, Ministry of Science and Technology, Government Complex-Gwacheon, Kyunggi 427-715 (Korea, Republic of); Byun, Myung-Woo [Radiation Application Research Division, Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, PO Box 1266, Jeongeup, Jeonbuk 580-185 (Korea, Republic of)]. E-mail: mwbyun@kaeri.re.kr

2007-05-15

The effect of irradiation temperature on the non-enzymatic browning reaction in a sugar-glycine solution and cooked rice generated by gamma irradiation was evaluated in the present study. When the sugar-glycine solution and cooked rice were irradiated at room temperature, the browning reaction was dramatically increased during the post-irradiation period. In the case of irradiation at below the freezing point, the browning by irradiation was retarded during not only irradiation but also a post-irradiation period. The changes of the sugar profile, such as a sugar loss or reducing power of the irradiated sugar-glycine solution and the electron spin resonance signal intensity of the irradiated cooked rice were also decreased with lower irradiation temperature. The present results may suggest that the production of free radicals and a radiolysis product is inhibited during gamma irradiation in the frozen state and it may prevent the browning reaction generated by gamma irradiation from occurring.

The effect of irradiation temperature on the non-enzymatic browning reaction in cooked rice

International Nuclear Information System (INIS)

Lee, Ju-Woon; Oh, Sang-Hee; Kim, Jae-Hun; Byun, Eui-Hong; Ree Kim, Mee; Baek, Min; Byun, Myung-Woo

2007-01-01

The effect of irradiation temperature on the non-enzymatic browning reaction in a sugar-glycine solution and cooked rice generated by gamma irradiation was evaluated in the present study. When the sugar-glycine solution and cooked rice were irradiated at room temperature, the browning reaction was dramatically increased during the post-irradiation period. In the case of irradiation at below the freezing point, the browning by irradiation was retarded during not only irradiation but also a post-irradiation period. The changes of the sugar profile, such as a sugar loss or reducing power of the irradiated sugar-glycine solution and the electron spin resonance signal intensity of the irradiated cooked rice were also decreased with lower irradiation temperature. The present results may suggest that the production of free radicals and a radiolysis product is inhibited during gamma irradiation in the frozen state and it may prevent the browning reaction generated by gamma irradiation from occurring

PHAST Version 2-A Program for Simulating Groundwater Flow, Solute Transport, and Multicomponent Geochemical Reactions

Science.gov (United States)

Parkhurst, David L.; Kipp, Kenneth L.; Charlton, Scott R.

2010-01-01

The computer program PHAST (PHREEQC And HST3D) simulates multicomponent, reactive solute transport in three-dimensional saturated groundwater flow systems. PHAST is a versatile groundwater flow and solute-transport simulator with capabilities to model a wide range of equilibrium and kinetic geochemical reactions. The flow and transport calculations are based on a modified version of HST3D that is restricted to constant fluid density and constant temperature. The geochemical reactions are simulated with the geochemical model PHREEQC, which is embedded in PHAST. Major enhancements in PHAST Version 2 allow spatial data to be defined in a combination of map and grid coordinate systems, independent of a specific model grid (without node-by-node input). At run time, aquifer properties are interpolated from the spatial data to the model grid; regridding requires only redefinition of the grid without modification of the spatial data. PHAST is applicable to the study of natural and contaminated groundwater systems at a variety of scales ranging from laboratory experiments to local and regional field scales. PHAST can be used in studies of migration of nutrients, inorganic and organic contaminants, and radionuclides; in projects such as aquifer storage and recovery or engineered remediation; and in investigations of the natural rock/water interactions in aquifers. PHAST is not appropriate for unsaturated-zone flow, multiphase flow, or density-dependent flow. A variety of boundary conditions are available in PHAST to simulate flow and transport, including specified-head, flux (specified-flux), and leaky (head-dependent) conditions, as well as the special cases of rivers, drains, and wells. Chemical reactions in PHAST include (1) homogeneous equilibria using an ion-association or Pitzer specific interaction thermodynamic model; (2) heterogeneous equilibria between the aqueous solution and minerals, ion exchange sites, surface complexation sites, solid solutions, and gases; and

Theoretical study of chemical reaction effects on vertical oscillating plate with variable temperature

Directory of Open Access Journals (Sweden)

Muthucumaraswamy R.

2006-01-01

Full Text Available An exact solution to the flow of a viscous incompressible unsteady flow past an infinite vertical oscillating plate with variable temperature and mass diffusion is presented here, taking into account of the homogeneous chemical reaction of first-order. Both the plate temperature and the concentration level near the plate are raised linearly with respect to time. The dimensionless governing equations has been obtained by the Laplace transform method, when the plate is oscillating harmonically in its own plane. The effects of velocity and concentration are studied for different parameters like phase angle, chemical reaction parameter, thermal Grashof number, mass Grashof number, Schmidt number and time are studied. The solutions are valid only for small values of time t. It is observed that the velocity increases with decreasing phase angle ωt or chemical reaction parameter. .

Effect of reaction temperature on structure and fluorescence properties of nitrogen-doped carbon dots

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yi [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Department of Chemistry and Chemical Engineering, Lyuliang University, Lyuliang 033001 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Wang, Yaling [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Feng, Xiaoting [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Zhang, Feng [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Yang, Yongzhen, E-mail: yyztyut@126.com [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); Research Center on Advanced Materials Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Liu, Xuguang, E-mail: liuxuguang@tyut.edu.cn [Key Laboratory of Interface Science and Engineering in Advanced Materials (Taiyuan University of Technology), Ministry of Education, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China)

2016-11-30

Highlights: • Nitrogen-doped carbon dots (NCDs) from ammonia solution and citric acid were synthesized at different temperatures. • Quantum yield (QY) of NCDs depends largely on the amount of fluorescent polymer chains (FPC), more FPC gives higher QY. • The law of QY of NCDs first increase and then decrease with the reaction temperature increased is found and explained. • Nitrogen doping plays significant role in getting increased UV–vis absorption and QY. - Abstract: To investigate the effect of reaction temperature and nitrogen doping on the structure and fluorescence properties of carbon dots (CDs), six kinds of nitrogen-doped CDs (NCDs) were synthesized at reaction temperatures of 120, 140, 160, 180, 200 and 220 °C, separately, by using citric acid as carbon source and ammonia solution as nitrogen source. Nitrogen-free CDs (N-free CDs-180) was also prepared at 180 °C by using citric acid as the only carbon source for comparison. Results show that reaction temperature has obvious effect on carbonization degree, quantum yield (QY), ultraviolet-visible (UV–vis) absorption and photoluminescence (PL) spectra but less effect on functional groups, nitrogen doping degree and fluorescence lifetime of NCDs. Compared with N-free CDs-180, NCDs-180 possesses enchanced QY and longer fluorescence lifetime. Doping nitrogen has obvious effect on UV–vis absorption and PL spectra but less effect on particles sizes and carbonization degree. The formation mechanism of NCDs is explored: QY of NCDs depends largely on the number of fluorescent polymer chains (FPC), the competition between FPC formation on the surface of NCDs and carbon core growth leads to the change in number of FPC, and consequently to the NCDs with highest QY at appropriate hydrothermal temperature.

Pycnonuclear 12C+12C reaction at zero temperature

International Nuclear Information System (INIS)

Gasques, L R; Beard, M; Chamon, L C; Wiescher, M

2005-01-01

We present pycnonuclear reaction calculations for a one-component ionic crystal at zero temperature considering different theoretical approaches. The rates depend directly on the determination of the astrophysical S-factor at low energies, which has been obtained through the barrier penetration formalism. A totally parameter-free model for the real part of the nuclear interaction has been employed in the calculation of 12 C+ 12 C fusion cross sections

A green synthesis of a layered titanate, potassium lithium titanate; lower temperature solid-state reaction and improved materials performance

International Nuclear Information System (INIS)

Ogawa, Makoto; Morita, Masashi; Igarashi, Shota; Sato, Soh

2013-01-01

A layered titanate, potassium lithium titanate, with the size range from 0.1 to 30 µm was prepared to show the effects of the particle size on the materials performance. The potassium lithium titanate was prepared by solid-state reaction as reported previously, where the reaction temperature was varied. The reported temperature for the titanate preparation was higher than 800 °C, though 600 °C is good enough to obtain single-phase potassium lithium titanate. The lower temperature synthesis is cost effective and the product exhibit better performance as photocatalysts due to surface reactivity. - Graphical abstract: Finite particle of a layered titanate, potassium lithium titanate, was prepared by solid-state reaction at lower temperature to show modified materials performance. Display Omitted - Highlights: • Potassium lithium titanate was prepared by solid-state reaction. • Lower temperature reaction resulted in smaller sized particles of titanate. • 600 °C was good enough to obtain single phased potassium lithium titanate. • The product exhibited better performance as photocatalyst

Thermodynamics of aqueous association and ionization reactions at high temperatures and pressures

International Nuclear Information System (INIS)

Mesmer, R.E.; Marshall, W.L.; Palmer, D.A.; Simonson, J.M.; Holmes, H.F.

1990-01-01

Electrochemical and electrical conductance cells have been widely used at ORNL over the years to quantitatively determine equilibrium constants and their salt effects to 300 degree C (EMF) and 800 degree C (conductance) at the saturation pressure of water (EMF) and to 4000 bars (conductance). The most precise results to 300 degree C for a large number of weak acids and bases show very similar thermodynamic behavior, which will be discussed. Results for the ionization constants of water, NH 3 (aq), HCl(aq), and NaCl(aq), which extend well into the supercritical region, have been fitted in terms of a model with dependence on density and temperature. The entropy change is found to be the driving force for ion-association reactions and this tendency increases (as it must) with increasing temperature at a given pressure. Also, the variation of all thermodynamic properties is greatly reduced at high fixed densities. Considerable variation occurs at low densities. From this analysis, the dependence of the reaction thermodynamics on the P-V-T properties of the solvent is shown, and the implication of large changes in hydration for solutes in the vicinity of the critical temperature will be discussed. Finally, the change in the molar compressibility coefficient for all reactions in water is shown to be the same and dependent only on the compressibility of the solvent

CHEMSIMUL - A program package for numerical simulation of chemical reaction systems

International Nuclear Information System (INIS)

Lang Rasmussen, O.; Bjergbakke, E.

1984-01-01

A description is given of a program package, CHEMSIMUL, for numerical simulation of chemical reaction systems. The main components in the package are a translator of chemical equations to differential equations, a balance equation program, a differential equation solver, EPISODE, and an input/output program. The performance of the program is demonstrated by four examples. A manual for the input file and the complete program text with comments are given in Appendices I and II. (author)

The effect of addition of primary positive salts, complex salt, on the ionic strength and rate constant at various temperatures by reaction kinetics

Science.gov (United States)

Kurade, S. S.; Ramteke, A. A.

2018-05-01

In this work, we have investigated the rate of reaction by using ionic strength at different temperatures. The main goal of this experiment is to determine the relation between ionic strength with reaction rate, reaction time and rate constant with temperature. It is observed that the addition of positive salt indicate the increasing ionic strength with increase in run time at various temperatures. Thus the temperature affects the speed of reaction and mechanism by which chemical reaction occurs and time variable plays vital role in the progress of reaction at different temperatures.

The Plutonium Temperature Effect Experimental Program

Energy Technology Data Exchange (ETDEWEB)

Haeck, Wim; Leclaire, Nicolas; Letang, Eric [IRSN, Fontenay-aux-Roses (France); Girault, Emmanuel; Fouillaud, Patrick [CEA, VALDUC (France)

2008-07-01

Various theoretical studies have shown that highly diluted plutonium solutions could have a positive temperature effect but (up to now) no experimental program has confirmed this effect. The main goal of the French Plutonium Temperature Effect Experimental Program (or PU+ in short) is to effectively show that such a positive temperature effect exists for diluted plutonium solutions. The experiments were conducted in the 'Apparatus B' facility at the CEA Valduc research centre in France and involved several sub-critical approach type of experiments using plutonium nitrate solutions with concentrations of 14.3, 15 and 20 g/l at temperatures ranging from 20 to 40 deg. C. A total number of 14 phase I experiments (consisting of independent subcritical approaches) have been performed (5 at 20 g/l, 4 at 15 g/l and 5 at 14.3 g/l) between 2006 and 2007. The impact of the uncertainties on the solution acidity and the plutonium concentration makes it difficult to clearly demonstrate the positive temperature effect, requiring an additional phase II experiment (in which the use of the same plutonium solution was ensured) from 22 to 28 deg. C performed in July 2007. This experiment has shown the existence of a positive temperature effect approx +2 pcm/deg. C (from 22 to 28 deg. C for a plutonium concentration of 14.3 g/l). (authors)

Defect reactions on the phosphorus sublattice in low-temperature electron-irradiated InP

International Nuclear Information System (INIS)

Sibille, A.; Suski, J.

1985-01-01

This Rapid Communication describes several thermally or electronically stimulated defect reactions involving the dominant deep centers in low-temperature (25--300 K) electron-irradiated InP. Some of these reactions result in an increased concentration of the centers, thereby revealing the existence of a secondary production mechanism of the related defects. Low-energy irradiations allows one to select the type of the ejected atom (P) and gives direct evidence that only a phosphorus species, interstitial or vacancy, is involved in the creation-reaction-annealing events

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.

The contact-temperature ignition (CTI) criteria for propagating chemical reactions including the effect of moisture and application to Hanford waste

International Nuclear Information System (INIS)

Cash, R.J.

1995-01-01

To assure the continued absence of uncontrolled condensed-phase chemical reactions in connection with the Hanford waste materials, efforts have been underway including both theoretical and experimental investigations to clarify the requirements for such reactions. This document defines the differences and requirements for homogeneous runaway and propagating chemical reactions incuding a discussion of general contact-temperature ignition (CTI) condition for propagating reactions that include the effect of moisture. The CTI condition implies that the contact temperature or interface temperature between reacted and unreacted materials must exceed the ignition temperature and is compared to experimental data including both synthetic ferrocyanide and surrogate organic materials. In all cases, the occurrences of ignition accompanied by self-propagating reactions are consistent with the theoretical anticipations of the CTI condition

PTOLEMY, a program for heavy-ion direction-reaction calculations

International Nuclear Information System (INIS)

Gloeckner, D.H.; Macfarlane, M.H.; Pieper, S.C.

1976-03-01

Ptolemy is an IBM/360 program for the computation of nuclear elastic and direct-reaction cross sections. It carries out both optical-model fits to elastic-scattering data at one or more energies, and DWBA calculations for nucleon-transfer reactions. Ptolemy has been specifically designed for heavy-ion calculations. It is fast and does not require large amounts of core. The input is exceptionally flexible and easy to use. This report outlines the types of calculation that Ptolemy can carry out, summarizes the formulas used, and gives a detailed description of its input

An MHD heat source based on intermetallic reactions

Energy Technology Data Exchange (ETDEWEB)

Sadjian, H.; Zavitsanos, P. (General Sciences, Inc., Souderton, PA (United States)); Marston, C.H. (Villanova Univ., PA (United States))

1991-05-06

The main objective of this program was the development of an MHD heat source of potential use in Space - Based Multi Megawatt, MHD Power Systems. The approach is based on extension of high temperature chemical/ion release technology developed by the General Sciences, Incorporated (GSI) team and successfully applied in other Space Applications. Solid state reactions have been identified which can deliver energy densities and electrons in excess of those from high energy explosives as well as other conventional fuels. The use of intermetallic reactions can be used to generate hot hydrogen plasma from the reaction, to create a high level of seedant ionization, can be packaged as a cartridge type fuels for discrete pulses. The estimated weight for energizing a (100 MW - 1000 sec) Pulsed MHD Power System can range from 12 to 25 {times} 10{sup 3} kg depending on reaction system and strength of the magnetic field. The program consisted of two major tasks with eight subtasks designed to systematically evaluate these concepts in order to reduce fuel weight requirements. Laboratory measurements on energy release, reaction product identification and levels of ionization were conducted in the first task to screen candidate fuels. The second task addressed the development of a reaction chamber in which conductivity, temperature and pressure were measured. Instrumentation was developed to measure these parameters under high temperature pulsed conditions in addition to computer programs to reduce the raw data. Measurements were conducted at GSI laboratories for fuel weights of up to 120 grams and at the Franklin Research Center* for fuel weights up to 1 kilogram. The results indicate that fuel weight can be scaled using modular packaging. Estimates are presented for fuel weight requirements. 15 refs.

PHAST--a program for simulating ground-water flow, solute transport, and multicomponent geochemical reactions

Science.gov (United States)

Parkhurst, David L.; Kipp, Kenneth L.; Engesgaard, Peter; Charlton, Scott R.

2004-01-01

The computer program PHAST simulates multi-component, reactive solute transport in three-dimensional saturated ground-water flow systems. PHAST is a versatile ground-water flow and solute-transport simulator with capabilities to model a wide range of equilibrium and kinetic geochemical reactions. The flow and transport calculations are based on a modified version of HST3D that is restricted to constant fluid density and constant temperature. The geochemical reactions are simulated with the geochemical model PHREEQC, which is embedded in PHAST. PHAST is applicable to the study of natural and contaminated ground-water systems at a variety of scales ranging from laboratory experiments to local and regional field scales. PHAST can be used in studies of migration of nutrients, inorganic and organic contaminants, and radionuclides; in projects such as aquifer storage and recovery or engineered remediation; and in investigations of the natural rock-water interactions in aquifers. PHAST is not appropriate for unsaturated-zone flow, multiphase flow, density-dependent flow, or waters with high ionic strengths. A variety of boundary conditions are available in PHAST to simulate flow and transport, including specified-head, flux, and leaky conditions, as well as the special cases of rivers and wells. Chemical reactions in PHAST include (1) homogeneous equilibria using an ion-association thermodynamic model; (2) heterogeneous equilibria between the aqueous solution and minerals, gases, surface complexation sites, ion exchange sites, and solid solutions; and (3) kinetic reactions with rates that are a function of solution composition. The aqueous model (elements, chemical reactions, and equilibrium constants), minerals, gases, exchangers, surfaces, and rate expressions may be defined or modified by the user. A number of options are available to save results of simulations to output files. The data may be saved in three formats: a format suitable for viewing with a text editor; a

High-temperature epoxidation of soybean oil in flow : speeding up elemental reactions wanted and unwanted

NARCIS (Netherlands)

Cortese, B.; Croon, de M.H.J.M.; Hessel, V.

2012-01-01

The soybean oil epoxidation reaction is investigated theoretically through kinetic modeling of temperature effects enabled through flow processing under superheated conditions. Different from previous studies on such processing, here a complex reaction network superimposed by multiphase transport is

Waste-rock interactions and bedrock reactions

International Nuclear Information System (INIS)

White, W.B.

1977-01-01

The experimental program is designed to discover possible reactions between shale repository rocks and radioactive wastes. The canister can be regarded in three ways: (a) As a source of heat that modifies the mineralogy and therefore the physical properties of the surrounding rock (dry heat). (b) As a source of heat that activates reactions between minerals in the surrounding rock and slowly percolating ground water. (c) As a source of reaction materials of different composition from the surrounding rock and which therefore may react to form completely new ''minerals'' in a contact aureole around the canister. The matrix of interactions contains two composition axes. The waste compositions are defined by the various prototype waste forms usually investigated: glass, calcine, ''spent fuel'' and the ceramic supercalcine. The temperatures and pressures at which these reactions take place must be investigated. Thus each node on the ''wiring diagram'' is itself a matrix of experiments in which the T and to some extent P are varied. Experiments at higher pressure and temperature allow reactions to take place on a laboratory time scale and thus identify what could happen. These reactions are then followed downward in temperature to determine both phase boundaries and kinetic cut-offs below which equilibrium cannot be achieved on a laboratory time scale

Effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage

DEFF Research Database (Denmark)

Lu, Henna Fung Sieng; Bruheim, I.; Haugsgjerd, B.O.

2014-01-01

was assessed by peroxide value and anisidine value, measurement of lipid derived volatiles, lipid classes and antioxidants. The non-enzymatic browning reactions were assessed through the measurement of pyrroles, free amino acids content and Strecker-derived volatiles. The increase of incubation temperature......The main objective of this study was to investigate the effect of temperature towards lipid oxidation and non-enzymatic browning reactions in krill oil upon storage. Krill oil was incubated at two different temperatures (20 and 40°C) for 28 or 42 days. The oxidative stability of krill oil...

Effect of reaction temperature on the PM10 features during coal combustion

International Nuclear Information System (INIS)

Sui, J.C.; Du, Y.G.; Liu, Q.C.

2008-01-01

Coal-fired power plants produce fine fly ash consisting of particulate matter (PM). Particulate matter less than 10 micrometers in aerodynamic diameter (PM 1 0) is of significant concern because of its adverse environmental and health impacts. This paper studied the effect of reaction temperature on particulate matter (PM 1 0) emission and its chemical composition. The emission characteristics and elemental partition of PM 1 0 from coal combustion were investigated in a drop tube furnace. The paper discussed the experimental apparatus and conditions as well as the coal properties and sample analysis. Liupanshui (LPS) bituminous coal from China was used for the study. The fuel composition of LPS coal and the composition of low temperature ash of Chinese LPS coal were described. The paper also presented the results of the study with reference to particle size distribution and emission characteristic of PM 1 0; elemental partition within PM 1 0; and effect of the reaction temperature on elemental partition within PM 1 0. The PM mass size distribution was found to be bimodal. 14 refs., 2 tabs., 6 figs

Modification of reference temperature program in reactor regulating system

Energy Technology Data Exchange (ETDEWEB)

Yu, Sung Sik; Lee, Byung Jin; Kim, Se Chang; Cheong, Jong Sik [Korea Power Engineering Company, Inc., Seoul (Korea, Republic of); Kim, Ji In; Doo, Jin Yong [Korea Electric Power Cooperation, Yonggwang (Korea, Republic of)

1999-12-31

In Yonggwang nuclear units 3 and 4 currently under commercial operation, the cold temperature was very close to the technical specification limit of 298 deg C during initial startup testing, which was caused by the higher-than-expected reactor coolant system flow. Accordingly, the reference temperature (Tref) program needed to be revised to allow more flexibility for plant operations. In this study, the method of a specific test performed at Yonggwang nuclear unit 4 to revise the Tref program was described and the test results were discussed. In addition, the modified Tref program was evaluated on its potential impacts on system performance and safety. The methods of changing the Tref program and the associated pressurizer level setpoint program were also explained. Finally, for Ulchin nuclear unit 3 and 4 currently under initial startup testing, the effects of reactor coolant system flow rate on the coolant temperature were evaluated from the thermal hydraulic standpoint and an optimum Tref program was recommended. 6 refs., 4 figs., 2 tabs. (Author)

Modification of reference temperature program in reactor regulating system

Energy Technology Data Exchange (ETDEWEB)

Yu, Sung Sik; Lee, Byung Jin; Kim, Se Chang; Cheong, Jong Sik [Korea Power Engineering Company, Inc., Seoul (Korea, Republic of); Kim, Ji In; Doo, Jin Yong [Korea Electric Power Cooperation, Yonggwang (Korea, Republic of)

1998-12-31

In Yonggwang nuclear units 3 and 4 currently under commercial operation, the cold temperature was very close to the technical specification limit of 298 deg C during initial startup testing, which was caused by the higher-than-expected reactor coolant system flow. Accordingly, the reference temperature (Tref) program needed to be revised to allow more flexibility for plant operations. In this study, the method of a specific test performed at Yonggwang nuclear unit 4 to revise the Tref program was described and the test results were discussed. In addition, the modified Tref program was evaluated on its potential impacts on system performance and safety. The methods of changing the Tref program and the associated pressurizer level setpoint program were also explained. Finally, for Ulchin nuclear unit 3 and 4 currently under initial startup testing, the effects of reactor coolant system flow rate on the coolant temperature were evaluated from the thermal hydraulic standpoint and an optimum Tref program was recommended. 6 refs., 4 figs., 2 tabs. (Author)

The [sup 26]Al(p,[gamma])[sup 27]Si reaction at low stellar temperature

Energy Technology Data Exchange (ETDEWEB)

Champagne, A E [North Carolina Univ., Chapel Hill, NC (United States). Dept. of Physics and Astronomy Duke Univ., Durham, NC (United States). Triangle Universities Nuclear Lab.; Brown, B A [Michigan State Univ., East Lansing, MI (United States). Dept. of Physics and Astronomy Michigan State Univ., East Lansing, MI (United States). National Superconducting Cyclotron Lab.; Sherr, R [Princeton Univ., NJ (United States). Dept. of Physics

1993-05-03

Shell-model calculations have been used to predict the locations of states in [sup 27]Si which are analogous to well-studied states in [sup 27]Al. From this, we have determined the resonance properties of the known states in [sup 27]Si near the [sup 26]Al+p threshold. The resulting thermonuclear reaction rate is uncertain by about a factor of ten at low temperatures, but it appears that the [sup 26]Al(p, [gamma])[sup 27]Si reaction is too slow to destroy a significant amount of [sup 26]Al at these temperatures. (orig.)

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

Science.gov (United States)

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

2016-07-01

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

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

Science.gov (United States)

Bedjanian, Yuri

2018-03-29

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

Temperature-dependent reactions of phthalic acid on Ag(100)

Czech Academy of Sciences Publication Activity Database

Franke, M.; Marchini, M.; Zhang, L.; Tariq, Q.; Tsud, N.; Vorokhta, M.; Vondráček, Martin; Prince, K.; Röckert, M.; Williams, F.J.; Steinrück, H.-P.; Lytken, O.

2015-01-01

Roč. 119, č. 41 (2015), 23580-23585 ISSN 1932-7447 Institutional support: RVO:68378271 Keywords : phthalic acid * NEXAFS * photoemission spectroscopy * temperature - programmed desoprtion Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.509, year: 2015

Real-time observation of coadsorption layers on Ru(001) using a temperature-programmed ESDIAD/TOF system

Science.gov (United States)

Sasaki, T.; Itai, Y.; Iwasawa, Y.

1997-11-01

For the purpose of utilizing ESDIAD as a real-time probe for surface processes, we have developed an instrument which can measure ESDIAD images and time of flight (TOF) spectra of desorbing ions in temperature-programmed surface processes. TOF measurements are carried out to identify the mass and to determine the kinetic energy distribution of the desorbed ions. This temperature-programmed (TP-) ESDIAD/TOF system was used to observe coadsorption layers of methylamine and CO on Ru(001) which have been previously studied by our group using LEED, TPD and HREELS, also drawing upon a comparison of findings with the coadsorption system of CO and ammonia. ESDIAD images acquired for temperature-programmed surface processes in real time were found to provide new insight into the dynamic behaviour of the coadsorption layers. As to the pure adsorption of ammonia and methylamine, the second and the first (chemisorbed) layers can be easily discriminated in their different ESD detection efficiency due to the difference in neutralization rate. The intensity change of H + ions with temperature shows the process of the decomposition of methylamine to be dependent on CO coverage. The intensity of O + originating from CO changes due to the change of CO adsorption site in the reaction process. The angular distribution of H + ions which correspond to CH2NH…Ru species appears at 250-300 K in the presence of high CO pre-coverage.

Low-Cost Temperature Logger for a Polymerase Chain Reaction Thermal Cycler

Directory of Open Access Journals (Sweden)

Chan-Young Park

2016-10-01

Full Text Available Polymerase chain reaction (PCR is a method of amplifying DNA which is normally carried out with a thermal cycler. To obtain more accurate and reliable PCR results, the temperature change within the chamber of the thermal cycler needs to be verified and calibrated regularly. Commercially available temperature loggers commonly used for temperature verification tests usually require a graphical user interface (GUI attached to the logger for convenience and straightforward understanding of the device. In this study, a host-local architecture for the temperature logger that significantly reduces the development time and cost is proposed. Employing standard computing devices as the host gives better development environment and user-friendly GUI. This paper presents the hardware and software design of the host-local temperature logger, and demonstrates the use of the local temperature logger connected to a personal computer with a Windows operating system. The probe design, thermistor resistance measurement, temperature filtering, and temperature calibration is described in detail. The thermistor self-heating problem was investigated in particular to determine the reference resistor that was serially connected to the thermistor. The temperature accuracy and temporal precision of the proposed system was 0.1 K.

Ptolemy: a program for heavy-ion direct-reaction calculations

International Nuclear Information System (INIS)

Macfarlane, M.H.; Pieper, S.C.

1978-04-01

Ptolemy is an IBM/360 program for the computation of nuclear elastic and direct-reaction cross sections. It carries out optical-model fits to elastic-scattering data at one or more energies and for one or more combinations of projectile and target, collective model DWBA calculations of excitation processes, and finite-range DWBA calculations of nucleon-transfer reactions. It is fast and does not require large amounts of core. The input is exceptionally flexible and easy to use. The types of calculations that Ptolemy can carry out are outlined, the formulas used are summarized, and a detailed description of its input is given

Reaction of chlorine nitrate with hydrogen chloride and water at Antarctic stratospheric temperatures

Science.gov (United States)

Tolbert, Margaret A.; Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

1987-01-01

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO2) with H2O and HCl on surfacers that simulate polar stratospheric clouds are studied at temperatures relevant to the Antarctic stratosphere. The gaseous products of the resulting reactions, HOCl, Cl2O, and Cl2, could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the additional formation of condensed-phase HNO3 could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.

Finite difference program for calculating hydride bed wall temperature profiles

International Nuclear Information System (INIS)

Klein, J.E.

1992-01-01

A QuickBASIC finite difference program was written for calculating one dimensional temperature profiles in up to two media with flat, cylindrical, or spherical geometries. The development of the program was motivated by the need to calculate maximum temperature differences across the walls of the Tritium metal hydrides beds for thermal fatigue analysis. The purpose of this report is to document the equations and the computer program used to calculate transient wall temperatures in stainless steel hydride vessels. The development of the computer code was motivated by the need to calculate maximum temperature differences across the walls of the hydrides beds in the Tritium Facility for thermal fatigue analysis

EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user's guide, and related documentation (Version 7.0)

International Nuclear Information System (INIS)

Wolery, T.J.; Daveler, S.A.

1992-01-01

EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ''single-point'' thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics

WO{sub 3} nanorods prepared by low-temperature seeded growth hydrothermal reaction

Energy Technology Data Exchange (ETDEWEB)

Ng, Chai Yan [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia); Abdul Razak, Khairunisak, E-mail: khairunisak@eng.usm.my [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia); NanoBiotechnology Research and Innovation (NanoBRI), Institute for Research in Molecular Medicine (INFORMM), Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lockman, Zainovia, E-mail: zainovia@eng.usm.my [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang (Malaysia)

2014-03-05

Highlights: • WO{sub 3} nanorods with 5–10 nm diameter were grown directly on seeded tungsten foil. • WO{sub 3} nanorods were successfully grown at low temperature of 80 °C. • WO{sub 3} nanorods were grown on the entire surface of the seed layer after 24 h. • Annealed nanorods showed better electrochromic properties than as-made nanorods. -- Abstract: This work describes the first tungsten oxide (WO{sub 3}) nanorods hydrothermally grown on W foil. WO{sub 3} nanorods were successfully grown at low hydrothermal temperature of 80 °C by seeded growth hydrothermal reaction. The seed layer was prepared by thermally oxidized the W foil at 400 °C for 0.5 h. This work discusses the effect of hydrothermal reaction and annealing period on the morphological, structural, and electrochromic properties of WO{sub 3} nanorods. Various hydrothermal reaction periods (8–24 h) were studied. Monoclinic WO{sub 3} nanorods with 5–10 nm diameter were obtained after hydrothermal reaction for 24 h. These 24 h WO{sub 3} nanorods were also annealed at 400 °C with varying dwelling periods (0.5–4 h). Electrochromic properties of WO{sub 3} nanorods in an acidic electrolyte were analyzed using cyclic voltammetry and UV–vis spectrophotometry. WO{sub 3} nanorods annealed at 400 °C for 1 h showed the highest charge capacity and the largest optical contrast among the 24 h WO{sub 3} films. The sample also showed good cycling stability without significant degradation. Based on the results, the reaction mechanism of WO{sub 3} nanorod formation on W foil was proposed.

Biogenic Methane Generation Potential in the Eastern Nankai Trough, Japan: Effect of Reaction Temperature and Total Organic Carbon

Science.gov (United States)

Aung, T. T.; Fujii, T.; Amo, M.; Suzuki, K.

2017-12-01

Understanding potential of methane flux from the Pleistocene fore-arc basin filled turbiditic sedimentary formation along the eastern Nankai Trough is important in the quantitative assessment of gas hydrate resources. We considered generated methane could exist in sedimentary basin in the forms of three major components, and those are methane in methane hydrate, free gas and methane dissolved in water. Generation of biomethane strongly depends on microbe activity and microbes in turn survive in diverse range of temperature, salinity and pH. This study aims to understand effect of reaction temperature and total organic carbon on generation of biomethane and its components. Biomarker analysis and cultural experiment results of the core samples from the eastern Nankai Trough reveal that methane generation rate gets peak at various temperature ranging12.5°to 35°. Simulation study of biomethane generation was made using commercial basin scale simulator, PetroMod, with different reaction temperature and total organic carbon to predict how these effect on generation of biomethane. Reaction model is set by Gaussian distribution with constant hydrogen index and standard deviation of 1. Series of simulation cases with peak reaction temperature ranging 12.5°to 35° and total organic carbon of 0.6% to 3% were conducted and analyzed. Simulation results show that linear decrease in generation potential while increasing reaction temperature. But decreasing amount becomes larger in the model with higher total organic carbon. At higher reaction temperatures, >30°, extremely low generation potential was found. This is due to the fact that the source formation modeled is less than 1 km in thickness and most of formation do not reach temperature more than 30°. In terms of the components, methane in methane hydrate and free methane increase with increasing TOC. Drastic increase in free methane was observed in the model with 3% of TOC. Methane amount dissolved in water shows almost

Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions

Science.gov (United States)

Lupinetti, Anthony J [Los Alamos, NM; Garcia, Eduardo [Los Alamos, NM; Abney, Kent D [Los Alamos, NM

2004-12-14

The synthesis of actinide tetraborides including uranium tetraboride (UB.sub.4), plutonium tetraboride (PuB.sub.4) and thorium tetraboride (ThB.sub.4) by a solid-state metathesis reaction are demonstrated. The present method significantly lowers the temperature required to .ltoreq.850.degree. C. As an example, when UCl.sub.4 is reacted with an excess of MgB.sub.2, at 850.degree. C., crystalline UB.sub.4 is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl.sub.3 as the initial step in the reaction. The UB.sub.4 product is purified by washing water and drying.

Effect of Reaction Temperature on Structure, Appearance and Bonding Type of Functionalized Graphene Oxide Modified P-Phenylene Diamine

Directory of Open Access Journals (Sweden)

Hong-Juan Sun

2018-04-01

Full Text Available In this study, graphene oxides with different functionalization degrees were prepared by a facile one-step hydrothermal reflux method at various reaction temperatures using graphene oxide (GO as starting material and p-phenylenediamine (PPD as the modifier. The effects of reaction temperature on structure, appearance and bonding type of the obtained materials were investigated by X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR, X-ray photoelectron spectroscopy (XPS, and scanning electron microscopy (SEM. The results showed that when the reaction temperature was 10–70 °C, the GO reacted with PPD through non-covalent ionic bonds (–COO−H3+N–R and hydrogen bonds (C–OH…H2N–X. When the reaction temperature reached 90 °C, the GO was functionalized with PPD through covalent bonds of C–N. The crystal structure of products became more ordered and regular, and the interlayer spacing (d value and surface roughness increased as the temperature increased. Furthermore, the results suggested that PPD was grafted on the surface of GO through covalent bonding by first attacking the carboxyl groups and then the epoxy groups of GO.

Transfusion-related adverse reactions: From institutional hemovigilance effort to National Hemovigilance program

Directory of Open Access Journals (Sweden)

Rahul Vasudev

2016-01-01

Full Text Available Aims: In this study we have evaluated the various adverse reactions related to transfusion occurring in our institution as a pilot institutional effort toward a hemovigilance program. This study will also help in understanding the problems faced by blood banks/Transfusion Medicine departments in implementing an effective hemovigilance program. Materials and Methods: All the adverse reactions related to transfusion of whole blood and its components in various clinical specialties were studied for a period of 1 year. Any transfusion-related adverse event was worked up in accordance with guidelines laid down by the Directorate General of Health Services (DGHS and departmental standard operating procedures. Results: During the study period from November 1, 2011 to October 31, 2012, 45812 components were issued [30939 WB/PRBC; 12704 fresh frozen plasma (FFP; 2169 platelets]. Risk estimation per 1000 units of red cells (WB/PRBC transfused was estimated to be: 0.8 for febrile nonhemolytic transfusion reaction (FNHTR, 0.7 for allergic reaction, 0.19 for acute hemolytic transfusion reaction (AcHTR, 0.002 for anaphylactoid reactions, 0.1 for bacterial sepsis, and 0.06 for hypervolemia and hypocalcemia. 0.09 is the risk for delayed transfusion reaction and 0.03 is the risk for transfusion-related acute lung injury (TRALI. Risk estimate per 1,000 units of platelets transfused was estimated to be 1.38 for FNHTR, 1.18 for allergic reaction, and 1 in case of bacterial sepsis. Risk estimation per 1,000 units of FFP was estimated to be 0.15 for FNHTR and 0.2 for allergic reactions. Conclusions: Factors such as clerical checks at various levels, improvement in blood storage conditions outside blood banks, leukodepletion, better inventory management, careful donor screening, bedside monitoring of transfusion, and documentation of adverse events may decrease transfusion-related adverse events. Better coordination between transfusion specialists and various clinical

Novel bimetallic dispersed catalysts for temperature-programmed coal liquefaction. Final report

Energy Technology Data Exchange (ETDEWEB)

Chunshan Song; Schobert, H.H.; Parfitt, D.P. [and others

1997-11-01

Development of new catalysts is a promising approach to more efficient coal liquefaction. It has been recognized that dispersed catalysts are superior to supported catalysts for primary liquefaction of coals, because the control of initial coal dissolution or depolymerization requires intimate contact between the catalyst and coal. This research is a fundamental and exploratory study on catalytic coal liquefaction, with the emphasis on exploring novel bimetallic dispersed catalysts for coal liquefaction and the effectiveness of temperature-programmed liquefaction using dispersed catalysts. The primary objective of this research was to explore novel bimetallic dispersed catalysts from organometallic molecular precursors, that could be used in low concentrations but exhibit relatively high activity for efficient hydroliquefaction of coals under temperature-programmed conditions. We have synthesized and tested various catalyst precursors in liquefaction of subbituminous and bituminous coals and in model compound studies to examine how do the composition and structure of the catalytic precursors affect their effectiveness for coal liquefaction under different reaction conditions, and how do these factors affect their catalytic functions for hydrogenation of polyaromatic hydrocarbons, for cleavage of C-C bonds in polycyclic systems such as 4-(1-naphthylmethyl)bibenzyl, for hydrogenolysis of C-O bond such as that in dinaphthylether, for hydrodeoxygenation of phenolic compounds and other oxygen-containing compounds such as xanthene, and for hydrodesulfurization of polycyclic sulfur compounds such as dibenzothiophene. The novel bimetallic and monometallic precursors synthesized and tested in this project include various Mo- and Fe-based compounds.

Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes

KAUST Repository

Wang, Zhandong

2016-01-20

Comprehensive low-temperature oxidation mechanisms are needed to accurately predict fuel auto-ignition properties. This paper studies the effects of a previously unconsidered third O2 addition reaction scheme on the simulated auto-ignition of n-alkanes. We demonstrate that this extended low-temperature oxidation scheme has a minor effect on the simulation of n-pentane ignition; however, its addition significantly improves the prediction of n-hexane auto-ignition under low-temperature rapid compression machine conditions. Additional simulations of n-hexane in a homogeneous charge compression ignition engine show that engine-operating parameters (e.g., intake temperature and combustion phasing) are significantly altered when the third O2 addition kinetic mechanism is considered. The advanced combustion phasing is initiated by the formation and destruction of additional radical chain-branching intermediates produced in the third O2 addition process, e.g. keto-dihydroperoxides and/or keto-hydroperoxy cyclic ethers. Our results indicate that third O2 addition reactions accelerate low-temperature radical chain branching at conditions of relevance to advance engine technologies, and therefore these chemical pathways should also be considered for n-alkanes with 6 or more carbon atoms. © 2015 The Combustion Institute.

Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

Science.gov (United States)

Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

2015-04-01

Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

Perry Nuclear Power Plant Area/Equipment Temperature Monitoring Program

International Nuclear Information System (INIS)

McGuire, L.L.

1991-01-01

The Perry Nuclear Power Plant Area/Equipment Temperature Monitoring Program serves two purposes. The first is to track temperature trends during normal plant operation in areas where suspected deviations from established environmental profiles exist. This includes the use of Resistance Temperature Detectors, Recorders, and Temperature Dots for evaluation of equipment qualified life for comparison with tested parameters and the established Environmental Design Profile. It also may be used to determine the location and duration of steam leaks for effect on equipment qualified life. The second purpose of this program is to aid HVAC design engineers in determining the source of heat outside anticipated design parameters. Resistance Temperature Detectors, Recorders, and Temperature Dots are also used for this application but the results may include design changes to eliminate the excess heat or provide qualified equipment (cable) to withstand the elevated temperature, splitting of environmental zones to capture accurate temperature parameters, or continued environmental monitoring for evaluation of equipment located in hot spots

Optimization of Si–C reaction temperature and Ge thickness in C-mediated Ge dot formation

Energy Technology Data Exchange (ETDEWEB)

Satoh, Yuhki, E-mail: yu-ki@ecei.tohoku.ac.jp; Itoh, Yuhki; Kawashima, Tomoyuki; Washio, Katsuyoshi

2016-03-01

To form Ge dots on a Si substrate, the effect of thermal reaction temperature of sub-monolayer C with Si (100) was investigated and the deposited Ge thickness was optimized. The samples were prepared by solid-source molecular beam epitaxy with an electron-beam gun for C sublimation and a Knudsen cell for Ge evaporation. C of 0.25 ML was deposited on Si (100) at a substrate temperature of 200 °C, followed by a high-temperature treatment at the reaction temperature (T{sub R}) of 650–1000 °C to create Si–C bonds. Ge equivalent to 2 to 5 nm thick was subsequently deposited at 550 °C. Small and dense dots were obtained for T{sub R} = 750 °C but the dot density decreased and the dot diameter varied widely in the case of lower and higher T{sub R}. A dot density of about 2 × 10{sup 10} cm{sup −2} was achieved for Ge deposition equivalent to 3 to 5 nm thick and a standard deviation of dot diameter was the lowest of 10 nm for 5 nm thick Ge. These results mean that C-mediated Ge dot formation was strongly influenced not only by the c(4 × 4) reconstruction condition through the Si–C reaction but also the relationship between the Ge deposition thickness and the exposed Si (100)-(2 × 1) surface area. - Highlights: • The effect of Si–C reaction temperature on Ge dot formation was investigated. • Small and dense dots were obtained for T{sub R} = 750 °C. • The dot density of about 2 × 10{sup 10} cm{sup −2} was achieved for Ge = 3 to 5 nm. • The standard deviation of dot diameter was the lowest of 10 nm at Ge = 5 nm.

Babcock and Wilcox revisions to CONTEMPT, computer program for predicting containment pressure-temperature response to a loss-of-coolant accident

International Nuclear Information System (INIS)

Hsii, Y.H.

1976-06-01

The CONTEMPT computer program predicts the pressure-temperature response of a single-volume reactor building to a loss-of-coolant accident. The report describes the analytical model used for the program. CONTEMPT assumes that the loss-of-coolant accident can be separated into two phases; the primary system blowdown and reactor building pressurization. The results of the blowdown analysis serve as the boundary conditions and are input to the CONTEMPT program. Thus, the containment model is only concerned with the pressure and temperature in the reactor building and the temperature distribution through the reactor building structures. The user is required to input the description of the discharge of coolant, the boiling of residual water by reactor decay heat, the superheating of steam passing through the core, and metal-water reactions. The reactor building is separated into liquid and vapor regions. Each region is in thermal equilibrium itself, but the two may not be in thermal equilibrium; the liquid and gaseous regions may have different temperatures. The reactor building is represented as consisting of several heat-conducting structures whose thermal behavior can be described by the one-dimensional multi-region heat conduction equation. The program also calculates building leakage and the effects of engineered safety features such as reactor building sprays, decay heat coolers, sump coolers, etc

Effect of Reaction Temperature on Carbon Yield and Morphology of CNTs on Copper Loaded Nickel Nanoparticles

Directory of Open Access Journals (Sweden)

Hu Ming

2016-01-01

Full Text Available This investigation was attempted to introduce carbon nanotubes (CNTs onto surface of copper powders in order to improve heat transfer performance of copper matrix for engineering application of electrical packaging materials. The Ni/MgO catalyst was formed on the copper powders surface by means of codeposition method. CVD technique was executed to fabricate uniform CNTs on copper powders and effect of reaction temperature on the morphology of CNTs was surveyed. The results showed that CNTs products on the copper powder surface were distributed uniformly even if reaction temperature was different. The diameter dimension of CNTs was within the scope of 30~60 nm. Growth behaviors of CNTs by CVD method were considered to be “tip-growth” mechanism. Raman spectra of CNTs proved that intensity ratio of D-band to G-band (ID/IG increased as deposition reaction temperature increased, which implied that order degree of graphitic structure in synthesized CNTs improved.

Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

Science.gov (United States)

Adamovich, Igor V; Li, Ting; Lempert, Walter R

2015-08-13

This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N(2) vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H(2)-air, CH(4)-air and C(2)H(4)-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C(3)H(8)-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C(3)H(8)-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H(2)-air, CH(4)-air and C(2)H(4)-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate

Laser thermal effect on silicon nitride ceramic based on thermo-chemical reaction with temperature-dependent thermo-physical parameters

International Nuclear Information System (INIS)

Pan, A.F.; Wang, W.J.; Mei, X.S.; Wang, K.D.; Zhao, W.Q.; Li, T.Q.

2016-01-01

Highlights: • A two-dimensional thermo-chemical reaction model is creatively built. • Thermal conductivity and heat capacity of β-Si_3N_4 are computed accurately. • The appropriate thermo-chemical reaction rate is fitted and reaction element length is set to assure the constringency. • The deepest ablated position was not the center of the ablated area due to plasma absorption. • The simulation results demonstrate the thermo-chemical process cant be simplified to be physical phase transition. - Abstract: In this study, a two-dimensional thermo-chemical reaction model with temperature-dependent thermo-physical parameters on Si_3N_4 with 10 ns laser was developed to investigate the ablated size, volume and surface morphology after single pulse. For model parameters, thermal conductivity and heat capacity of β-Si_3N_4 were obtained from first-principles calculations. Thermal-chemical reaction rate was fitted by collision theory, and then, reaction element length was deduced using the relationship between reaction rate and temperature distribution. Furthermore, plasma absorption related to energy loss was approximated as a function of electron concentration in Si_3N_4. It turned out that theoretical ablated volume and radius increased and then remained constant with increasing laser energy, and the maximum ablated depth was not in the center of the ablated zone. Moreover, the surface maximum temperature of Si_3N_4 was verified to be above 3000 K within pulse duration, and it was much higher than its thermal decomposition temperature of 1800 K, which indicated that Si_3N_4 was not ablated directly above the thermal decomposition temperature. Meanwhile, the single pulse ablation of Si_3N_4 was performed at different powers using a TEM_0_0 10 ns pulse Nd:YAG laser to validate the model. The model showed a satisfactory consistence between the experimental data and numerical predictions, presenting a new modeling technology that may significantly increase the

Analyses for experiment on sodium-water reaction temperature by the CHAMPAGNE code

International Nuclear Information System (INIS)

Yoshioka, Naoki; Kishida, Masako; Yamada, Yumi

2000-03-01

In this work, analyses on sodium-water reaction temperature in the new SWAT-1(SWAT-1R) test were completed by the CHAMPAGNE code in order to understand void and velocity distribution in sodium system, which was difficult to be measured in experiments. The application method of the RELAP5/Mod2 code was investigated to LMFBR steam generator (SG) blow down analysis, too. The following results were obtained. (1) Analyses on sodium-water reaction temperature in the SWAT-1R test. 1) Analyses were carried out for the SWAT-1R test under the condition water leak rate 600 g/s by treating the pressure loss coefficient, the interface friction coefficient and the coefficient related to reaction rate as parameters. The effect and mechanism of each parameter on the shape of reaction zone were well understood by these analyses. 2) The void and velocity distribution in sodium system were estimated by use of the most suitable parameters. These analytical results are expected to be useful for planning of the SWAT-1R test and evaluation of test result. (2) Investigation of the RELAP5/Mod2 code. 1) The items to be improved in the RELAP5/Mod2 code were clarified to apply this code to the FBR SG blow down analysis. 2) One of these items was an addition of the shell-side (sodium-side) model. A sodium-side model was designed and added to the RELAP5/Mod2 code. Test calculations were carried out by this improved code and the basic function of this code was confirmed. (author)

High-temperature reaction of ''anisotropic'' pyrolitic graphite with oxygen

International Nuclear Information System (INIS)

Lavrenko, V.A.; Pomytkin, A.P.; Neshpor, V.S.; Vinokur, F.L.

1980-01-01

Investigated is the kinetics of initial interaction stages of highly dense crystalloorientated pyrographite with oxygen. Oxidation was carried out in pure oxygen within 0.1-740 mm Hg pressure range and 500-1100 deg C temperature range. It is stated, that at the temperatures below 700 deg C pyrographite oxidation is subjected to a linear law. Above 700-800 deg C the linear law is preserved only at the initial oxidation stage, then the process is described by a parabolic law. Extension of the linear site is decreased in time with the reduction of oxygen pressure. The reaction has apparent fractional order. Activation energy of pyrogrpahite oxidation by the linear low constitutes approximately 58 kcal/mol within 600-800 deg C range and 14 kcal/mol within 800-1100 deg C range. The apparent activation energy constitutes approximately 13 kcal/mol in the region of correspondence to the parabolic law

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

DEFF Research Database (Denmark)

Christensen, H.; Sehested, K.; Løgager, T.

1994-01-01

The temperature dependence of the rate constants, for the reactions of hydrated electrons with H atoms, OH radicals and H2O2 has been determined. The reaction with H atoms, studied in the temperature range 20-250-degrees-C gives k(20-degrees-C) = 2.4 x 10(10) M-1 s-1 and the activation energy E......-1 and E(A) = 15.6 kJ mol-1 (3.7 kcal mol-1) measured from 5-150-degrees-C. Thus, the activation energy for all three fast reactions is close to that expected for diffusion controlled reactions. As phosphates were used as buffer system, the rate constant and activation energy for the reaction......(A) = 14.0 kJ mol-1 (3.3 kcal mol-1). For reaction with OH radicals the corresponding values are, k(20-degrees-C) = 3.1 x 10(10) M-1 s-1 and E(A) = 14.7 kJ mol-1 (3.5 kcal mol-1) determined in the temperature range 5-175-degrees-C. For reaction with H2O2 the values are, k(20-degrees-C) = 1.2 x 10(10) M-1 s...

Kinetics and mechanisms of iron redox reactions in silicate melts: The effects of temperature and alkali cations

Energy Technology Data Exchange (ETDEWEB)

Magnien, V.; Pinet, O. [CEA VALRHO, SCDV/LEBV, F-30207 Bagnols Sur Ceze, (France); Magnien, V.; Neuville, D. R.; Roux, J.; Richet, P. [IPGP, CNRS, Physique des Mineraux et Magmas, F-75252 Paris 05, (France); Cormier, L. [Univ Paris 06, IMPMC, F-75015 Paris, (France); Hazemann, J. L. [CNRS, Inst Neel, F-38043 Grenoble, (France); De Ligny, D. [Univ Lyon 1, LMLC, CNRS, UMR 5620, F-69622 Villeurbanne, (France); Pascarelli, S. [European Synchrotron Radiat Facil, F-38043 Grenoble, (France); Vickridge, I. [Univ Paris 06, INSP, F-75015 Paris, (France)

2008-07-01

The kinetics and the mechanisms of iron redox reactions in molten Fe-bearing pyroxene compositions have been investigated by Raman spectroscopy and X-ray absorption Near Edge Structure (XANES) experiments at the iron K-edge. The former experiments have been made only near the glass transition whereas the latter have also been performed from about 1300 to 2100 K. The same kinetics are observed with both techniques. They are described by characteristic times that depend primarily on temperature and not on the initial redox state. At high temperatures, where both kinds of reactions could be investigated, these times are similar for oxidation and reduction. From these characteristic times we have calculated as a function of temperature and composition a parameter termed effective redox diffusivity. For a given melt, the diffusivities follow two distinct Arrhenius laws, which indicate that the mechanisms of the redox reaction are not the same near the glass transition and at high temperatures. As is now well established, diffusion of divalent cations is the dominant mechanism at low temperatures but the enhanced kinetics observed for alkali-bearing melts indicate that Li{sup +} and Na{sup +} also participate in ionic transport. At super-liquidus temperatures, in contrast, diffusion of oxygen represents the dominant mechanism. (authors)

Female Juvenile Delinquents' Reactions to a Reading Program: A Mixed Methods Study

Science.gov (United States)

Sanger, Dixie; Ritzman, Mitzi; Schaefer, Lauren; Belau, Don

2010-01-01

Older students who struggle with reading are more motivated to participate in instructional intervention if they are interested in the program. This mixed methods study examined opinions and reactions of 41 female juvenile delinquents on a 1-hour demonstration of the START-IN (STudents Are Responding To INtervention) reading program. Following a…

General method and thermodynamic tables for computation of equilibrium composition and temperature of chemical reactions

Science.gov (United States)

Huff, Vearl N; Gordon, Sanford; Morrell, Virginia E

1951-01-01

A rapidly convergent successive approximation process is described that simultaneously determines both composition and temperature resulting from a chemical reaction. This method is suitable for use with any set of reactants over the complete range of mixture ratios as long as the products of reaction are ideal gases. An approximate treatment of limited amounts of liquids and solids is also included. This method is particularly suited to problems having a large number of products of reaction and to problems that require determination of such properties as specific heat or velocity of sound of a dissociating mixture. The method presented is applicable to a wide variety of problems that include (1) combustion at constant pressure or volume; and (2) isentropic expansion to an assigned pressure, temperature, or Mach number. Tables of thermodynamic functions needed with this method are included for 42 substances for convenience in numerical computations.

Equilibrium adsorption data from temperature-programmed desorption measurements

NARCIS (Netherlands)

Foeth, F.; Mugge, J.M.; van der Vaart, R.; van der Vaart, Rick; Bosch, H.; Reith, T.

1996-01-01

This work describes a novel method that enables the calculation of a series of adsorption isotherms basically from a single Temperature-Programmed Desorption (TPD) experiment. The basic idea is to saturate an adsorbent packed in a fixed bed at a certain feed concentration and temperature and to

Temperature influence on the malonic acid decomposition in the Belousov-Zhabotinsky reaction

Science.gov (United States)

Blagojević, S. M.; Anić, S. R.; Čupić, Ž. D.; Pejić, N. D.; Kolar-Anić, Lj. Z.

2009-09-01

The kinetic investigations of the malonic acid decomposition (8.00 × 10-3 mol dm-3 ≤ [CH2(COOH)2]0 ≤ 4.30 × 10-2 mol dm-3) in the Belousov-Zhabotinsky (BZ) system in the presence of bromate, bromide, sulfuric acid and cerium sulfate, were performed in the isothermal closed well stirred reactor at different temperatures (25.0°C ≤ T ≤ 45.0°C). The formal kinetics of the overall BZ reaction, and particularly kinetics in characteristic periods of BZ reaction, based on the analyses of the bromide oscillograms, was accomplished. The evolution as well as the rate constants and the apparent activation energies of the reactions, which exist in the preoscillatory and oscillatory periods, are also successfully calculated by numerical simulations. Simulations are based on the model including the Br2O species.

Fabrication of intermetallic NiAl by self-propagating high-temperature synthesis reaction using aluminium nanopowder under high pressure

CERN Document Server

Dong Shu Shan; Cheng Hai Yong; Yang Hai Bin; Zou Guang Tian

2002-01-01

By using aluminium nanopowder prepared by wire electrical explosion, pure monophase NiAl compound with fine crystallites (<=10 mu m) and good densification (98% of the theoretical green density) was successfully fabricated by means of self-propagating high-temperature synthesis (SHS) under a high pressure of 50 MPa. Investigation shows that, due to the physical and chemical characteristics of the nanoparticles, the SHS reaction mode and mechanism are distinct from those when using conventional coarse-grained reactants. The SHS reaction process depends on the thermal conditions related to pressure and can occur at a dramatically low temperature of 308 sup o C, which cannot be expected in conventional SHS reaction. With increasing pressure, the SHS explosive ignition temperature (T sub i sub g) of forming NiAl decreases due to thermal and kinetic effects.

Co-Liquefaction of Elbistan Lignite with Manure Biomass; Part 3 - Effect of Reaction Time and Temperature

Science.gov (United States)

Koyunoglu, Cemil; Karaca, Hüseyin

2017-12-01

Most of the liquefaction process were carried out in a batch reactor, in which the residence time of the liquefaction products is long enough to favour the retrogressive reactions. To minimize retrogressive reactions, the liquefaction of coal was carried out in a flowing solvent reactor in which a fixed bed of coal is continuously permeated by hot solvent. Solvent flowing through the coal bed carries the liquefaction products out of the reactor. Unlike experiments carried out under similar conditions in a batch reactor no increase in solid residue is observed during long time high temperature runs in the flowing solvent reactor. There is a greater appreciation of the importance of retrograde, or polymerization, reactions. If the free radicals formed when coal breaks down are not quickly capped with hydrogen, they react with each other to form large molecules that are much harder to break down than the original coal. Reaction time impacts both the co-liquefaction cost and the product yield. So as to study this idea, the experiments of Elbistan Lignite (EL) with manure co-liquefaction carried out by changing the reaction time from 30 to 120 minutes. As a result, the greatest oil products yields obtained at 60 minutes. Therefore, by thinking about the oil products yield values acquired, the optimal reaction time was obtained to be 60 minutes for Elbistan lignite (EL) with manure liquefied with the temperature of 350°C and 400°C. Above 425°C did not examine because solvent (tetraline) loses its function after 425 °C. The obtained optimum temperature found 400°C due to higher total conversion of liquefaction products and also oil+gas yields.

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.

Temperature effect on radiation induced reactions in ethylene and tetrafluoroethylene copolymer (ETFE)

International Nuclear Information System (INIS)

Oshima, Akihiro; Tabata, Yoneho; Ikeda, Shigetoshi; Seguchi, Tadao

1997-01-01

Ethylene and tetrafluoroethylene copolymer (ETFE) was irradiated by γ-rays or electron beam (EB) under oxygen-free atmosphere at various temperatures ranging from 77 to 573 K. Mechanical and thermal properties, and absorption spectra of the irradiated ETFEs were measured. The mechanical properties of the film have been observed to change by irradiation. The modulus and yield strength increase with increasing dose, and these phenomena are clearly distinguished above the melting temperature of ETFE (533 K). Heat of crystallization changes drastically as a function of irradiation dose around the melting , compared with other temperatures. The absorption band around 250 nm of irradiated ETFE shifts to a longer wavelength region with increase of irradiation temperature. Therefore, it was concluded from those experimental results mentioned above that crosslinking takes place and conjugated double bonds formation proceeds in a wide range of irradiation temperatures. Those reactions are enhanced by increasing temperature. The homogeneous crosslinking takes place in the molten state, while the heterogeneous crosslinking does in the crystalline solid state. (author)

Reactions of metal-substituted myoglobins with excess electrons studied by pulse radiolysis and low-temperature gamma-radiolysis

International Nuclear Information System (INIS)

Miki, Hideho; Nakajima, Atushi; Ogasawara, Masaaki; Tamura, Mamoru

1990-01-01

Reactions of metal-substituted myoglobins with excess electrons in electron-pulse-irradiated aqueous solutions at room temperature and γ-irradiated aqueous matrices at 77 K were studied for the purpose of probing the functional role of heme iron. The rate constants for the reactions of various myoglobins with hydrated electrons were not much different from each other, and were close to those of diffusion-controlled reactions. In contrast, the reduction rates of myoglobins with dithionite depended markedly on the kind of central metals in the myoglobins. The difference was interpreted in terms of Marcus' theory for electron-transfer reactions. Effects of the 6-coordinate structure of the cobalt(III) species on the reaction with dithionite was also discussed. The steady-state optical-absorption measurements of γ-irradiated matrices containing cobaltimyoglobin at 77 K demonstrated the reduction of cobalt(III) species by excess electrons produced by the action of ionizing radiation. It was shown, by electron-spin resonance spectroscopy, that a 6-coordinated cobalt(II) species produced at 77 K transformed to a 5-coordinate one at higher temperatures, as reported previously. However, structural relaxation was not observed by optical spectroscopy either in the solutions or in the low-temperature matrices. It was concluded, therefore, that the intermediate 6-coordinate cobalt(II) species gave an optical absorption spectrum which was indistinguishable from that of the relaxed 5-coordinate cobalt(II) species. (author)

Characteristics and mechanism of explosive reactions of Purex solvents with Nitric Acid at elevated temperatures

Energy Technology Data Exchange (ETDEWEB)

Miyata, Teijiro [Radiation Application Development Association, Tokai, Ibaraki (Japan); Takada, Junichi; Koike, Tadao; Tsukamoto, Michio; Watanabe, Koji [Department of Fuel Cycle Safety Research, Nuclear Safety Research Center, Tokai Research Establishment, Japan Atomic Energy Research Institute, Tokai, Ibaraki (Japan); Ida, Masaaki [JGC PLANTECH CO., LTD (Japan); Nakagiri, Naotaka [JGC Corp., Tokyo (Japan); Nishio, Gunji [Research Organization for Information Science and Technology, Tokai, Ibaraki (Japan)

2000-03-01

This investigation was undertaken to make clear the energetic properties and mechanism of explosive decomposition of Purex solvent systems (TBP/n-Dodecane/HNO{sub 3}) by Nitric Acid at elevated temperatures using a calorimetric technique (DSC, ARC) and a chromatographic technique (GC, GC/MS). The measurement of exothermic events of solvent-HNO{sub 3} reactions using DSC with a stainless steel sealed cell showed distinct two peaks with maxima at around 170 and 320degC, respectively. The peak at around 170degC was mainly attributed to the reactions of dealkylation products (n-butyl nitrate) of TBP and the solvent with nitric acid, and the peak at around 320degC was attributed to the exothermic decomposition of nitrated dodecanes formed in the foregoing exothermic reaction of dodecane with nitric acid. By using the data obtained in ARC experiments, activation energies of 123.2 and 152.5 kJ/mol were determined for the exothermic reaction of TBP with nitric acid and for the exothermic pyrolysis of n-butyl nitrate, respectively. Some possible pathways were considered for the explosive decomposition of TBP by nitric acid at elevated temperatures. (author)

High-Pressure-High-Temperature Processing Reduces Maillard Reaction and Viscosity in Whey Protein-Sugar Solutions.

Science.gov (United States)

Avila Ruiz, Geraldine; Xi, Bingyan; Minor, Marcel; Sala, Guido; van Boekel, Martinus; Fogliano, Vincenzo; Stieger, Markus

2016-09-28

The aim of the study was to determine the influence of pressure in high-pressure-high-temperature (HPHT) processing on Maillard reactions and protein aggregation of whey protein-sugar solutions. Solutions of whey protein isolate containing either glucose or trehalose at pH 6, 7, and 9 were treated by HPHT processing or conventional high-temperature (HT) treatments. Browning was reduced, and early and advanced Maillard reactions were retarded under HPHT processing at all pH values compared to HT treatment. HPHT induced a larger pH drop than HT treatments, especially at pH 9, which was not associated with Maillard reactions. After HPHT processing at pH 7, protein aggregation and viscosity of whey protein isolate-glucose/trehalose solutions remained unchanged. It was concluded that HPHT processing can potentially improve the quality of protein-sugar-containing foods, for which browning and high viscosities are undesired, such as high-protein beverages.

Children's direct fright and worry reactions to violence in fiction and news television programs.

Science.gov (United States)

van der Molen, Juliette H Walma; Bushman, Brad J

2008-09-01

To examine whether violence in fictional and news television content frightens and worries children. Mixed factorial. Type of reaction (fright, worry) and television programming (violent news, violent fiction) were within-subjects factors, whereas age, sex, and television viewing frequency were between-subjects factors. Participants included 572 children (47% boys), aged 8 to 12 years, from 9 urban and rural primary schools in the Netherlands. The main exposure was to descriptions of 8 threats frequently depicted in fictional and news programs (eg, murder, war, house fires). Children reported whether they were frightened or worried by these threats. Violent threats increased both fright and worry. These 2 reactions could be distinguished from one another in a factor analysis. When violent content was described as news, it produced more fear reactions than when it was described as fiction. Fright and worry were greater in girls than in boys, in younger children than in older children, and in light television viewers than in heavy television viewers. Pediatricians should inform parents, educators, policy makers, and broadcasters about the potentially harmful effect of violent programming on children's emotions, especially in the case of news programming.

Temperature-dependent cross sections for meson-meson nonresonant reactions in hadronic matter

International Nuclear Information System (INIS)

Zhang Yiping; Xu Xiaoming; Ge Huijun

2010-01-01

We present a potential of which the short-distance part is given by one gluon exchange plus perturbative one- and two-loop corrections and of which the large-distance part exhibits a temperature-dependent constant value. The Schroedinger equation with this temperature-dependent potential yields a temperature dependence of the mesonic quark-antiquark relative-motion wave function and of meson masses. The temperature dependence of the potential, the wave function and the meson masses brings about temperature dependence of cross sections for the nonresonant reactions ππ→ρρ for I=2, KK→K*K* for I=1, KK*→K*K* for I=1, πK→ρK* for I=3/2, πK*→ρK* for I=3/2, ρK→ρK* for I=3/2 and πK*→ρK for I=3/2. As the temperature increases, the rise or fall of peak cross sections is determined by the increased radii of initial mesons, the loosened bound states of final mesons, and the total-mass difference of the initial and final mesons. The temperature-dependent cross sections and meson masses are parametrized.

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

Science.gov (United States)

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

2017-12-01

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

Thermodynamic analysis of dust sulphation reactions

Energy Technology Data Exchange (ETDEWEB)

Yang Yongxiang; Jokilaakso, A.

1997-12-31

Sulphation reactions of metal oxides with SO{sub 2} and O. or SO{sub 3} play significant roles in sulphation roasting of sulphide and oxide minerals as well as in desulphurisation process of combustion gases. In metallurgical waste-heat boilers for sulphide smelting, the sulphation of the oxidic flue dust in the atmosphere containing sulphur oxides is an unavoidable process, and the sulphation reactions have to be guided in a controlled way in the proper parts of the gas handling equipment. In this report, some thermodynamic analyses were conducted for the oxide sulphation reactions in relation to sulphide smelting processes. The phase stability of Me-S-O systems especially for oxides - sulphates equilibrium was studied under different thermodynamic conditions of gas compositions and temperatures. The sulphate stability was analysed for an example of gas compositions in the copper flash smelter of Outokumpu Harjavalta Metals Oy, in relation to temperature. In the report, most of the information was from literature. Moreover, a number of thermodynamic computations were carried out with the HSC program, and the constructed phase stability diagrams were compared with those from the literature whenever possible. The maximum temperatures for stable sulphates under normal operating conditions of the waste-heat boilers in sulphide smelting processes were obtained. This report will serve as the basis for the kinetic studies of the sulphation reactions and the sulphation reaction modelling in pyrometallurgical processes. (orig.) SULA 2 Programme. 36 refs.

Intermediate energy heavy ion reactions. A program for CELSIUS

International Nuclear Information System (INIS)

Jakobsson, B.

1986-02-01

The accelerator system under construction in Uppsala with the ECR-source + the K equals 200 synchrocyclotron + the CELSIUS synchrotron ring for storage, cooling and acceleration opens up possibilities for a very fruitful heavy ion physics program. Some recently obtained results and some recent ideas on intermediate energy reactions are discussed and speculations are made about some experiments where the unconventional qualities of CELSIUS beams could be utilized. (author)

EQ6, a computer program for reaction path modeling of aqueous geochemical systems: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 4

Energy Technology Data Exchange (ETDEWEB)

Wolery, T.J.; Daveler, S.A.

1992-10-09

EQ6 is a FORTRAN computer program in the EQ3/6 software package (Wolery, 1979). It calculates reaction paths (chemical evolution) in reacting water-rock and water-rock-waste systems. Speciation in aqueous solution is an integral part of these calculations. EQ6 computes models of titration processes (including fluid mixing), irreversible reaction in closed systems, irreversible reaction in some simple kinds of open systems, and heating or cooling processes, as well as solve ``single-point`` thermodynamic equilibrium problems. A reaction path calculation normally involves a sequence of thermodynamic equilibrium calculations. Chemical evolution is driven by a set of irreversible reactions (i.e., reactions out of equilibrium) and/or changes in temperature and/or pressure. These irreversible reactions usually represent the dissolution or precipitation of minerals or other solids. The code computes the appearance and disappearance of phases in solubility equilibrium with the water. It finds the identities of these phases automatically. The user may specify which potential phases are allowed to form and which are not. There is an option to fix the fugacities of specified gas species, simulating contact with a large external reservoir. Rate laws for irreversible reactions may be either relative rates or actual rates. If any actual rates are used, the calculation has a time frame. Several forms for actual rate laws are programmed into the code. EQ6 is presently able to model both mineral dissolution and growth kinetics.

Catalytic Depolymerization of Lignin and Woody Biomass in Supercritical Ethanol : Influence of Reaction Temperature and Feedstock

NARCIS (Netherlands)

Huang, Xiaoming; Atay, Ceylanpinar; Zhu, Jiadong; Palstra, Sanne W L; Korányi, Tamás I; Boot, Michael D; Hensen, Emiel J M

2017-01-01

The one-step ethanolysis approach to upgrade lignin to monomeric aromatics using a CuMgAl mixed oxide catalyst is studied in detail. The influence of reaction temperature (200-420 °C) on the product distribution is investigated. At low temperature (200-250 °C), recondensation is dominant, while

HIgh Temperature Photocatalysis over Semiconductors

Science.gov (United States)

Westrich, Thomas A.

temperature-dependent quantum efficiency term, and is directly driven by bulk photocatalyst crystal parameters: maximum phonon energy and the number of phonons allowed per unit cell. This analysis extends to multiple photocatalysts and can explain experimental observations of photocatalytic oxidation rates with varied reactant concentrations. Lastly, this dissertation applies this knowledge to a thermo-catalytic reaction (CO-oxidation) using a Au/TiO 2 catalyst. The combined photo/thereto-catalytic reaction showed a 10-25% increase in CO conversion during a temperature programmed reaction experiment.

The reaction of hydrogen peroxide with Fe(II) ions at elevated temperatures

DEFF Research Database (Denmark)

Christensen, H.; Sehested, K.; Løgager, T.

1993-01-01

The rate constant for the reaction between Fe(II) ions and H2O2 has been determined at pH 0.4-2 as a function of temperature in the range 5-300-degrees-C. H2O2 was produced by irradiating the aqueous solution with a pulse of electrons. The rate constants at 20 and 300-degrees-C were determined...

Environmentally friendly room temperature strecker reaction:one-pot synthesis of α-aminonitriles in ionic liquid

International Nuclear Information System (INIS)

Mojtahedi, M. M.; Abaee, M.S.; Abbasi, H.

2006-01-01

A three component efficient and facile procedure is developed for the synthesis of a-aminonitriles from aromatic-and aliphatic aldehydes, amines, and trimethylsilyl cyanide in 1-butyl-3-methyl-1H-imidazolium perchlorate ([bmim][C1O 4 ]) ionic liquid as the reaction medium at room temperature. Excellent yields are obtained in this one-pot procedure with short reaction times and the ionic liquid medium reused several times in a row

Evaluation of thermal network correction program using test temperature data

Science.gov (United States)

Ishimoto, T.; Fink, L. C.

1972-01-01

An evaluation process to determine the accuracy of a computer program for thermal network correction is discussed. The evaluation is required since factors such as inaccuracies of temperatures, insufficient number of temperature points over a specified time period, lack of one-to-one correlation between temperature sensor and nodal locations, and incomplete temperature measurements are not present in the computer-generated information. The mathematical models used in the evaluation are those that describe a physical system composed of both a conventional and a heat pipe platform. A description of the models used, the results of the evaluation of the thermal network correction, and input instructions for the thermal network correction program are presented.

Local adaptation at the transcriptome level in brown trout: evidence from early life history temperature genomic reaction norms.

Directory of Open Access Journals (Sweden)

Kristian Meier

Full Text Available Local adaptation and its underlying molecular basis has long been a key focus in evolutionary biology. There has recently been increased interest in the evolutionary role of plasticity and the molecular mechanisms underlying local adaptation. Using transcriptome analysis, we assessed differences in gene expression profiles for three brown trout (Salmo trutta populations, one resident and two anadromous, experiencing different temperature regimes in the wild. The study was based on an F2 generation raised in a common garden setting. A previous study of the F1 generation revealed different reaction norms and significantly higher QST than FST among populations for two early life-history traits. In the present study we investigated if genomic reaction norm patterns were also present at the transcriptome level. Eggs from the three populations were incubated at two temperatures (5 and 8 degrees C representing conditions encountered in the local environments. Global gene expression for fry at the stage of first feeding was analysed using a 32k cDNA microarray. The results revealed differences in gene expression between populations and temperatures and population × temperature interactions, the latter indicating locally adapted reaction norms. Moreover, the reaction norms paralleled those observed previously at early life-history traits. We identified 90 cDNA clones among the genes with an interaction effect that were differently expressed between the ecologically divergent populations. These included genes involved in immune- and stress response. We observed less plasticity in the resident as compared to the anadromous populations, possibly reflecting that the degree of environmental heterogeneity encountered by individuals throughout their life cycle will select for variable level of phenotypic plasticity at the transcriptome level. Our study demonstrates the usefulness of transcriptome approaches to identify genes with different temperature reaction

T/sub hot/ reduction: a program for lowering primary temperatures on a PWR

International Nuclear Information System (INIS)

Augustine, D.B.; DiTommaso, S.M.; Manz, E.M.; Reister, P.

1987-01-01

This paper focuses on the key technical issues addressed in a program to support operation of the Byron Unit 1 pressurized water reactor at primary side temperatures significantly lowered with respect at primary side temperatures significantly lowered with respect to the original design temperatures. These operating temperatures were lowered in order to reduce the potential for initiation of primary water stress corrosion cracking in the steam generator tubing. The efforts of this program were aimed at maintaining operation of the unit at the maximum possible power level at the reduced temperatures. In addition, the program is designed to allow for cycle-to-cycle flexibility within a range of operating temperatures from the original design temperatures to temperatures lowered by ∼ 11 0 C (20 0 F)

The temperature dependences of the N2+ + N2 → N4+ and O2+ + O2 → O4+ association reactions

International Nuclear Information System (INIS)

Boehringer, H.; Arnold, F.; Smith, D.; Adams, N.G.

1983-01-01

The temperature dependencies of three body association reactions have been investigated in attempts to elucidate the mechanisms of ion-molecule association. The variation with temperature of the three-body rate coefficients is described usually as a power law k approximately Tsup(-n). Experience has shown that with measurements over limited temperature ranges as with previous methods the derived coefficients n are wrong and measurements over large temperature ranges are desirable. The selected ion flow-tube and the drift tube methods developed in Birmingham and Heidelberg provide measurements over (overlapping) wide temperature rang. In collaboration of the Birmingham and the Heidelberg group the He stabilized reactions N 2 + + N 2 + He → N 4 + + He and O 2 + + O 2 + He → O 4 + + He reactions over 30 to 600 deg K. A power law dependence is found above 100 K. The temperature dependencies of the rate constants are interpred and used as a critical test of recent theories of association reactions by D.R. Bates and E. Herbst. (G.Q.)

Rotational state dependence of ion-polar molecule reactions at very low temperature

International Nuclear Information System (INIS)

Dubernet, M.L.; McCarroll, R.

1989-01-01

The adiabatic rotational state method is used to investigate the rotational state dependence of the rate coefficients for ion-polar molecule reactions in the very low temperature regime characteristic of interstellar molecular clouds. Results obtained for the systems H 3 + +HCl and H 3 + +HCN indicate that all the methods based on the adiabatic separation of the rotational and radial motion of the collision complex - adiabatic capture centrifugal sudden approximation (ACCSA), statistical adiabatic channel model, classical adiabatic invariance method - agree very satisfactorily in the low temperature limit. Discrepancies observed between some of the published data would appear to arise from numerical inaccuracies rather than from any defect of the theory. (orig.)

Influence of reactions heats on variation of radius, temperature, pressure and chemical species amounts within a single acoustic cavitation bubble.

Science.gov (United States)

Kerboua, Kaouther; Hamdaoui, Oualid

2018-03-01

The scientific interest toward the study of acoustic bubble is mainly explained by its practical benefit in providing a reactional media favorable to the rapid evolution of chemical mechanism. The evolution of this mechanism is related to the simultaneous and dependent variation of the volume, temperature and pressure within the bubble, retrieved by the resolution of a differential equations system, including among others the thermal balance. This last one is subject to different assumptions, some authors deem simply that the temperature varies adiabatically during the collapsing phase, without considering the reactions heat of the studied mechanism. This paper aims to evaluate the pertinence of neglecting reactions heats in the thermal balance, by analyzing their effect on the variation of radius, temperature, pressure and chemical species amounts. The results show that the introduction of reactions heats conducts to a decrease of the temperature, an increase of the pressure and a reduction of the bubble volume. As a consequence, this leads to a drop of the quantities of free radicals produced by the chemical mechanism evolving within the bubble. This paper also proved that the impact of the consideration of reactions heats is dependent of the frequency and the acoustic amplitude of the ultrasonic wave. Copyright © 2017 Elsevier B.V. All rights reserved.

SATCAP-B: a program for thermal-hydraulic design of 'Saturated Temperature Capsule'

International Nuclear Information System (INIS)

Harayama, Yasuo; Someya, Hiroyuki; Niimi, Motoji

1989-11-01

As an advanced irradiation technique, the JMTR (Japan Materials Testing Reactor) project is developing a 'Saturated Temperature Capsule' which water is injected in and boiled. When the water is kept at a constant pressure, the water temperature does not become higher than the saturated temperature. This type capsule is based on the conception of keeping the coolant to the saturated temperature and using the temperature control. In designing the capsule in which the inner coolant is injected, thermal performances have to be understood as exactly as possible. Then, a program (named SATCAP) was compiled to graps the thermal performance within the capsule. On the other hand, a 'Saturated Temperature Capsule' was made and irradiated in the JMTR core. It was indicated from supplied water temperatures recorded by thermo-couples attached in the capsule that heat transfer coefficients prefered models due to natural convection to models incorporated in the initial version of the program. Then, the program was revised by adding mainly heat transfer model based on natural convection. The present report describes the calculation procedure and guides of input and output for the revised program (SATCAP version-B). (author)

High temperature reaction kinetics

International Nuclear Information System (INIS)

Jonah, C.D.; Beno, M.F.; Mulac, W.A.; Bartels, D.

1985-01-01

During the last year the dependence of the apparent rate of OD + CO on water pressure was measured at 305, 570, 865 and 1223 K. An explanation was found and tested for the H 2 O dependence of the apparent rate of OH(OD) + CO at high temperatures. The isotope effect for OH(D) with CO was determined over the temperature range 330 K to 1225 K. The reason for the water dependence of the rate of OH(OD) + CO near room temperatures has been investigated but no clear explanation has been found. 1 figure

Evaluation of biochars by temperature programmed oxidation/mass spectrometry

Science.gov (United States)

Michael Jackson; Thomas Eberhardt; Akwasi Boateng; Charles Mullen; Les Groom

2013-01-01

Biochars produced from thermochemical conversions of biomass were evaluated by temperature programmed oxidation (TPO). This technique, used to characterize carbon deposits on petroleum cracking catalysts, provides information on the oxidative stability of carbonaceous solids, where higher temperature reactivity indicates greater structural order, an important property...

Thermogravimetric studies of high temperature reactions between potassium salts and chromium

International Nuclear Information System (INIS)

Lehmusto, J.; Lindberg, D.; Yrjas, P.; Skrifvars, B.-J.; Hupa, M.

2012-01-01

Highlights: ► K 2 CO 3 reacted with Cr 2 O 3 forming K 2 CrO 4 . ► Presence of chlorine did not alone explain the initiation of accelerated oxidation. ► More light was shed to the role of chromates in accelerated oxidation. ► Accelerated oxidation of chromia protected steels occurs in two consecutive stages. ► Both potassium and chloride are required, so that both stages of reaction occur. - Abstract: This study compares the high temperature reactions of potassium chloride (KCl) and potassium carbonate (K 2 CO 3 ), two salts found in fly ashes formed in biomass combustion, with both pure metallic chromium (Cr) and chromium oxide (Cr 2 O 3 ). The reactions were investigated with thermogravimetric measurements and the results discussed based on thermodynamic calculations. In simple terms: potassium chloride reacted with chromium forming potassium chromate (K 2 CrO 4 ) and chromium oxide. Potassium chloride did not react with chromium oxide. Potassium carbonate reacted with chromium oxide, but not with chromium. The presence of potassium is sufficient to initiate accelerated oxidation, but chloride is needed to sustain it.

DCHAIN: A user-friendly computer program for radioactive decay and reaction chain calculations

International Nuclear Information System (INIS)

East, L.V.

1994-05-01

A computer program for calculating the time-dependent daughter populations in radioactive decay and nuclear reaction chains is described. Chain members can have non-zero initial populations and be produced from the preceding chain member as the result of radioactive decay, a nuclear reaction, or both. As presently implemented, chains can contain up to 15 members. Program input can be supplied interactively or read from ASCII data files. Time units for half-lives, etc. can be specified during data entry. Input values are verified and can be modified if necessary, before used in calculations. Output results can be saved in ASCII files in a format suitable for including in reports or other documents. The calculational method, described in some detail, utilizes a generalized form of the Bateman equations. The program is written in the C language in conformance with current ANSI standards and can be used on multiple hardware platforms

Thermal reaction norms and the scale of temperature variation: latitudinal vulnerability of intertidal nacellid limpets to climate change.

Science.gov (United States)

Morley, Simon A; Martin, Stephanie M; Day, Robert W; Ericson, Jess; Lai, Chien-Houng; Lamare, Miles; Tan, Koh-Siang; Thorne, Michael A S; Peck, Lloyd S

2012-01-01

The thermal reaction norms of 4 closely related intertidal Nacellid limpets, Antarctic (Nacella concinna), New Zealand (Cellana ornata), Australia (C. tramoserica) and Singapore (C. radiata), were compared across environments with different temperature magnitude, variability and predictability, to test their relative vulnerability to different scales of climate warming. Lethal limits were measured alongside a newly developed metric of "duration tenacity", which was tested at different temperatures to calculate the thermal reaction norm of limpet adductor muscle fatigue. Except in C. tramoserica which had a wide optimum range with two break points, duration tenacity did not follow a typical aerobic capacity curve but was best described by a single break point at an optimum temperature. Thermal reaction norms were shifted to warmer temperatures in warmer environments; the optimum temperature for tenacity (T(opt)) increased from 1.0°C (N. concinna) to 14.3°C (C. ornata) to 18.0°C (an average for the optimum range of C. tramoserica) to 27.6°C (C. radiata). The temperature limits for duration tenacity of the 4 species were most consistently correlated with both maximum sea surface temperature and summer maximum in situ habitat logger temperature. Tropical C. radiata, which lives in the least variable and most predictable environment, generally had the lowest warming tolerance and thermal safety margin (WT and TSM; respectively the thermal buffer of CT(max) and T(opt) over habitat temperature). However, the two temperate species, C. ornata and C. tramoserica, which live in a variable and seasonally unpredictable microhabitat, had the lowest TSM relative to in situ logger temperature. N. concinna which lives in the most variable, but seasonally predictable microhabitat, generally had the highest TSMs. Intertidal animals live at the highly variable interface between terrestrial and marine biomes and even small changes in the magnitude and predictability of their

Sodium-water wastage and reactions program performed by general electric in support of the US. AEC LMFBR steam generator development

International Nuclear Information System (INIS)

Greene, D.A.

1975-01-01

This paper constitutes an interim report on the sodium-water reaction programs performed, using the GE-SOWAT, GE-SMALL LEAK BEHAVIOR RIG, and GE-PTTR facilities in support of LMFBR steam generator development and its application to the Clinch River Breeder Reactor Plant. Test data from these rigs are presented, including wastage data as a function of water injection rate, sodium temperature, and orifice geometry. Initial results for self-wastage of defects under prototypical conditions, and from proof-of-principle tests of a protected heat transfer tube concept are also presented. An analytical basis for wastage phenomena is suggested. (author)

Sodium-water wastage and reactions program performed by general electric in support of the US. AEC LMFBR steam generator development

Energy Technology Data Exchange (ETDEWEB)

Greene, D A

1975-07-01

This paper constitutes an interim report on the sodium-water reaction programs performed, using the GE-SOWAT, GE-SMALL LEAK BEHAVIOR RIG, and GE-PTTR facilities in support of LMFBR steam generator development and its application to the Clinch River Breeder Reactor Plant. Test data from these rigs are presented, including wastage data as a function of water injection rate, sodium temperature, and orifice geometry. Initial results for self-wastage of defects under prototypical conditions, and from proof-of-principle tests of a protected heat transfer tube concept are also presented. An analytical basis for wastage phenomena is suggested. (author)

The effect of temperature and pressure on the oxygen reduction reactions in polyelectrolyte membranes

Energy Technology Data Exchange (ETDEWEB)

Holdcroft, S.; Abdou, M.S.; Beattie, P.; Basura, V. [Simon Fraser Univ., Burnaby, BC (Canada). Dept. of Chemistry

1997-12-31

The effect of temperature and pressure on the oxygen reduction reaction in polyelectrolyte membranes was described. Polyelectrolytes chosen for the experiment differed in composition, weight and flexibility of the polymer chains. The study was conducted in a solid state electrochemical cell at temperatures between 30 and 95 degrees C and in the pressure range of 1 to 5 atm. The solubility of oxygen in these membranes was found to follow Henry`s Law, while the diffusion coefficient decreased with pressure. The effect of temperature on the solubility of oxygen and the diffusion coefficient of oxygen in the membranes was similar to that observed in solution electrolytes. 2 refs., 3 figs.

Equilibrium chemical reaction of supersonic hydrogen-air jets (the ALMA computer program)

Science.gov (United States)

Elghobashi, S.

1977-01-01

The ALMA (axi-symmetrical lateral momentum analyzer) program is concerned with the computation of two dimensional coaxial jets with large lateral pressure gradients. The jets may be free or confined, laminar or turbulent, reacting or non-reacting. Reaction chemistry is equilibrium.

Temperature and Pressure Dependence of the Reaction S plus CS (+M) -> CS2 (+M)

DEFF Research Database (Denmark)

Glarborg, Peter; Marshall, Paul; Troe, Juergen

2015-01-01

Experimental data for the unimolecular decomposition of CS2 from the literature are analyzed by unimolecular rate theory with the goal of obtaining rate constants for the reverse reaction S + CS (+M) -> CS2 (+M) over wide temperature and pressure ranges. The results constitute an important input...

Improved Geothermometry Through Multivariate Reaction-path Modeling and Evaluation of Geomicrobiological Influences on Geochemical Temperature Indicators: Final Report

Energy Technology Data Exchange (ETDEWEB)

Mattson, Earl [Idaho National Lab. (INL), Idaho Falls, ID (United States); Smith, Robert [Idaho National Lab. (INL), Idaho Falls, ID (United States); Fujita, Yoshiko [Idaho National Lab. (INL), Idaho Falls, ID (United States); McLing, Travis [Idaho National Lab. (INL), Idaho Falls, ID (United States); Neupane, Ghanashyam [Idaho National Lab. (INL), Idaho Falls, ID (United States); Palmer, Carl [Idaho National Lab. (INL), Idaho Falls, ID (United States); Reed, David [Idaho National Lab. (INL), Idaho Falls, ID (United States); Thompson, Vicki [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2015-03-01

The project was aimed at demonstrating that the geothermometric predictions can be improved through the application of multi-element reaction path modeling that accounts for lithologic and tectonic settings, while also accounting for biological influences on geochemical temperature indicators. The limited utilization of chemical signatures by individual traditional geothermometer in the development of reservoir temperature estimates may have been constraining their reliability for evaluation of potential geothermal resources. This project, however, was intended to build a geothermometry tool which can integrate multi-component reaction path modeling with process-optimization capability that can be applied to dilute, low-temperature water samples to consistently predict reservoir temperature within ±30 °C. The project was also intended to evaluate the extent to which microbiological processes can modulate the geochemical signals in some thermal waters and influence the geothermometric predictions.

HTP kinetics studies on isolated elementary combustion reactions over wide temperature ranges

Energy Technology Data Exchange (ETDEWEB)

Fontijn, A.; Adusei, G.Y.; Hranisavlevic, J.; Bajaj, P.N. [Rensselaer Polytechnic Institute, Troy, NY (United States)

1993-12-01

The goals of this project are to provide accurate data on the temperature dependence of the kinetics of elementary combustion reactions, (i) for use by combustion modelers, and (ii) to gain a better fundamental understanding of, and hence predictive ability for, the chemistry involved. Experimental measurements are made mainly by using the pseudo-static HTP (high-temperature photochemistry) technique. While continuing rate coefficient measurements, further aspects of kinetics research are being explored. Thus, starting from the data obtained, a method for predicting the temperature dependence of rate coefficients of oxygen-atom olefin experiment and confirms the underlying mechanistic assumptions. Mechanistic information of another sort, i.e. by product analysis, has recently become accessible with the inauguration of our heated flow tube mass spectrometer facility; early results are reported here. HTP experiments designed to lead to measurements of product channels by resonance fluorescence have started.

Reaction of yttria-stabilized zirconia with zirconium, silicon and Zircaloy-4 at high temperature: a compatibility study for cermet fuels

International Nuclear Information System (INIS)

Arima, T.; Tateyama, T.; Idemitsu, K.; Inagaki, Y.

2003-01-01

Compatibility studies for cermet (ceramic and metal) fuels have been completed for a temperature range of 1073-1423 K. A reaction between yttria-stabilized zirconia (YSZ), as a simulated fuel, and Zr, as a candidate for a metallic matrix, has been observed at temperatures ≥1273 K, which means the formation of a metallic reaction layer at the interface between YSZ and Zr and the occurrence of metallic phases inside the YSZ. Similar results were observed for the YSZ-Zry4 (cladding) system. On the other hand, the degree of reaction was relatively large for the YSZ-Si (metallic matrix) system, and Si diffused into the YSZ. However, the maximum fuel center-line temperature can be predicted to be less than ∼1273 K for cermet fuels. Therefore, compatibility between the ceramic fuel and the metallic matrix should be good under normal reactor operational conditions. Furthermore, since the temperature of the fuel-cladding gap is lower, the cermet fuel and the cladding material are compatible

KAPSIES: A program for the calculation of multi-step direct reaction cross sections

International Nuclear Information System (INIS)

Koning, A.J.; Akkermans, J.M.

1994-09-01

We present a program for the calculation of continuum cross sections, sepctra, angular distributions and analyzing powers according to various quantum-mechanical theories for statistical multi-step direct nuclear reactions. (orig.)

Temperature-dependent kinetics of charge transfer, hydrogen-atom transfer, and hydrogen-atom expulsion in the reaction of CO+ with CH4 and CD4.

Science.gov (United States)

Melko, Joshua J; Ard, Shaun G; Johnson, Ryan S; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A

2014-09-18

We have determined the rate constants and branching ratios for the reactions of CO(+) with CH4 and CD4 in a variable-temperature selected ion flow tube. We find that the rate constants are collisional for all temperatures measured (193-700 K for CH4 and 193-500 K for CD4). For the CH4 reaction, three product channels are identified, which include charge transfer (CH4(+) + CO), H-atom transfer (HCO(+) + CH3), and H-atom expulsion (CH3CO(+) + H). H-atom transfer is slightly preferred to charge transfer at low temperature, with the charge-transfer product increasing in contribution as the temperature is increased (H-atom expulsion is a minor product for all temperatures). Analogous products are identified for the CD4 reaction. Density functional calculations on the CO(+) + CH4 reaction were also conducted, revealing that the relative temperature dependences of the charge-transfer and H-atom transfer pathways are consistent with an initial charge transfer followed by proton transfer.

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Magnetic properties of ZnFe2O4 nanoparticles produced by a low-temperature solid-state reaction method

International Nuclear Information System (INIS)

Li Fashen; Wang Haibo; Wang Li; Wang Jianbo

2007-01-01

ZnFe 2 O 4 nanoparticles with average grain size ranging from 40 to 60 nm behaving superparamagnetic at room temperature have been produced using a low-temperature solid-state reaction (LTSSR) method without ball-milling process. Abnormal magnetic properties such as S-shape hysteresis loops and non-zero magnetic moments were observed. ZnFe 2 O 4 nanoparticles were also synthesized using a NaOH coprecipitation method and a PVA sol-gel method to study the relationship between the preparation processes and the magnetic properties. Spin-glass behavior was observed in the low temperature solid-state reaction produced Zn ferrite in the zero-field cooled (ZFC) measurement. Our work proves that the various preparation methods will to some extent determine the properties of magnetic nanoparticles

Effect of the Reduction Temperature of PdAg Nanoparticles during the Polyol Process in the Ethanol Electrooxidation Reaction

Directory of Open Access Journals (Sweden)

R. Carrera-Cerritos

2018-01-01

Full Text Available This work reports the effect of reduction temperature during the synthesis of PdAg catalysts through the polyol process and their evaluation in the ethanol electrooxidation reaction (EOR. The characterization was performed using Transmission Electron Microscopy (TEM and X-Ray Diffraction (XRD. The electrochemical evaluation for the ethanol electrooxidation reaction was implemented in alkaline medium using chronoamperometry (CA and cyclic voltammetry (CV. An important effect of the reduction temperature on electroactivity and catalytic stability was observed: both the maximum current density and the catalytic stability were higher in the catalyst synthesized at the highest temperature (135°C. This performance was associated with the extent of the interaction between Pd and Ag which was measured in terms of the structural expansion of Pd.

The investigation of degradation reaction of various saccharides in high temperature and high pressure water

Science.gov (United States)

Saito, T.; Noguchi, S.; Matsumoto, T.; Sasaki, M.; Goto, M.

2008-07-01

Recently, conversions of polysaccharides included in biomass resources have been studied in order to recover valuable chemicals. Degradation of polysaccharides has been attracted by many researchers, whereas by-products from secondary reactions of the materials have not been studied very well. For the purpose of understanding reaction behavior of various monosaccharides in high-temperature and high-pressure water regions, we investigated reaction pathway and kinetics through reaction experiments of degradation of saccharides in subcritical water. The experiment was conducted by using continuous flow-type micro-reactors. Glucose was used as the starting material. From the experimental results, the conversion of glucose increased with increasing the residence time. The yields of fructose and 1, 6-anhydro-β-D-glucose decreased with increasing the residence time. The yields of organic acids and some aldehydes increased with increasing the residence time.

The investigation of degradation reaction of various saccharides in high temperature and high pressure water

International Nuclear Information System (INIS)

Saito, T; Noguchi, S; Matsumoto, T; Sasaki, M; Goto, M

2008-01-01

Recently, conversions of polysaccharides included in biomass resources have been studied in order to recover valuable chemicals. Degradation of polysaccharides has been attracted by many researchers, whereas by-products from secondary reactions of the materials have not been studied very well. For the purpose of understanding reaction behavior of various monosaccharides in high-temperature and high-pressure water regions, we investigated reaction pathway and kinetics through reaction experiments of degradation of saccharides in subcritical water. The experiment was conducted by using continuous flow-type micro-reactors. Glucose was used as the starting material. From the experimental results, the conversion of glucose increased with increasing the residence time. The yields of fructose and 1, 6-anhydro-β-D-glucose decreased with increasing the residence time. The yields of organic acids and some aldehydes increased with increasing the residence time

Geothermal low-temperature reservoir assessment program: A new DOE geothermal initiative

International Nuclear Information System (INIS)

Wright, P.M.; Lienau, P.J.; Mink, L.L.

1992-01-01

In Fiscal Year 1991, Congress appropriated money for the Department of Energy to begin a new program in the evaluation and use of low- and moderate-temperature geothermal resources. The objective of this program is to promote accelerated development of these resources to offset fossil-fuel use and help improve the environment. The program will consist of several components, including: (1) compilation of all available information on resource location and characteristics, with emphasis on resources located within 5 miles of population centers; (2) development and testing of techniques to discover and evaluate low- and moderate-temperature geothermal resources; (3) technical assistance to potential developers of low- and moderate-temperature geothermal resources; and (4) evaluation of the use of geothermal heat pumps in domestic and commercial applications. Program participants will include the Geo-Heat Center at the Oregon Institute of Technology, the University of Utah Research Institute, the Idaho Water Resources Research Institute and agencies of state governments in most of the western states

Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

Science.gov (United States)

Barkalov, I. M.; Kiryukhin, D. P.

schemes are described [1-5]. However, despite the high working characteristics of modern calorimeters (Perkin-Elmer, Du Pont, LKB, etc.), all of them have one principal disadvantage: a cell with a sample is placed in them at room temperature. In cryochemical investigation, when the sample has metastable formations, the loading is made `from nitrogen to nitrogen', i.e. the sample prepared at 77 K should be loaded into a calorimeter at 77 K. Besides, the existing installations do not allow measurements at the temperatures Cryochemistry and Radiation Chemistry at the Institute of Chemical Physics in Chernogolovka has created original calorimetric techniques which allow: (1) the carrying out phase analysis and the determination of the main thermodynamic characteristic of individual substances and complicated systems in the temperature range 5 300 K. Sample loading can be conducted at 77 K that allows us to study the systems containing: tetrafiuoroethylene, hexafluoropropylene, ethylene, carbon monoxide, nitrogen, methane, hydrogen, oxygen, ozone, formaldehyde and many other gaseous substances; (2) the study of the dynamics of chemical reactions and to measure the main kinetic parameters of the processes-the elementary rate constants and the activation energies. The experiment can be conducted both under direct action of radiation and UV light and in the post-effect mode [5,6].

On the impedance of galvanic cells XXVII. The temperature-dependence of the kinetic parameters of the hydrogen electrode reaction on mercury in concentrated HI

NARCIS (Netherlands)

Dekker, B.G.; Sluyters-Rehbach, M.; Sluyters, J.H.

1969-01-01

The impedance of a dropping mercury electrode in 57% HI (7.6 M) was measured at temperatures between −35° and +25°C. In a certain potential and temperature region, two reactions were found to be proceeding simultaneously: the reversible Hg/HgI4−2 reaction and the irreversible H+/H2(Hg) reaction.

Key role of temperature monitoring in interpretation of microwave effect on transesterification and esterification reactions for biodiesel production.

Science.gov (United States)

Mazubert, Alex; Taylor, Cameron; Aubin, Joelle; Poux, Martine

2014-06-01

Microwave effects have been quantified, comparing activation energies and pre-exponential factors to those obtained in a conventionally-heated reactor for biodiesel production from waste cooking oils via transesterification and esterification reactions. Several publications report an enhancement of biodiesel production using microwaves, however recent reviews highlight poor temperature measurements in microwave reactors give misleading reaction performances. Operating conditions have therefore been carefully chosen to investigate non-thermal microwave effects alone. Temperature is monitored by an optical fiber sensor, which is more accurate than infrared sensors. For the transesterification reaction, the activation energy is 37.1kJ/mol (20.1-54.2kJ/mol) in the microwave-heated reactor compared with 31.6kJ/mol (14.6-48.7kJ/mol) in the conventionally-heated reactor. For the esterification reaction, the activation energy is 45.4kJ/mol (31.8-58.9kJ/mol) for the microwave-heated reactor compared with 56.1kJ/mol (55.7-56.4kJ/mol) for conventionally-heated reactor. The results confirm the absence of non-thermal microwave effects for homogenous-catalyzed reactions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermal reaction norms and the scale of temperature variation: latitudinal vulnerability of intertidal nacellid limpets to climate change.

Directory of Open Access Journals (Sweden)

Simon A Morley

Full Text Available The thermal reaction norms of 4 closely related intertidal Nacellid limpets, Antarctic (Nacella concinna, New Zealand (Cellana ornata, Australia (C. tramoserica and Singapore (C. radiata, were compared across environments with different temperature magnitude, variability and predictability, to test their relative vulnerability to different scales of climate warming. Lethal limits were measured alongside a newly developed metric of "duration tenacity", which was tested at different temperatures to calculate the thermal reaction norm of limpet adductor muscle fatigue. Except in C. tramoserica which had a wide optimum range with two break points, duration tenacity did not follow a typical aerobic capacity curve but was best described by a single break point at an optimum temperature. Thermal reaction norms were shifted to warmer temperatures in warmer environments; the optimum temperature for tenacity (T(opt increased from 1.0°C (N. concinna to 14.3°C (C. ornata to 18.0°C (an average for the optimum range of C. tramoserica to 27.6°C (C. radiata. The temperature limits for duration tenacity of the 4 species were most consistently correlated with both maximum sea surface temperature and summer maximum in situ habitat logger temperature. Tropical C. radiata, which lives in the least variable and most predictable environment, generally had the lowest warming tolerance and thermal safety margin (WT and TSM; respectively the thermal buffer of CT(max and T(opt over habitat temperature. However, the two temperate species, C. ornata and C. tramoserica, which live in a variable and seasonally unpredictable microhabitat, had the lowest TSM relative to in situ logger temperature. N. concinna which lives in the most variable, but seasonally predictable microhabitat, generally had the highest TSMs. Intertidal animals live at the highly variable interface between terrestrial and marine biomes and even small changes in the magnitude and predictability of their

Nano-nitride cathode catalysts of Ti, Ta, and Nb for polymer electrolyte fuel cells: Temperature-programmed desorption investigation of molecularly adsorbed oxygen at low temperature

KAUST Repository

Ohnishi, Ryohji

2013-01-10

TiN, NbN, TaN, and Ta3N5 nanoparticles synthesized using mesoporous graphitic (mpg)-C3N4 templates were investigated for the oxygen reduction reaction (ORR) as cathode catalysts for polymer electrolyte fuel cells. The temperature-programmed desorption (TPD) of molecularly adsorbed O2 at 120-170 K from these nanoparticles was examined, and the resulting amount and temperature of desorption were key factors determining the ORR activity. The size-dependent TiN nanoparticles (5-8 and 100 nm) were then examined. With decreasing particle size, the density of molecularly adsorbed O2 per unit of surface area increased, indicating that a decrease in particle size increases the number of active sites. It is hard to determine the electrochemical active surface area for nonmetal electrocatalysts (such as oxides or nitrides), because of the absence of proton adsorption/desorption peaks in the voltammograms. In this study, O2-TPD for molecularly adsorbed O2 at low temperature demonstrated that the amount and strength of adsorbed O2 were key factors determining the ORR activity. The properties of molecularly adsorbed O2 on cathode catalysts are discussed against the ORR activity. © 2012 American Chemical Society.

Continuous thermal degradation of pyrolytic oil in a bench scale CSTR reaction system

Energy Technology Data Exchange (ETDEWEB)

Lee, Kyong Hwan; Nam, Ki Yun [Climate Change Technology Research Division, Korea Institute of Energy Research, 102 Gajeong-ro, Yuseong-gu, Daejeon 305-343 (Korea)

2010-05-15

Continuous thermal degradation of two pyrolytic oils with low (LPO) and high boiling point distribution (HPO) was conducted in a constant stirrer tank reactor (CSTR) with bench scale. Raw pyrolytic oil as a reactant was obtained from the commercial rotary kiln pyrolysis plant for municipal plastic waste. The degradation experiment was conducted by temperature programming with 10 C/min of heating rate up to 450 C and then maintained with long lapse time at 450 C. Liquid product was sampled at initial reaction time with different degradation temperatures up to 450 C and then constant interval lapse time at 450 C. The product characteristics over two pyrolytic oils were compared by using a continuous reaction system. As a reactant, heavy pyrolytic oil (HPO) showed higher boiling point distribution than that of diesel and also light pyrolytic oil (LPO) was mainly consisting of a mixture of gasoline and kerosene range components. In the continuous reaction, LPO showed higher yield of liquid product and lower residue than those of HPO. The characteristics of liquid products were influenced by the type of raw pyrolytic oil. Also, the result obtained under degradation temperature programming was described. (author)

An Unexpected Reaction between 5-Hydroxymethylfurfural and Imidazolium-Based Ionic Liquids at High Temperatures

Directory of Open Access Journals (Sweden)

Zongbao K. Zhao

2011-10-01

Full Text Available A new compound was detected during the production of 5-hydroxymethylfurfural (HMF from glucose and cellulose in the ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl at high temperatures. Further experiments found that it was derived from the reaction of HMF with [Bmim]Cl. The structure of new compound was established as 1-butyl-2-(5’-methyl-2’-furoylimidazole (BMI based on nuclear magnetic resonance and mass spectrometry analysis, and a possible mechanism for its formation was proposed. Reactions of HMF with other imidazolium-based ionic liquids were performed to check the formation of BMI. Our results provided new insights in terms of side reactions between HMF and imidazolium-based ionic liquids, which should be valuable for designing better processes for the production of furans using biomass and related materials.

Temperature effects on multiphase reactions of organic molecular markers: A modeling study

Science.gov (United States)

Pratap, Vikram; Chen, Ying; Yao, Guangming; Nakao, Shunsuke

2018-04-01

Various molecular markers are used in source apportionment studies. In early studies, molecular markers were assumed to be inert. However, recent studies suggest that molecular markers can decay rapidly through multiphase reactions, which makes interpretation of marker measurements challenging. This study presents a simplified model to account for the effects of temperature and relative humidity on the lifetime of molecular markers through a shift in gas-particle partitioning as well as a change in viscosity of the condensed phase. As a model case, this study examines the stability of levoglucosan, a key marker species of biomass burning, over a wide temperature range relevant to summertime and wintertime. Despite the importance of wood combustion for space heating in winter, the lifetime of levoglucosan in wintertime is not well understood. The model predicts that in low-temperature conditions, levoglucosan predominantly remains in the particle phase, and therefore its loss due to gas-phase oxidation reactions is significantly reduced. Furthermore, the movement of the levoglucosan from the bulk of the particle to the particle surface is reduced due to low diffusivity in the semi-solid state. The simplified model developed in this study reasonably reproduces upper and lower bounds of the lifetime of levoglucosan investigated in previous studies. The model results show that the levoglucosan depletion after seven days reduces significantly from ∼98% at 25 °C to marker (lifetime > 1 week) even at 60% relative humidity irrespective of the assumed fragility parameter D that controls estimated diffusivity. The model shows that lifetime of an organic molecular marker strongly depends on assumed D especially when a semi-volatile marker is in semi-solid organic aerosol.

Reaction CH3 + OH studied over the 294-714 K temperature and 1-100 bar pressure ranges.

Science.gov (United States)

Sangwan, Manuvesh; Chesnokov, Evgeni N; Krasnoperov, Lev N

2012-08-30

Reaction of methyl radicals with hydroxyl radicals, CH(3) + OH → products (1) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 294-714 K temperature and 1-100 bar pressure ranges (bath gas He). Methyl radicals were produced by photolysis of acetone at 193.3 nm. Hydroxyl radicals were generated in reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N(2)O at 193.3 nm, with H(2)O. Temporal profiles of CH(3) were recorded via absorption at 216.4 nm using xenon arc lamp and a spectrograph; OH radicals were monitored via transient absorption of light from a dc discharge H(2)O/Ar low pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light inside the reactor was determined by an accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The results of this study indicate that the rate constant of reaction 1 is pressure independent within the studied pressure and temperature ranges and has slight negative temperature dependence, k(1) = (1.20 ± 0.20) × 10(-10)(T/300)(-0.49) cm(3) molecule(-1) s(-1).

Tribological reactions of perfluoroalkyl polyether oils with stainless steel under ultrahigh vacuum conditions at room temperature

Science.gov (United States)

Mori, Shigeyuki; Morales, Wilfredo

1989-01-01

The reaction between three types of commercial perfluoroalkyl polyether (PFPE) oils and stainless steel 440C was investigated experimentally during sliding under ultrahigh vacuum conditions at room temperature. It is found that the tribological reaction of PFPE is mainly affected by the activity of the mechanically formed fresh surfaces of metals rather than the heat generated at the sliding contacts. The fluorides formed on the wear track act as a boundary layer, reducing the friction coefficient.

Cationic Pd(II-catalyzed C–H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies

Directory of Open Access Journals (Sweden)

Takashi Nishikata

2016-05-01

Full Text Available Cationic palladium(II complexes have been found to be highly reactive towards aromatic C–H activation of arylureas at room temperature. A commercially available catalyst [Pd(MeCN4](BF42 or a nitrile-free cationic palladium(II complex generated in situ from the reaction of Pd(OAc2 and HBF4, effectively catalyzes C–H activation/cross-coupling reactions between aryl iodides, arylboronic acids and acrylates under milder conditions than those previously reported. The nature of the directing group was found to be critical for achieving room temperature conditions, with the urea moiety the most effective in promoting facile coupling reactions at an ortho C–H position. This methodology has been utilized in a streamlined and efficient synthesis of boscalid, an agent produced on the kiloton scale annually and used to control a range of plant pathogens in broadacre and horticultural crops. Mechanistic investigations led to a proposed catalytic cycle involving three steps: (1 C–H activation to generate a cationic palladacycle; (2 reaction of the cationic palladacycle with an aryl iodide, arylboronic acid or acrylate, and (3 regeneration of the active cationic palladium catalyst. The reaction between a cationic palladium(II complex and arylurea allowed the formation and isolation of the corresponding palladacycle intermediate, characterized by X-ray analysis. Roles of various additives in the stepwise process have also been studied.

Effect of degree of polymerization and of temperature on the reactivity of poly(vinyl alcohol) by applying T-for-H exchange reaction

International Nuclear Information System (INIS)

Imaizumi, Hiroshi; Imai, Kazunari

1999-01-01

In order to reveal the effect of the degree of polymerization and of temperature on the reactivity of functional polymers, the hydrogen-isotope exchange reaction between poly(vinyl alcohol) (PVA) having each degree of polymerization and tritiated water vapor (HTO vapor) was dynamically observed at 35-80 deg C in a gas-solid system. The reason of the observation at 35 deg C is to clarify the possibility of the T-for-H exchange reaction at a temperature near the environment. The degree of polymerization of PVA used in this work was 500, 1000, 2000, 2800, or 3500. Applying the A''-McKay plot method to the data obtained in each observation, the rate constant (k) for each PVA in the reaction was calculated. Moreover, the Arrhenius plot for each PVA was made by using the k values. Comparing the k values and the results obtained previously, the following six matters have been clarified. In the temperature range of 35-80 deg C, the T-for-H exchange reaction between HTO vapor and each PVA occurred, and in this case, the atoms participating in the reaction are the H atoms in the OH groups in PVA and T atoms in HTO vapor. The reactivity of each PVA increases with rising temperature, and decreases with increasing the degree of polymerization. The rate of the decreasing of k with increasing the degree of polymerization changes at near the degree of polymerization of 1000, and the rate is fairly large under the degree of 1000. Under the degree of polymerization of 1000, the reactivity of PVA is more affected by the effect of the degree of polymerization than by the effect of temperature, and the reactivity is large when the degree of polymerization is small. Over the degree of polymerization of 1000, the reactivity of PVA is affected by both the degree of polymerization and temperature, and the reactivity is large when temperature is high. For the T-for-H exchange reaction in a gas-solid system, the reaction form is unchanged in the range of 35-80 deg C, and the reactivity at 35

Phenol hydroxylation on Al-Fe modified-bentonite: Effect of Fe loading, temperature and reaction time

Science.gov (United States)

Widi, R. K.; Budhyantoro, A.; Christianto, A.

2017-11-01

The present work reflects the study of the phenol hydroxylation reactions to synthesize hydroquinone and catechol on Al-Fe modified-bentonite. This study started with synthesizes the catalyst material based on the modified bentonite. Natural bentonite from Pacitan, Indonesia was intercalated with Cetyl-TetramethylammoniumBromida (CTMA-Br) followed by pillarization using Alumina. The pillared bentonite was then impregnated with Fe solution (0.01 M, 0.05 M, and 0.1 M). The solid material obtained was calcined at 723 K for 4 hours. All the materials were characterized using BET N2 adsorption. Their catalytic activity and selectivity were studied for phenol hydroxylation using H2O2 (30%). The reaction conditions of this reaction were as follows: ratio of phenol/H2O2 = 1:1 (molar ratio), concentration of phenol = 1 M and ratio of catalyst/phenol was 1:10. Reaction temperatures were varied at 333, 343 and 353 K. The reaction time was also varied at 3, 4 and 5 hours. The result shows that the materials have potential catalyst activity.

An alternative preparation method for ion exchanged catalysts: Solid state redox reaction

DEFF Research Database (Denmark)

Schneider, E.; Hagen, A.; Grunwaldt, J.-D.

2004-01-01

A new method for modifying zeolites with zinc is proposed. The solid state redox reaction between metallic zinc and ZSM-5 zeolites with different Si/Al ratios was investigated by temperature programmed hydrogen evolution (TPHE), X-ray absorption near edge structure (XANES) and diffuse reflectance...... infrared Fourier transform spectroscopy (DRIFTS). The evolution of hydrogen was detected at temperatures above 620 K. The source of hydrogen was the solid state redox reaction of the metal with protons of the support. The samples exhibit catalytic activity in ethane aromatization indicating that zinc...... should be located at the same sites as in catalysts prepared by conventional methods. Combination of XANES and catalytic activity point to zinc being mainly present in tetrahedral geometry under reaction conditions....

Evaluation of enthalpy of interfacial reactions from temperature dependency of interfacial equilibrium

International Nuclear Information System (INIS)

Kallay, Nikola; Cop, Ana

2005-01-01

Temperature dependency of equilibrium at metal oxide-aqueous electrolyte solution interface was analyzed by numerical simulation. Derivations of inner surface potential with respect to temperature were performed at constant values of several different parameters. When surface charge density in inner plane was kept constant the reasonable results were obtained, i.e. the electrostatic contribution to enthalpy of protonation of amphotheric surface sites was found to be positive in the pH region below the point of zero potential and negative above this point. All other examined possibilities produced opposite results. Derivation of empirical interfacial equilibrium constant at constant surface potential indicated that electrostatic effect on protonation entropy is negligible and that electrostatic contributions to reaction Gibbs energy and enthalpy are equal and directly related to the surface potential in the inner plane

Reduction and Analysis of Low Temperature Shift Heterogeneous Catalyst for Water Gas Reaction in Ammonia Production

Directory of Open Access Journals (Sweden)

Zečević, N.

2013-09-01

Full Text Available In order to obtain additional quantities of hydrogen after the reforming reactions of natural gas and protect the ammonia synthesis catalyst, it is crucial to achieve and maintain maximum possible activity, selectivity and stability of the low temperature shift catalyst for conversion of water gas reaction during its lifetime. Whereas the heterogeneous catalyst comes in oxidized form, it is of the utmost importance to conduct the reduction procedure properly. The proper reduction procedure and continuous analysis of its performance would ensure the required activity, selectivity and stability throughout the catalyst’s service time. For the proper reduction procedure ofthe low temperature shift catalyst, in addition to process equipment, also necessary is a reliable and realistic system for temperature measurements, which will be effective for monitoring the exothermal temperature curves through all catalyst bed layers. For efficiency evaluation of low shift temperature catalyst reduction and its optimization, it is necessary to determine at regular time intervals the temperature approach to equilibrium and temperature profiles of individual layers by means of "S" and "die off" temperature exothermal curves. Based on the obtained data, the optimum inlet temperature could be determined, in order to maximally extend the service life of the heterogeneous catalyst as much as possible, and achieve the optimum equilibrium for conversion of the water gas. This paper presents the methodology for in situ reduction of the low temperature shift heterogeneous catalyst and the developed system for monitoring its individual layers to achieve the minimum possible content of carbon monoxide at the exit of the reactor. The developed system for temperature monitoring through heterogeneous catalyst layers provides the proper procedure for reduction and adjustment of optimum process working conditions for the catalyst by the continuous increase of reactor inlet

Investigation into boron reaction with titanium at extreme temperature gradients

International Nuclear Information System (INIS)

Korchagin, M.A.; Gusenko, S.N.; Aleksandrov, V.V.; Neronov, V.A.

1981-01-01

The mechanism of self-propagation high-temperature synthesis of titanium boride is studied using the translucent electron microscopy. Titanium interaction with boron film (approximately 1000 A thick) starts with the metal partial melting. A twozone layer of the reaction products, separating the reagents, is formed. In the zone adjacent to B, Ti 3 B 4 and fusible liquid phases are present. The second zone consists of TiB. The subsequent interaction is realized by Means of the dissolving and absorption by titanium of the layer of products during its continuous increase in boron. TiB 2 formation takes place at subsequent stages of interaction inside Ti liquid particles during their saturation by boron from the products absorbed [ru

Effect of temperature on photochemical smog reactions

Energy Technology Data Exchange (ETDEWEB)

Bufalini, J J; Altshuller, A P

1963-01-01

In the present investigation the photo-oxidation reactions to trans-2-butene-nitric oxide and 1,3,5-trimethylbenzene (mesitylene)-nitric oxide in air have been followed. The rates of formation and disappearance of nitrogen dioxide and the rate of reaction of the hydrocarbons have been measured at 20 and 40/sup 0/. The results obtained indicate about a twofold decrease in conversion times over the 20/sup 0/ interval and a corresponding increase in rates of reactions. 5 references.

Dynamic behavior of the bray-liebhafsky oscillatory reaction controlled by sulfuric acid and temperature

Science.gov (United States)

Pejić, N.; Vujković, M.; Maksimović, J.; Ivanović, A.; Anić, S.; Čupić, Ž.; Kolar-Anić, Lj.

2011-12-01

The non-periodic, periodic and chaotic regimes in the Bray-Liebhafsky (BL) oscillatory reaction observed in a continuously fed well stirred tank reactor (CSTR) under isothermal conditions at various inflow concentrations of the sulfuric acid were experimentally studied. In each series (at any fixed temperature), termination of oscillatory behavior via saddle loop infinite period bifurcation (SNIPER) as well as some kind of the Andronov-Hopf bifurcation is presented. In addition, it was found that an increase of temperature, in different series of experiments resulted in the shift of bifurcation point towards higher values of sulfuric acid concentration.

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

The bimolecular reaction of radiolysis product of hydrated electron at temperature up to 473K; Reaksi bimolekular antar produk radiolisis elektron terhidrasi pada temperatur hingga 473K

Energy Technology Data Exchange (ETDEWEB)

Sunaryo, G R [Reactor Safety Technology Research Centre, National Atomic Energy Agency, Serpong (Indonesia)

1996-06-01

Rate constant from the bimolecular reaction of hydrated electron was determined by using radiolysis method. The methanol solution with concentration of 5 x 10{sup -2} dm{sup 3} mol{sup -1} was used as a scavenger of H and OH radicals. The pH was kept by adding the buffer solution of 1.0 x 10{sup -3} dm{sup 3} mol{sup -1} Na{sub 2}HPO{sub 4} + 1.0 x 10{sup 4} dm{sup 3} mol{sup -1} NaH{sub 2}PO{sub 4}. The irradiation was done by using the electron beam which come from linear accelerator 28 MeV with pulse width 10ns and dose of 80 Gy per pulse. The absorbance of hydrated electron was observed at wavelength of 824 nm. By using the kinetic equation the rate reaction constants were obtained. The bimolecular reaction of hydrated electron increase with temperature up to 423K. The activation energy was 19.3 kJ mol{sup -1} and the 2 k (298K) was 1.1 x 10{sup 10} dm{sup 3} mol{sup -1}. Then this bimolecular reaction decrease at temperature higher than 423K and the rate reaction constant at 473K almost similar with that at 298K. (author)

Fast screening of analytes for chemical reactions by reactive low-temperature plasma ionization mass spectrometry.

Science.gov (United States)

Zhang, Wei; Huang, Guangming

2015-11-15

Approaches for analyte screening have been used to aid in the fine-tuning of chemical reactions. Herein, we present a simple and straightforward analyte screening method for chemical reactions via reactive low-temperature plasma ionization mass spectrometry (reactive LTP-MS). Solution-phase reagents deposited on sample substrates were desorbed into the vapor phase by action of the LTP and by thermal desorption. Treated with LTP, both reagents reacted through a vapor phase ion/molecule reaction to generate the product. Finally, protonated reagents and products were identified by LTP-MS. Reaction products from imine formation reaction, Eschweiler-Clarke methylation and the Eberlin reaction were detected via reactive LTP-MS. Products from the imine formation reaction with reagents substituted with different functional groups (26 out of 28 trials) were successfully screened in a time of 30 s each. Besides, two short-lived reactive intermediates of Eschweiler-Clarke methylation were also detected. LTP in this study serves both as an ambient ionization source for analyte identification (including reagents, intermediates and products) and as a means to produce reagent ions to assist gas-phase ion/molecule reactions. The present reactive LTP-MS method enables fast screening for several analytes from several chemical reactions, which possesses good reagent compatibility and the potential to perform high-throughput analyte screening. In addition, with the detection of various reactive intermediates (intermediates I and II of Eschweiler-Clarke methylation), the present method would also contribute to revealing and elucidating reaction mechanisms. Copyright © 2015 John Wiley & Sons, Ltd.

Temperature dependence of He(2 3PJ) reactions: Collision-induced mixing and conversion to He2( 3Πg) molecules

International Nuclear Information System (INIS)

Zhao, X.; Soletsky, P.A.; Bryan, W.H.; Dunning, F.B.; Walters, G.K.

1993-01-01

The rate coefficients for mixing between He(2 3 P J, MJ) levels during collisions with ground-state helium atoms and for conversion of He(2 3 P J ) atoms to He 2 (b 3 Π g ) molecules via three-body reactions in helium gas have been investigated over the temperature range 1.6--300 K. The measured rate coefficients for collisionally induced P-state mixing decrease slowly with decreasing temperature, from (1.8±0.5)x10 -9 cm 3 s -1 at 300 K to (4.5±0.5)x10 -10 cm 3 s -1 at 4.2 K. The rate coefficients for the production of He 2 (b 3 Π g ) molecules via three-body reactions are observed to increase with decreasing temperature and are described by the relation k P congruent(2.5+267T -1 )x10 -32 cm 6 s -1 . This behavior, which is very different from that noted in earlier studies of the conversion of He(2 3 S 1 ) atoms to He 2 (a 3 Σ u + ) molecules through three-body reactions, suggests that the reaction is not thermally activated

SATCAP: a program for thermal-hydraulic design of saturated temperature capsule

International Nuclear Information System (INIS)

Harayama, Yasuo; Niimi, Motoji; Someya, Hiroyuki; Kobayashi, Toshiki.

1988-02-01

For material irradiation tests at JMTR, user's technical requirements are gradually becoming more rigid, permitting only a small temperature deviation from the desired during irradiation of test materials. As specimen temperature control equipment, several conception were proposed and some of them were translated into actual machines with the capsule having electrical seath heaters in it. This system is highly reliable unless the integrity of the heaters is threatened. However, in a test with the object of achieving a high exposure of specimen to neutrons, the break of a heater or deterioration of a heater caused by irradiation lowers the reliability of the system. To cope with this drawback, as a part of the irradiation technique improvement program, ''Satulated Temperature Capsule'' has been developing. This type capsule, in which the water suplied is boiled, bases on the conception of keeping the coolant at the saturated temperature facilitates the temperature control. Though there are various types of capsules employed at JMTR, the experience of the capsule into which the coolant is injected lacks. In designing, thermal performances have to fully understood. Therefore, a program was compiled to evaluate the thermal behavior in the capsule. The present report describes the calculation procedure and guides of input and output for the program. (author)

Temperature-programmed technique accompanied with high-throughput methodology for rapidly searching the optimal operating temperature of MOX gas sensors.

Science.gov (United States)

Zhang, Guozhu; Xie, Changsheng; Zhang, Shunping; Zhao, Jianwei; Lei, Tao; Zeng, Dawen

2014-09-08

A combinatorial high-throughput temperature-programmed method to obtain the optimal operating temperature (OOT) of gas sensor materials is demonstrated here for the first time. A material library consisting of SnO2, ZnO, WO3, and In2O3 sensor films was fabricated by screen printing. Temperature-dependent conductivity curves were obtained by scanning this gas sensor library from 300 to 700 K in different atmospheres (dry air, formaldehyde, carbon monoxide, nitrogen dioxide, toluene and ammonia), giving the OOT of each sensor formulation as a function of the carrier and analyte gases. A comparative study of the temperature-programmed method and a conventional method showed good agreement in measured OOT.

The Effect of Temperature on Selectivity in the Oscillatory Mode of the Phenylacetylene Oxidative Carbonylation Reaction.

Science.gov (United States)

Parker, Julie; Novakovic, Katarina

2017-08-05

Reaction temperature plays a major role in product selectivity in the oscillatory mode of the palladium-catalyzed phenylacetylene oxidative carbonylation reaction. At 40 °C, dimethyl (2Z)-2-phenyl-2-butenedioate is the major product whereas at 0 °C the major product is 5,5-dimethoxy-3-phenyl-2(5H)-furanone. The occurrence of oscillations in pH coincides with an increase in the rate of phenylacetylene consumption and associated product formation. Experiments were performed isothermally in a reaction calorimeter to correlate reactant consumption and product formation with the occurrence of pH oscillations and the heat released by the reaction. An increase in the size of the pH drop in a single oscillation correlates with an increase in energy, indicating that this section of a single oscillation relates to reactant consumption. Based on these observations, a reaction pathway responsible for product formation is provided. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Effect of Gd{sup 3+} doping and reaction temperature on structural and optical properties of CdS nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Pandey, Gajanan, E-mail: pandeygajanan@rediffmail.com [Department of Applied Chemistry, Babasaheb Bhimrao Ambedkar University, Lucknow, 226025, (U.P.) (India); Dixit, Supriya; Shrivastava, A.K. [School of Studies in Physics, Jiwaji University, Gwalior, 474011, (M.P.) (India)

2015-10-15

Graphical abstract: - Highlights: • Cd{sub 1−x}Gd{sub x}S nanoparticles have been prepared in aqueous medium in presence of CTAB. • From XRD, EDX and ICP-OES study, successful doping of Gd{sup 3+} in CdS has been proved. • Gd{sup 3+} doping reduced size of NCs, while temperature increased size and altered shape. • Gd{sup 3+} doping and reaction temperature influenced the optical properties of NCs. - Abstract: CdS and Gd{sup 3+} ions doped CdS nanoparticles have been prepared at two reaction temperatures 90 and 120 °C in aqueous medium in presence of cationic surfactant cetyltrimethylammonium bromide. X-ray diffraction study revealed predominant formation of zinc blend CdS and Gd:CdS at 90 °C, while at 120 °C, phase pure wurtzite CdS and Gd:CdS were formed. From EDX spectra and ICP-OES analysis, successful doping of Gd{sup 3+} ions in CdS host has been proved. Fourier transform infrared spectroscopy results show the interaction of CTAB through headgroup at the nanoparticles surface. In the transmission electron microscopy images, it has been observed that the reaction temperature and Gd{sup 3+} doping played critical role on size and shape of nanocrystals. In UV–visible absorption as well as photoluminescence emission spectra, size and shape-dependent quantum confinement effect has been observed. On Gd{sup 3+} doping, surface states related emission peak shifted to higher wavelength, while intensity of peaks increased on increasing temperature.

High-Pressure-High-Temperature Processing Reduces Maillard Reaction and Viscosity in Whey Protein-Sugar Solutions

NARCIS (Netherlands)

Avila Ruiz, Geraldine; Xi, Bingyan; Minor, Marcel; Sala, Guido; Boekel, van Tiny; Fogliano, Vincenzo; Stieger, Markus

2016-01-01

The aim of the study was to determine the influence of pressure in high-pressure-high-temperature (HPHT) processing on Maillard reactions and protein aggregation of whey protein-sugar solutions. Solutions of whey protein isolate containing either glucose or trehalose at pH 6, 7, and 9 were

Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K.

Science.gov (United States)

Akhgarnusch, Amou; Tang, Wai Kit; Zhang, Han; Siu, Chi-Kit; Beyer, Martin K

2016-09-14

The recombination reactions of gas-phase hydrated electrons (H2O)n˙(-) with CO2 and O2, as well as the charge exchange reaction of CO2˙(-)(H2O)n with O2, were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry in the temperature range T = 80-300 K. Comparison of the rate constants with collision models shows that CO2 reacts with 50% collision efficiency, while O2 reacts considerably slower. Nanocalorimetry yields internally consistent results for the three reactions. Converted to room temperature condensed phase, this yields hydration enthalpies of CO2˙(-) and O2˙(-), ΔHhyd(CO2˙(-)) = -334 ± 44 kJ mol(-1) and ΔHhyd(O2˙(-)) = -404 ± 28 kJ mol(-1). Quantum chemical calculations show that the charge exchange reaction proceeds via a CO4˙(-) intermediate, which is consistent with a fully ergodic reaction and also with the small efficiency. Ab initio molecular dynamics simulations corroborate this picture and indicate that the CO4˙(-) intermediate has a lifetime significantly above the ps regime.

Accurate prediction of severe allergic reactions by a small set of environmental parameters (NDVI, temperature).

Science.gov (United States)

Notas, George; Bariotakis, Michail; Kalogrias, Vaios; Andrianaki, Maria; Azariadis, Kalliopi; Kampouri, Errika; Theodoropoulou, Katerina; Lavrentaki, Katerina; Kastrinakis, Stelios; Kampa, Marilena; Agouridakis, Panagiotis; Pirintsos, Stergios; Castanas, Elias

2015-01-01

Severe allergic reactions of unknown etiology,necessitating a hospital visit, have an important impact in the life of affected individuals and impose a major economic burden to societies. The prediction of clinically severe allergic reactions would be of great importance, but current attempts have been limited by the lack of a well-founded applicable methodology and the wide spatiotemporal distribution of allergic reactions. The valid prediction of severe allergies (and especially those needing hospital treatment) in a region, could alert health authorities and implicated individuals to take appropriate preemptive measures. In the present report we have collecterd visits for serious allergic reactions of unknown etiology from two major hospitals in the island of Crete, for two distinct time periods (validation and test sets). We have used the Normalized Difference Vegetation Index (NDVI), a satellite-based, freely available measurement, which is an indicator of live green vegetation at a given geographic area, and a set of meteorological data to develop a model capable of describing and predicting severe allergic reaction frequency. Our analysis has retained NDVI and temperature as accurate identifiers and predictors of increased hospital severe allergic reactions visits. Our approach may contribute towards the development of satellite-based modules, for the prediction of severe allergic reactions in specific, well-defined geographical areas. It could also probably be used for the prediction of other environment related diseases and conditions.

Room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders prepared by combustion reaction method

International Nuclear Information System (INIS)

Franco, A.; Pessoni, H.V.S.; Soares, M.P.

2014-01-01

Nanoparticulate powders of Eu-doped ZnO with 1.0, 1.5, 2.0 and 3.0 at% Eu were synthesized by combustion reaction method using zinc nitrate, europium nitrate and urea as fuel without subsequent heat treatments. X-ray diffraction patterns (XRD) of all samples showed broad peaks consistent with the ZnO wurtzite structure. The absence of extra reflections in the diffraction patterns ensures the phase purity, except for x=0.03 that exhibits small reflection corresponding to Eu 2 O 3 phase. The average crystallite size determined from the most prominent (1 0 1) peak of the diffraction using Scherrer's equation was in good agreement with those determined by transmission electron microscopy (TEM); being ∼26 nm. The magnetic properties measurements were performed using a vibrating sample magnetometer (VSM) in magnetic fields up to 2.0 kOe at room temperature. The hysteresis loops, typical of magnetic behaviors, indicating that the presence of an ordered magnetic structure can exist in the Eu-doped ZnO wurtzite structure at room temperature. The room temperature ferromagnetism behavior increases with the Eu 3+ doping concentration. All samples exhibited the same Curie temperature (T C ) around ∼726 K, except for x=0.01; T C ∼643 K. High resolution transmission electron microscopy (HRTEM) images revealed defects/strain in the lattice and grain boundaries of Eu-doped ZnO nanoparticulate powders. The origin of room temperature ferromagnetism in Eu-doped ZnO nanoparticulate powders was discussed in terms of these defects, which increase with the Eu 3+ doping concentration. - Highlights: • Room-temperature ferromagnetism. • Structural and magnetic properties of nanoparticulate powders of Zn 1−x Eu x O. • Combustion reaction method

Influence of refreshment/activation cycles and temperature rise on the reaction rate of sodium hypochlorite with bovine dentine during ultrasonic activated irrigation.

Science.gov (United States)

Macedo, R G; Verhaagen, B; Wesselink, P R; Versluis, M; van der Sluis, L W M

2014-02-01

To evaluate the effect of multiple refreshment/activation cycles and temperature on the reaction rate of sodium hypochlorite (NaOCl) with bovine dentine during ultrasonic activated irrigation (UAI) under laboratory conditions. The root canal walls of 24 standardized root canals in bovine incisors were exposed to a standardized volume of NaOCl at different temperatures (24 °C and 38 °C) and exposure times (20, 60 and 180 s). The irrigant was refreshed and ultrasonically activated four times for 20 s followed by a 40 s rest interval, with no refreshment and no activation as the controls. The reaction rate was determined by measuring the amount of active chlorine in the NaOCl solution before and after being exposed to dentine during the specific experimental conditions. Calorimetry was used to measure the electrical-to-sonochemical conversion efficiency during ultrasonic activation. Refreshment, activation and exposure time all increased the reaction rate of NaOCl (P reaction rate of NaOCl (P > 0.125). The reaction rate of NaOCl with dentine is enhanced by refreshment, ultrasonic activation and exposure time. Temperature rise of irrigant during ultrasonic activation was not sufficient to alter the reaction rate. © 2013 International Endodontic Journal. Published by John Wiley & Sons Ltd.

Effect of radiative transfer of heat released from combustion reaction on temperature distribution: A numerical study for a 2-D system

International Nuclear Information System (INIS)

Zhou Huaichun; Ai Yuhua

2006-01-01

Both light and heat are produced during a chemical reaction in a combustion process, but traditionally all the energy released is taken as to be transformed into the internal energy of the combustion medium. So the temperature of the medium increases, and then the thermal radiation emitted from it increases too. Chemiluminescence is generated during a chemical reaction and independent of the temperature, and has been used widely for combustion diagnostics. It was assumed in this paper that the total energy released in a combustion reaction is divided into two parts, one part is a self-absorbed heat, and the other is a directly emitted heat. The former is absorbed immediately by the products, becomes the internal energy and then increases the temperature of the products as treated in the traditional way. The latter is emitted directly as radiation into the combustion domain and should be included in the radiation transfer equation (RTE) as a part of radiation source. For a simple, 2-D, gray, emitting-absorbing, rectangular system, the numerical study showed that the temperatures in reaction zones depended on the fraction of the directly emitted energy, and the smaller the gas absorption coefficient was, the more strong the dependence appeared. Because the effect of the fraction of the directly emitted heat on the temperature distribution in the reacting zones for gas combustion is significant, it is required to conduct experimental measurements to determine the fraction of self-absorbed heat for different combustion processes

Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

Science.gov (United States)

McCollom, Thomas M.; Donaldson, Christopher

2016-06-01

Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

Temperature dependence on plasma-induced damage and chemical reactions in GaN etching processes using chlorine plasma

Science.gov (United States)

Liu, Zecheng; Ishikawa, Kenji; Imamura, Masato; Tsutsumi, Takayoshi; Kondo, Hiroki; Oda, Osamu; Sekine, Makoto; Hori, Masaru

2018-06-01

Plasma-induced damage (PID) on GaN was optimally reduced by high-temperature chlorine plasma etching. Energetic ion bombardments primarily induced PID involving stoichiometry, surface roughness, and photoluminescence (PL) degradation. Chemical reactions under ultraviolet (UV) irradiation and chlorine radical exposure at temperatures higher than 400 °C can be controlled by taking into account the synergism of simultaneous photon and radical irradiations to effectively reduce PID.

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

Science.gov (United States)

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

2017-11-22

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

Application of SSNTDs for measurements of fusion reaction products in high-temperature plasma experiments

Energy Technology Data Exchange (ETDEWEB)

Malinowska, A., E-mail: a.malinowska@ipj.gov.p [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Szydlowski, A.; Malinowski, K. [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Sadowski, M.J. [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Institute of Plasma Physics and Laser Microfusion (IPPLM), 00-908 Warsaw (Poland); Zebrowski, J. [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland); Scholz, M.; Paduch, M.; Zielinska, E. [Institute of Plasma Physics and Laser Microfusion (IPPLM), 00-908 Warsaw (Poland); Jaskola, M.; Korman, A. [Andrzej Soltan Institute for Nuclear Studies (IPJ), 05-400 Otwock-Swierk (Poland)

2009-10-15

The paper describes the application of SSNTDs of the PM-355 type to diagnostics of reaction products emitted from high-temperature deuterium plasmas produced in Plasma Focus (PF) facilities. Acceleration processes occurring in plasma lead often to the generation of high-energy ion beams. Such beams induce nuclear reactions and contribute to the emission of fast neutrons, fusion protons and alpha particles from PF discharges with a deuterium gas. Ion measurements are of primary importance for understanding the mechanisms of the physical processes which drive the charged-particle acceleration. The main aim of the present studies was to perform measurements of spatial- and energy-distributions of fusion-reaction protons (about 3 MeV) within a PF facility. Results obtained from energy measurements were compared with the proton-energy spectra computed theoretically. The protons were measured by means of a set of ion pinhole cameras equipped with PM-355 detectors, which were placed at different angles relative to the electrode axis of the PF facility.

EFFECT OF TIME AND TEMPERATURE ON ISOMERIZATION REACTION OF ?-PINENEUSING CATALYST ZR 4+ Nanik Wijayati, Supartono, Nuni Widiarti, Tri Handayani /NATURAL ZEOLITE

Directory of Open Access Journals (Sweden)

Nanik Wijayati

2016-03-01

Full Text Available Effects of time and temperature on ?-pinene isomerization reaction using catalysts Zr/natural zeolitewas studied. Characterization of the catalysts include: crystallinity, observed using X-Ray Diffraction, count Zr 4+ carried observed using X-Ray Fluorescence, area and porosity catalyst was observed using the Surface Area Analyzer, and acidity catalyst observed through gravimetric method. Isomerization reaction carried out in a batch reactor with temperature variations 90, 120 and 150 C and reaction time variations of 60, 90, 120, 150 and 180 minutes. Best results of isomerisation in this study was obtained at 150 derajat C with a reaction time of 180 minutes. Kindsof isomer obtained was observed using GCMS. Catalyst characterization results indicate that modification of the catalyst by cation Zr increases the acidity from 2.76 to 6.64 mmol/g and does not damage the crystal structure significantly. The highest product conversion in this research is 9.24%, less than the maximum results caused by pre-treatment of the catalyst produces a low area. Thus, temperature and reaction time affect the concentration of ? pinene isomerization product in addition to the effect of the catalyst used.

Development program for the high-temperature nuclear process heat system

International Nuclear Information System (INIS)

Jiacoletti, R.J.

1975-09-01

A comprehensive development program plan for a high-temperature nuclear process heat system with a very high temperature gas-cooled reactor heat source is presented. The system would provide an interim substitute for fossil-fired sources and ultimately the vehicle for the production of substitute and synthetic fuels to replace petroleum and natural gas. The dwindling domestic reserves of petroleum and natural gas dictate major increases in the utilization of coal and nuclear sources to meet the national energy demand. The nuclear process heat system has significant potential in a unique combination of the two sources that is environmentally and economically attractive and technically sound: the production of synthetic fuels from coal. In the longer term, it could be the key component in hydrogen production from water processes that offer a substitute fuel and chemical feedstock free of dependence on fossil-fuel reserves. The proposed development program is threefold: a process studies program, a demonstration plant program, and a supportive research and development program. Optional development scenarios are presented and evaluated, and a selection is proposed and qualified. The interdependence of the three major program elements is examined, but particular emphasis is placed on the supportive research and development activities. A detailed description of proposed activities in the supportive research and development program with tentative costs and schedules is presented as an appendix with an assessment of current status and planning

A Novel Approach for Modeling Chemical Reaction in Generalized Fluid System Simulation Program

Science.gov (United States)

Sozen, Mehmet; Majumdar, Alok

2002-01-01

The Generalized Fluid System Simulation Program (GFSSP) is a computer code developed at NASA Marshall Space Flight Center for analyzing steady state and transient flow rates, pressures, temperatures, and concentrations in a complex flow network. The code, which performs system level simulation, can handle compressible and incompressible flows as well as phase change and mixture thermodynamics. Thermodynamic and thermophysical property programs, GASP, WASP and GASPAK provide the necessary data for fluids such as helium, methane, neon, nitrogen, carbon monoxide, oxygen, argon, carbon dioxide, fluorine, hydrogen, water, a hydrogen, isobutane, butane, deuterium, ethane, ethylene, hydrogen sulfide, krypton, propane, xenon, several refrigerants, nitrogen trifluoride and ammonia. The program which was developed out of need for an easy to use system level simulation tool for complex flow networks, has been used for the following purposes to name a few: Space Shuttle Main Engine (SSME) High Pressure Oxidizer Turbopump Secondary Flow Circuits, Axial Thrust Balance of the Fastrac Engine Turbopump, Pressurized Propellant Feed System for the Propulsion Test Article at Stennis Space Center, X-34 Main Propulsion System, X-33 Reaction Control System and Thermal Protection System, and International Space Station Environmental Control and Life Support System design. There has been an increasing demand for implementing a combustion simulation capability into GFSSP in order to increase its system level simulation capability of a liquid rocket propulsion system starting from the propellant tanks up to the thruster nozzle for spacecraft as well as launch vehicles. The present work was undertaken for addressing this need. The chemical equilibrium equations derived from the second law of thermodynamics and the energy conservation equation derived from the first law of thermodynamics are solved simultaneously by a Newton-Raphson method. The numerical scheme was implemented as a User

Temperature influence on the reaction kinetics of V(IV)/V(V) in methanesulfonic acid for all-vanadium redox flow battery

International Nuclear Information System (INIS)

Wang, Qiuhong; Daoud, Walid A.

2016-01-01

Highlights: • Diffusion coefficients and standard rate constants of V(IV) and V(V) in MSA at different temperatures are studied. • Carbon-based and metal electrodes are investigated under the same experimental condition at high temperature. • The influence of temperature on reaction kinetics is more significant on carbon-based electrode than metal electrode. • Gold electrode shows inefficient performance in MSA solution. - Abstract: In this study, methanesulfonic acid has been investigated as the supporting electrolyte for vanadium solutions due to the improvement of mass transfer rate and reaction kinetics. Here, we applied different temperatures (0–55 °C) for electrochemical experiments of 0.1 M vanadium ions in 1.0 M MSA electrolyte on gold, platinum and glassy carbon electrodes separately to study the temperature-related kinetics. Considering that electron transfer is the control path for the whole reduction potential window, the rotating disc electrode approach was utilized for the oxidation of V(IV) ions, while the reduction of V(V) ions was studied by cyclic voltammetry. The influence of temperature on charge-transfer resistance and mass transport for both V(IV) and V(V) solutions was studied by electrochemical impedance spectroscopy on glassy carbon electrode. The results showed that the diffusion coefficients in both redox reactions on all electrodes increased with temperature, and most were in the order of 10 −6 cm 2 s −1 . The positive influence of temperature was also observed on the standard rate constants for all conditions in this study, most significantly on the glassy carbon electrode. Comparison between glassy carbon electrode and metal electrodes indicates a promising potential of carbon-based material as electrode for redox flow battery.

Synthesis and regulation of α-LiZnPO4.H2O via a solid-state reaction at low-heating temperatures

International Nuclear Information System (INIS)

Liao Sen; Chen Zhipeng; Tian Xiaozhen; Wu Wenwei

2009-01-01

A simple and novel route for the synthesis of a lithium zinc phosphate hydrate, α-LiZnPO 4 .H 2 O, was studied, and the target product was obtained with LiH 2 PO 4 .H 2 O and ZnCO 3 as raw materials and polyethylene glycol-400 (PEG-400) as a surfactant via a one step solid-state reaction at room temperature (25 deg. C). The product was characterized with X-ray powder diffraction (XRD), thermogravimetric analysis and the 1st derivativative of thermogravimetric analysis (TG/DTG) and Fourier transform infrared spectroscopy (FTIR). The comparison experimental results suggested that aging temperature controlled the products of the synthesis, that is, the α-LiZnPO 4 .H 2 O was formed when the reaction mixture was aged at room temperature, and the α-LiZnPO 4 was obtained when the reaction mixture was aged at 80 deg. C.

Properties of ZnO Nano rods Arrays Growth via Low Temperature Hydrothermal Reaction

International Nuclear Information System (INIS)

Nur Syafinaz Ridhuan; Zainovia Lockman; Azlan Abdul Aziz; Azlan Abdul Aziz; Khairunisak Abdul Razak; Khairunisak Abdul Razak

2011-01-01

This work describes properties of 1- D ZnO nano rods (NRs) arrays growth using low temperature hydrothermal method on seeded substrate. The properties of ZnO seed were studied by varying annealed temperature from 250-450 degree Celsius. The optimum oxidation temperature to produce seeded ZnO template was 400 degree Celsius. The formations of ZnO NRs were further studied by varying hydrothermal reaction growth time from 1 to 24 hours. I-V characteristic of ZnO NRs photodetector in dark, ambient light and UV light were also studied. The change in the photoconductivity under UV illumination was found to be 1 order higher in magnitude compared to dark current and ambient light. With an incident wavelength of 370 nm and applied bias of 3V, the responsivity of photodetector was 5.0 mA/ W, which was higher compared to other reported works. The increase of photosensitivity indicated that the produced ZnO NRs were suitable for UV photodetector applications.(author)

Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

Science.gov (United States)

Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf; Cleemann, Lars N.; Li, Qingfeng

2018-01-01

Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at low temperatures and hence is not suitable for catalyst evaluation for HT-PEMFCs. In this study, we have designed and constructed a half-cell setup to measure the intrinsic activities of catalysts towards the oxygen reduction reaction (ORR) in conditions close to HT-PEMFC cathodes. By optimization of the hydrophobic characteristics of electrodes and the catalyst layer thickness, ORR activities of typical Pt/C catalysts are successfully measured in concentrated phosphoric acid at temperatures above 100 °C. In terms of mass-specific activities, the catalyst exhibits about two times higher activity in the half-cell electrode than that observed in fuel cells, indicating the feasibility of the technique as well as the potential for further improvement of fuel cell electrode performance.

Reaction OH + OH studied over the 298-834 K temperature and 1-100 bar pressure ranges.

Science.gov (United States)

Sangwan, Manuvesh; Chesnokov, Evgeni N; Krasnoperov, Lev N

2012-06-21

Self-reaction of hydroxyl radicals, OH + OH → H(2)O + O (1a) and OH + OH → H(2)O(2) (1b), was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 298-834 K temperature and 1-100 bar pressure ranges (bath gas He). A heatable high-pressure flow reactor was employed. Hydroxyl radicals were prepared using reaction of electronically excited oxygen atoms, O((1)D), produced in photolysis of N(2)O at 193 nm, with H(2)O. The temporal behavior of OH radicals was monitored via transient absorption of light from a dc discharge in H(2)O/Ar low-pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light was determined by accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The results of this study combined with the literature data indicate that the rate constant of reaction 1a, associated with the pressure independent component, decreases with temperature within the temperature range 298-414 K and increases above 555 K. The pressure dependent rate constant for (1b) was parametrized using the Troe expression as k(1b,inf) = (2.4 ± 0.6) × 10(-11)(T/300)(-0.5) cm(3) molecule(-1) s(-1), k(1b,0) = [He] (9.0 ± 2.2) × 10(-31)(T/300)(-3.5±0.5) cm(3) molecule(-1) s(-1), F(c) = 0.37.

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

Energy Technology Data Exchange (ETDEWEB)

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

2014-07-01

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

GaN CVD Reactions: Hydrogen and Ammonia Decomposition and the Desorption of Gallium

International Nuclear Information System (INIS)

Bartram, Michael E.; Creighton, J. Randall

1999-01-01

Isotopic labeling experiments have revealed correlations between hydrogen reactions, Ga desorption, and ammonia decomposition in GaN CVD. Low energy electron diffraction (LEED) and temperature programmed desorption (TPD) were used to demonstrate that hydrogen atoms are available on the surface for reaction after exposing GaN(0001) to deuterium at elevated temperatures. Hydrogen reactions also lowered the temperature for Ga desorption significantly. Ammonia did not decompose on the surface before hydrogen exposure. However, after hydrogen reactions altered the surface, N 15 H 3 did undergo both reversible and irreversible decomposition. This also resulted in the desorption of N 2 of mixed isotopes below the onset of GaN sublimation, This suggests that the driving force of the high nitrogen-nitrogen bond strength (226 kcal/mol) can lead to the removal of nitrogen from the substrate when the surface is nitrogen rich. Overall, these findings indicate that hydrogen can influence G-aN CVD significantly, being a common factor in the reactivity of the surface, the desorption of Ga, and the decomposition of ammonia

Numerical thermal-hydraulics study on sodium-water reaction phenomena

International Nuclear Information System (INIS)

Takashi, Takata; Akira, Yamaguchi

2003-01-01

A new computational program SERAPHIM (Sodium-watEr Reaction Analysis: PHysics of Interdisciplinary Multi-phase flow) is developed to investigate the Sodium-Water Reaction (SWR) phenomena based on parallel computation technology. A compressible three-fluid (liquid water, liquid sodium and mixture gas) and one-pressure model is adopted for multi-phase calculation. The Highly Simplified Maker And Cell (HSMAC) method considering with compressibility is implemented as the numerical solution. The Message-Passing Interface (MPI) is used for the parallel computation. Two types of reactions are considered for the SWR modeling; one is a surface reaction and the other is a gas phase reaction. The surface reaction model assumes that liquid sodium reacts with water vapor on the surface of liquid sodium. An analogy of heat transfer and mass transfer is applied in this model. Reaction heating vaporizes liquid sodium resulting in the gas phase reaction. The ab initio molecular orbital method is applied to investigate the reaction mechanism and evaluate the reaction rate described by the Arrhenius law. A performance of parallel computation is tested on the cluster-PC (16 CPUs) system. The execution time becomes 17.1 times faster in case of 16 CPUs. It seems promising that the SERAPHIM code is practicable for large-scale analysis of the SWR phenomena. Three-dimensional SWR analyses are also carried out to investigate the characteristics of the thermal-hydraulics with the SWR and an influence of initial pressure (0.2 MPa and 0.6 MPa) on an early stage of the SWR phenomenon. As a result, distribution of a gas region, in which water vapor or product of the SWR such as hydrogen and sodium hydroxide exits, velocity and high temperature region differs by 0.2 MPa and 0.6 MPa conditions. However, the maximum gas temperature has an upper bounding and is almost constant both in the analyses. The reason of the upper bounding is attributed to the fact that a hydrogen gas covers up a liquid

Development of an apparatus to study chemical reactions at high temperature - a progress report

Energy Technology Data Exchange (ETDEWEB)

Sturzenegger, M; Schelling, Th; Steiner, E; Wuillemin, D [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

1999-08-01

TREMPER is an apparatus that was devised to study kinetic and thermodynamic aspects of high-temperature reactions under concentrated solar irradiation. The design allows investigations on solid or liquid samples under inert or reactive atmospheres. The working temperature is adjustable; the upper limit that has yet been reached is about 1900 K. TREMPER will facilitate chemical reactivity studies on a temperature level that is difficult to access by other means. First experiments were conducted to study the decomposition of manganese oxide MnO{sub 2}. Chemical analysis of exposed samples confirmed that the parent MnO{sub 2} was decomposed to mixtures of Mn O and Mn{sub 3}O{sub 4}. The amount of Mn O ranged from 60 mol-% in air to 86 mol-% under inert atmosphere. (author) 1 fig., 1 tab., 2 refs.

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

Science.gov (United States)

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

1995-01-01

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

The reactions of magnesium and its alloys with moist gases at high temperatures; Les reactions du magnesium et de ses alliages avec les gaz humides aux temperatures elevees

Energy Technology Data Exchange (ETDEWEB)

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

1963-02-15

The kinetics and mechanisms of the reaction of pure or low alloyed magnesium with various gas saturated by water vapor: oxygen, argon, nitrogen, air, carbon dioxide, have been studied and compared in the temperature range 350-600 deg C. After picturing the large chemical reactivity of magnesium surface, the more or less properties of the oxide film, always made of magnesia, have been shown depending on the nature of the gas carrying water vapor; in fact, metal sublimation occurs the more easily as the surrounding atmosphere is less oxidizing. Moreover, an activation energy change is systematic, but at a temperature which depends also on the latter. In the case of the alloys, the linear oxidation rate is generally obtained only after short induction periods, parabolic in nature. Two possibilities of corrosion inhibition of magnesium by water vapor are then demonstrated and explained: either by a partial superficial fluoridation, or when the carrier gas is carbon dioxide. Also, the extreme conditions of oxidation were studied, that is the ignition processes that occur at a particular temperature in every gas mixture. Finally, it is tried to evolve the fundamental and practical significance of all the results. (author) [French] On a etudie et compare par voie thermogravimetrique, micrographique et radiocristallographique, les cinetiques et les mecanismes de reaction du magnesium et de certains de ses alliages avec diverses atmospheres saturees en vapeur d'eau: oxygene, argon, azote, air, gaz carbonique, dans un domaine de temperatures s'etendant de 350 a 600 deg C, Apres avoir illustre l'extreme sensibilite chimique de la surface du magnesium, on a tout d'abord montre que la valeur plus ou moins protectrice de la couche d'oxyde formee, pourtant toujours constituee de magnesie normale, depend de la nature du gaz porteur de la vapeur d'eau; en effet, la sublimation du metal intervient d'autant plus facilement que les atmospheres en presence sont moins oxydantes. De plus

Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods

KAUST Repository

Rachidi, Mariam El

2015-01-01

This paper investigates the high-temperature combustion kinetics of n-dibutyl ether (n-DBE), including unimolecular decomposition, H-abstraction by H, H-migration, and C{single bond}C/C{single bond}O β-scission reactions of the DBE radicals. The energetics of H-abstraction by OH radicals is also studied. All rates are determined computationally using the CBS-QB3 and G4 composite methods in conjunction with conventional transition state theory. The B3LYP/6-311++G(2df,2pd) method is used to optimize the geometries and calculate the frequencies of all reactive species and transition states for use in ChemRate. Some of the rates calculated in this study vary markedly from those obtained for similar reactions of alcohols or alkanes, particularly those pertaining to unimolecular decomposition and β-scission at the α-β C{single bond}C bond. These variations show that analogies to alkanes and alcohols are, in some cases, inappropriate means of estimating the reaction rates of ethers. This emphasizes the need to establish valid rates through computation or experimentation. Such studies are especially important given that ethers exhibit promising biofuel and fuel additive characteristics. © 2014.

Effect of the Reduction Temperature of PdAg Nanoparticles during the Polyol Process in the Ethanol Electrooxidation Reaction

OpenAIRE

Carrera-Cerritos, R.; Salazar-Hernandez, C.; Galindo-Esquivel, I. R.; Fuentes-Ramirez, R.

2018-01-01

This work reports the effect of reduction temperature during the synthesis of PdAg catalysts through the polyol process and their evaluation in the ethanol electrooxidation reaction (EOR). The characterization was performed using Transmission Electron Microscopy (TEM) and X-Ray Diffraction (XRD). The electrochemical evaluation for the ethanol electrooxidation reaction was implemented in alkaline medium using chronoamperometry (CA) and cyclic voltammetry (CV). An important effect of the reduct...

Estimating Arrhenius parameters using temperature programmed molecular dynamics

International Nuclear Information System (INIS)

Imandi, Venkataramana; Chatterjee, Abhijit

2016-01-01

Kinetic rates at different temperatures and the associated Arrhenius parameters, whenever Arrhenius law is obeyed, are efficiently estimated by applying maximum likelihood analysis to waiting times collected using the temperature programmed molecular dynamics method. When transitions involving many activated pathways are available in the dataset, their rates may be calculated using the same collection of waiting times. Arrhenius behaviour is ascertained by comparing rates at the sampled temperatures with ones from the Arrhenius expression. Three prototype systems with corrugated energy landscapes, namely, solvated alanine dipeptide, diffusion at the metal-solvent interphase, and lithium diffusion in silicon, are studied to highlight various aspects of the method. The method becomes particularly appealing when the Arrhenius parameters can be used to find rates at low temperatures where transitions are rare. Systematic coarse-graining of states can further extend the time scales accessible to the method. Good estimates for the rate parameters are obtained with 500-1000 waiting times.

Estimating Arrhenius parameters using temperature programmed molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Imandi, Venkataramana; Chatterjee, Abhijit, E-mail: abhijit@che.iitb.ac.in [Department of Chemical Engineering, Indian Institute of Technology Bombay, Mumbai 400076 (India)

2016-07-21

Kinetic rates at different temperatures and the associated Arrhenius parameters, whenever Arrhenius law is obeyed, are efficiently estimated by applying maximum likelihood analysis to waiting times collected using the temperature programmed molecular dynamics method. When transitions involving many activated pathways are available in the dataset, their rates may be calculated using the same collection of waiting times. Arrhenius behaviour is ascertained by comparing rates at the sampled temperatures with ones from the Arrhenius expression. Three prototype systems with corrugated energy landscapes, namely, solvated alanine dipeptide, diffusion at the metal-solvent interphase, and lithium diffusion in silicon, are studied to highlight various aspects of the method. The method becomes particularly appealing when the Arrhenius parameters can be used to find rates at low temperatures where transitions are rare. Systematic coarse-graining of states can further extend the time scales accessible to the method. Good estimates for the rate parameters are obtained with 500-1000 waiting times.

Effect of a perturbation-based balance training program on compensatory stepping and grasping reactions in older adults: a randomized controlled trial.

Science.gov (United States)

Mansfield, Avril; Peters, Amy L; Liu, Barbara A; Maki, Brian E

2010-04-01

Compensatory stepping and grasping reactions are prevalent responses to sudden loss of balance and play a critical role in preventing falls. The ability to execute these reactions effectively is impaired in older adults. The purpose of this study was to evaluate a perturbation-based balance training program designed to target specific age-related impairments in compensatory stepping and grasping balance recovery reactions. This was a double-blind randomized controlled trial. The study was conducted at research laboratories in a large urban hospital. Thirty community-dwelling older adults (aged 64-80 years) with a recent history of falls or self-reported instability participated in the study. Participants were randomly assigned to receive either a 6-week perturbation-based (motion platform) balance training program or a 6-week control program involving flexibility and relaxation training. Features of balance reactions targeted by the perturbation-based program were: (1) multi-step reactions, (2) extra lateral steps following anteroposterior perturbations, (3) foot collisions following lateral perturbations, and (4) time to complete grasping reactions. The reactions were evoked during testing by highly unpredictable surface translation and cable pull perturbations, both of which differed from the perturbations used during training. /b> Compared with the control program, the perturbation-based training led to greater reductions in frequency of multi-step reactions and foot collisions that were statistically significant for surface translations but not cable pulls. The perturbation group also showed significantly greater reduction in handrail contact time compared with the control group for cable pulls and a possible trend in this direction for surface translations. Further work is needed to determine whether a maintenance program is needed to retain the training benefits and to assess whether these benefits reduce fall risk in daily life. Perturbation-based training

IR laser induced reactions: temperature distributions and detection of primary products

International Nuclear Information System (INIS)

Bachmann, F.

1981-12-01

The products of laser-driven pyrolysis in the gas phase often differ drastically from those of conventional pyrolysis. In this work some reasons for this behaviour are considered. First, temperature distributions in cylindrical cells, filled with SF 6 at low pressure and heated by cw CO 2 laser radiation, are calculated by a simple model. The influence of convection is not taken into account. Comparison of theoretical prediction and corresponding experiments included the temperature-dependent absorption cross section. In the second part we describe a molecular-beam sampling system for real time monitoring of primary products in laser-driven reactions. With this system initial tests were made in nonreacting SF 6 /rare-gas mixtures. The influence of thermal diffusion was indicated by changes in concentration when the laser was switched on and off. A theoretical treatment is given solving the time-dependent heat-conduction and diffusion equation numerically. As an example for reacting systems, the laser-driven pyrolysis of methanol with SF 6 as an absorber was studied. (orig./HT)

Colour-Temperature Correspondences: When Reactions to Thermal Stimuli Are Influenced by Colour

Science.gov (United States)

Ho, Hsin-Ni; Van Doorn, George H.; Kawabe, Takahiro; Watanabe, Junji; Spence, Charles

2014-01-01

In our daily lives, information concerning temperature is often provided by means of colour cues, with red typically being associated with warm/hot, and blue with cold. While such correspondences have been known about for many years, they have primarily been studied using subjective report measures. Here we examined this correspondence using two more objective response measures. First, we used the Implicit Association Test (IAT), a test designed to assess the strength of automatic associations between different concepts in a given individual. Second, we used a priming task that involved speeded target discrimination in order to assess whether priming colour or thermal information could invoke the crossmodal association. The results of the IAT confirmed that the association exists at the level of response selection, thus indicating that a participant’s responses to colour or thermal stimuli are influenced by the colour-temperature correspondence. The results of the priming experiment revealed that priming a colour affected thermal discrimination reaction times (RTs), but thermal cues did not influence colour discrimination responses. These results may therefore provide important clues as to the level of processing at which such colour-temperature correspondences are represented. PMID:24618675

Program DDCS for nucleon and composite particle DDX of nucleon induced reactions up to tens of MeV

International Nuclear Information System (INIS)

Shen Qingbiao

1994-01-01

DDCS is a program for calculating the neutron or proton induced reactions of medium-heavy nuclei in the incident energy range up to 50 MeV including 5 emission processes. This program is written in FORTAN-77 on microscopic computer 486. DDCS is constructed within the framework of optical model, generalized master equation of the exciton model, and the evaporation model. The effect of recoil nucleus is considered in this program. DDCS has been used to calculate reactions of n + 56 Fe, n + 93 Nb, P + 120 Sn, P + 197 Au, and P + 209 Bi. Pretty good results in agreement with the experimental data were obtained

A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan

Czech Academy of Sciences Publication Activity Database

Zymak, Illia; Žabka, Ján; Polášek, Miroslav; Španěl, Patrik; Smith, D.

2016-01-01

Roč. 46, č. 4 (2016), s. 533-538 ISSN 0169-6149 R&D Projects: GA ČR(CZ) GA14-19693S Grant - others:COST(XE) TD1308 Institutional support: RVO:61388955 Keywords : titan ionosphere * variable temperature selected ions flow tube * ion-molecule reactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.000, year: 2016

Temperature dependent halogen activation by N2O5 reactions on halide-doped ice surfaces

Directory of Open Access Journals (Sweden)

J. A. Thornton

2012-06-01

Full Text Available We examined the reaction of N2O5 on frozen halide salt solutions as a function of temperature and composition using a coated wall flow tube technique coupled to a chemical ionization mass spectrometer (CIMS. The molar yield of photo-labile halogen compounds was near unity for almost all conditions studied, with the observed reaction products being nitryl chloride (ClNO2 and/or molecular bromine (Br2. The relative yield of ClNO2 and Br2 depended on the ratio of bromide to chloride ions in the solutions used to form the ice. At a bromide to chloride ion molar ratio greater than 1/30 in the starting solution, Br2 was the dominant product otherwise ClNO2 was primarily produced on these near pH-neutral brines. We demonstrate that the competition between chlorine and bromine activation is a function of the ice/brine temperature presumably due to the preferential precipitation of NaCl hydrates from the brine below 250 K. Our results provide new experimental confirmation that the chemical environment of the brine layer changes with temperature and that these changes can directly affect multiphase chemistry. These findings have implications for modeling air-snow-ice interactions in polar regions and likely in polluted mid-latitude regions during winter as well.

Reactions of the HO₂ radical with OH, H, Fe²⁺ and Cu²⁺ at elevated temperatures

DEFF Research Database (Denmark)

Lundström, T.; Christensen, H.; Sehested, K.

2004-01-01

was studied in the temperature range 20-296degreesC (k = 7.0 x 10(9), E-a = 7.4) and the reaction with H in the temperature range 5-149degreesC (k = 8.5 x 10(9), E-a = 17.5). The reaction with Fe2+ was studied in the temperature range 16-118degreesC (k = 7.9 x 10(5), E-a = 36.8) and the reaction with Cu2......+ in the temperature range 17-211degreesC (k = 1.1 x 10(8), E-a = 14.9). (C) 2003 Elsevier Ltd. All rights reserved....

CCl 4 chemistry on the magnetite selvedge of single-crystal hematite: competitive surface reactions

Science.gov (United States)

Adib, K.; Camillone, N., III; Fitts, J. P.; Rim, K. T.; Flynn, G. W.; Joyce, S. A.; Osgood, R. M., Jr.

2002-01-01

Temperature programmed reaction/desorption (TPR/D) studies were undertaken to characterize the surface chemistry which occurs between CCl 4 and the Fe 3O 4 (1 1 1) selvedge of single crystal α-Fe 2O 3 (0 0 0 1). Six separate desorption events are clearly observed and four desorbing species are identified: CCl 4, OCCl 2, C 2Cl 4 and FeCl 2. It is proposed that OCCl 2, CCl 4 and C 2Cl 4 are produced in reactions involving the same precursor, CCl 2. Three reaction paths compete for the CCl 2 precursor: oxygen atom abstraction (for OCCl 2), molecular recombinative desorption (for CCl 4) and associative desorption (for C 2Cl 4). During the TPR/D temperature ramp, the branching ratio is observed to depend upon temperature and the availability of reactive sites. The data are consistent with a rich site-dependent chemistry.

Spectroscopy and kinetics of combustion gases at high temperatures

Energy Technology Data Exchange (ETDEWEB)

Hanson, R.K.; Bowman, C.T. [Stanford Univ., CA (United States)

1993-12-01

This program involves two complementary activities: (1) development and application of cw ring dye laser absorption methods for sensitive detection of radical species and measurement of fundamental spectroscopic parameters at high temperatures; and (2) shock tube studies of reaction kinetics relevant to combustion. Species currently under investigation in the spectroscopic portion of the research include NO and CH{sub 3}; this has necessitated the continued operated at wavelengths in the range 210-230 nm. Shock tube studies of reaction kinetics currently are focussed on reactions involving CH{sub 3} radicals.

Temperature-controlled cross-linking of silver nanoparticles with Diels-Alder reaction and its application on antibacterial property

International Nuclear Information System (INIS)

Liu, Lian; Yang, Pengfei; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling

2017-01-01

Highlights: • Silver nanoparticles were functionalized by furan groups. • The DA reaction of furan with bismaleimide was used to cross-link the particles. • The reverse cross-linking could be controlled by temperature. • The antibacterial activity of silvers could be adjusted by the cross-linking. - Abstract: Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV–vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.

Temperature-controlled cross-linking of silver nanoparticles with Diels-Alder reaction and its application on antibacterial property

Energy Technology Data Exchange (ETDEWEB)

Liu, Lian; Yang, Pengfei, E-mail: ypf@qlu.edu.cn; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling

2017-05-01

Highlights: • Silver nanoparticles were functionalized by furan groups. • The DA reaction of furan with bismaleimide was used to cross-link the particles. • The reverse cross-linking could be controlled by temperature. • The antibacterial activity of silvers could be adjusted by the cross-linking. - Abstract: Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV–vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.

A study on sodium-concrete reaction

Energy Technology Data Exchange (ETDEWEB)

Bae, Jae Heum; Min, Byong Hun [Suwon University, Suwon (Korea, Republic of)

1997-07-01

A small sodium-concrete reaction facility was designed, manufactured and installed. this facility has been operated under inert gas(N{sub 2}) with different experimental variables such as sodium injection temperature, injection amount of sodium, aging period of concrete, sodium reservoir temperature. As a result, it was found that sodium injection temperature and injected amount of sodium has little effect on sodium-concrete reaction. However, sodium reservoir temperature and aging period of concrete has relatively high impact on sodium-concrete reaction. Sodium-concrete reaction model has also been developed and compared with experimental results. (Author) 51 refs., 16 tabs., 64 figs.

Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

International Nuclear Information System (INIS)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

2015-01-01

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

Effect of temperature on a free energy and equilibrium constants during dry flue gas desulphurisation chemical reactions

Directory of Open Access Journals (Sweden)

Kuburović Miloš

2002-01-01

Full Text Available During dry flue gas desulphurisation (FGD dry particles of reagents are inserted (injected in the stream of flue gas, where they bond SO2. As reagents, the most often are used compounds of calcium (CaCO3, CaO or Ca(OH2. Knowledge of free energy and equilibrium constants of chemical reactions during dry FGD is necessary for understanding of influence of flue gas temperature to course of these chemical reactions as well as to SO2 bonding from flue gases.

Energy-filtered environmental transmission electron microscopy for the assessment of solid–gas reactions at elevated temperature: NiO/YSZ–H{sub 2} as a case study

Energy Technology Data Exchange (ETDEWEB)

Jeangros, Q. [Interdisciplinary Centre for Electron Microscopy, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Photovoltaics and Thin Film Electronics Laboratory, Ecole Polytechnique Fédérale de Lausanne, Neuchâtel (Switzerland); Hansen, T.W.; Wagner, J.B. [Center for Electron Nanoscopy, Technical University of Denmark, Lyngby (Denmark); Dunin-Borkowski, R.E. [Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons and Peter Grünberg Institute, Jülich Research Centre, Jülich (Germany); Hébert, C. [Interdisciplinary Centre for Electron Microscopy, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Van herle, J. [Fuelmat Group, Ecole Polytechnique Fédérale de Lausanne, Sion (Switzerland); Hessler-Wyser, A. [Interdisciplinary Centre for Electron Microscopy, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Photovoltaics and Thin Film Electronics Laboratory, Ecole Polytechnique Fédérale de Lausanne, Neuchâtel (Switzerland)

2016-10-15

A novel approach, which is based on the analysis of sequences of images recorded using energy-filtered transmission electron microscopy and can be used to assess the reaction of a solid with a gas at elevated temperature, is illustrated for the reduction of a NiO/ceramic solid oxide fuel cell anode in 1.3 mbar of H{sub 2}. Three-window elemental maps and jump-ratio images of the O K edge and total inelastic mean free path images are recorded as a function of temperature and used to provide local and quantitative information about the reaction kinetics and the volume changes that result from the reaction. Under certain assumptions, the speed of progression of the reaction front in all three dimensions is obtained, thereby providing a three-dimensional understanding of the reaction. - Highlights: • EFTEM is used to assess solid–gas reactions at elevated temperatures. • This novel approach provides local, quantitative chemical and structural data. • A 3D insight into how the reaction proceeds is obtained under certain assumptions. • Reaction mechanisms and their link to microstructure can be established.

Genetic Programming and Standardization in Water Temperature Modelling

Directory of Open Access Journals (Sweden)

Maritza Arganis

2009-01-01

Full Text Available An application of Genetic Programming (an evolutionary computational tool without and with standardization data is presented with the aim of modeling the behavior of the water temperature in a river in terms of meteorological variables that are easily measured, to explore their explanatory power and to emphasize the utility of the standardization of variables in order to reduce the effect of those with large variance. Recorded data corresponding to the water temperature behavior at the Ebro River, Spain, are used as analysis case, showing a performance improvement on the developed model when data are standardized. This improvement is reflected in a reduction of the mean square error. Finally, the models obtained in this document were applied to estimate the water temperature in 2004, in order to provide evidence about their applicability to forecasting purposes.

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

Science.gov (United States)

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

1993-01-01

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

Characteristics of liquid product from the pyrolysis of waste plastic mixture at low and high temperatures: Influence of lapse time of reaction

International Nuclear Information System (INIS)

Lee, Kyong-Hwan; Shin, Dae-Hyun

2007-01-01

Pyrolysis of a waste plastic mixture (high-density polyethylene: low-density polyethylene: polypropylene: polystyrene = 3:2:3:1) into a liquid product was carried out in a stirred semi-batch reactor at low (350 deg. C) and high (400 deg. C) temperatures. The effect of lapse time of reaction in the reactor and also degradation temperature on the characteristics of the liquid product from pyrolysis of the mixture was investigated. Liquid products were described by cumulative amount distribution, paraffin, olefin, naphthene and aromatic (PONA) distribution and molecular weight distribution. Their characteristic was quite differed with a lapse time of reaction and also at a low and high degradation temperatures, because of the different physicochemical properties of the plastic types in the mixture. With increase of lapse time of reaction, the order for the main products in PONA components obtained at 350 deg. C was firstly aromatic products and then olefin products, while at 400 deg. C the order was firstly aromatic products, then olefin products and finally paraffin products. The experiments also showed from the molecular weight distribution of liquid PONA components that the paraffin and olefin products had a wide distribution by mainly random scission of polymer, but in the case of olefin products were produced by an end-chain scission mechanism as well as random scission mechanism, as evidenced by much more light olefin products. This phenomenon was evident at a higher degradation temperature. Also, both the light olefin and naphthene products with a molecular weight of around 120, as a main product, showed a similar trend as a function of lapse time, which had a maximum fraction at 343 min (at 350 deg. C) and 83 min (at 400 deg. C). Among PONA components, the highest concentrations of aromatic products were obtained with a molecular weight of around 100 at the fastest lapse time of reaction, regardless of degradation temperature. It was concluded that the

Characteristics of liquid product from the pyrolysis of waste plastic mixture at low and high temperatures: influence of lapse time of reaction.

Science.gov (United States)

Lee, Kyong-Hwan; Shin, Dae-Hyun

2007-01-01

Pyrolysis of a waste plastic mixture (high-density polyethylene: low-density polyethylene: polypropylene: polystyrene = 3:2:3:1) into a liquid product was carried out in a stirred semi-batch reactor at low (350 degrees C) and high (400 degrees C) temperatures. The effect of lapse time of reaction in the reactor and also degradation temperature on the characteristics of the liquid product from pyrolysis of the mixture was investigated. Liquid products were described by cumulative amount distribution, paraffin, olefin, naphthene and aromatic (PONA) distribution and molecular weight distribution. Their characteristic was quite differed with a lapse time of reaction and also at a low and high degradation temperatures, because of the different physicochemical properties of the plastic types in the mixture. With increase of lapse time of reaction, the order for the main products in PONA components obtained at 350 degrees C was firstly aromatic products and then olefin products, while at 400 degrees C the order was firstly aromatic products, then olefin products and finally paraffin products. The experiments also showed from the molecular weight distribution of liquid PONA components that the paraffin and olefin products had a wide distribution by mainly random scission of polymer, but in the case of olefin products were produced by an end-chain scission mechanism as well as random scission mechanism, as evidenced by much more light olefin products. This phenomenon was evident at a higher degradation temperature. Also, both the light olefin and naphthene products with a molecular weight of around 120, as a main product, showed a similar trend as a function of lapse time, which had a maximum fraction at 343 min (at 350 degrees C) and 83 min (at 400 degrees C). Among PONA components, the highest concentrations of aromatic products were obtained with a molecular weight of around 100 at the fastest lapse time of reaction, regardless of degradation temperature. It was

The relationship of microstructure and temperature to fracture mechanics parameters in reaction bonded silicon nitride

International Nuclear Information System (INIS)

Jennings, H.M.; Dalgleish, B.J.; Pratt, P.L.

1978-01-01

The development of physical properties in reaction bonded silicon nitride has been investigated over a range of temperatures and correlated with microstructure. Fracture mechanics parameters, elastic moduli, strength and critical defect size have been determined. The nitrided microstructure is shown to be directly related to these observed properties and these basic relationships can be used to produce material with improved properties. (orig.) [de

Fast temperature programming in gas chromatography using resistive heating

NARCIS (Netherlands)

Dallüge, J.; Ou-Aissa, R.; Vreuls, J.J.; Brinkman, U.A.T.; Veraart, J.R.

1999-01-01

The features of a resistive-heated capillary column for fast temperature-programmed gas chromatography (GC) have been evaluated. Experiments were carried out using a commercial available EZ Flash GC, an assembly which can be used to upgrade existing gas chromatographs. The capillary column is placed

Interaction of chemical reactions and radiant heat transfer with temperature turbulent pulsations and its effect on heat traner in high-temperature gas flows

International Nuclear Information System (INIS)

Petukhov, B.S.; Zal'tsman, I.G.; Shikov, V.K.

1980-01-01

Methods of taking account of mutual effect of chemical transformations, radiation and turbulence in the calculations of heat transfer in gas flows are considered. Exponential functions of medium parameters are used to describe chemical sources and optical properties of media. It is shown using as an example the dissociation reaction C 2 reversible 2C that the effect of temperature and composition pulsations on recombination rates is negligibly small. It is also shown on the example of turbulent flow of hot molecular gas in a flat channel with cold walls that at moderate temperatures the effect of temperature pulsations on heat radiation flow can be significant (30-40%). The calculational results also show that there is a region in a turbulent boundary layer where the radiation greatly affects the coefficient of turbulent heat transfer

Eutectic reaction analysis between TRU-50%Zr alloy fuel and HT-9 cladding, and temperature prediction of eutectic reaction under steady-state

Energy Technology Data Exchange (ETDEWEB)

Hwang, Woan; Lee, Byoung Oon; Lee, Bong Sang; Park, Won Seok

2001-02-01

Blanket fuel assembly for HYPER contains a bundle of pins arrayed in triangular pitch, which has hexagonal bundle structure. The reference blanket fuel pin consists of the fuel slug of TRU-50wt%Zr alloy and the cladding material of ferritic martensite steel, HT-9. Chemical interaction between fuel slug and cladding is one of the major concerns in metallic fuel rod design. The contact of metallic fuel slug and stainless steel cladding in a fuel rod forms a complex multi-component diffusion couple at elevated temperatures. The potential problem of inter-diffusion of fuel and cladding components is essentially two-fold weakening of cladding mechanical strength due to the formation of diffusion zones in the cladding, and the formation of comparatively low melting point phases in the fuel/cladding interface to develop eutectic reaction. The main components of fuel slug are composed of zirconium alloying element in plutonium matrix, including neptunium, americium and uranium additionally. Therefore basic eutectic reaction change of Pu-Fe binary system can be assessed, while it is estimated how much other elements zirconium, uranium, americium and neptunium influence on plutonium phase stability. Afterwards it is needed that eutectic reaction is verified through experimental necessarily.

Eutectic reaction analysis between TRU-50%Zr alloy fuel and HT-9 cladding, and temperature prediction of eutectic reaction under steady-state

International Nuclear Information System (INIS)

Hwang, Woan; Lee, Byoung Oon; Lee, Bong Sang; Park, Won Seok

2001-02-01

Blanket fuel assembly for HYPER contains a bundle of pins arrayed in triangular pitch, which has hexagonal bundle structure. The reference blanket fuel pin consists of the fuel slug of TRU-50wt%Zr alloy and the cladding material of ferritic martensite steel, HT-9. Chemical interaction between fuel slug and cladding is one of the major concerns in metallic fuel rod design. The contact of metallic fuel slug and stainless steel cladding in a fuel rod forms a complex multi-component diffusion couple at elevated temperatures. The potential problem of inter-diffusion of fuel and cladding components is essentially two-fold weakening of cladding mechanical strength due to the formation of diffusion zones in the cladding, and the formation of comparatively low melting point phases in the fuel/cladding interface to develop eutectic reaction. The main components of fuel slug are composed of zirconium alloying element in plutonium matrix, including neptunium, americium and uranium additionally. Therefore basic eutectic reaction change of Pu-Fe binary system can be assessed, while it is estimated how much other elements zirconium, uranium, americium and neptunium influence on plutonium phase stability. Afterwards it is needed that eutectic reaction is verified through experimental necessarily

Determination of surface coverage of catalysts : temperature programmed experiments on platinum and iridium sponge catalysts after low temperature ammonia oxidation

NARCIS (Netherlands)

van den Broek, A.C.M.; Grondelle, van J.; Santen, van R.A.

1999-01-01

The activity of iridium and platinum sponge catalysts was studied in the low temperature gas phase oxidation of ammonia with oxygen. Under the reaction conditions used, iridium was found to be more active and more selective to nitrogen than platinum. Furthermore it was established from activity

Room Temperature, Hybrid Sodium-Based Flow Batteries with Multi-Electron Transfer Redox Reactions

Science.gov (United States)

Shamie, Jack S.; Liu, Caihong; Shaw, Leon L.; Sprenkle, Vincent L.

2015-01-01

We introduce a new concept of hybrid Na-based flow batteries (HNFBs) with a molten Na alloy anode in conjunction with a flowing catholyte separated by a solid Na-ion exchange membrane for grid-scale energy storage. Such HNFBs can operate at ambient temperature, allow catholytes to have multiple electron transfer redox reactions per active ion, offer wide selection of catholyte chemistries with multiple active ions to couple with the highly negative Na alloy anode, and enable the use of both aqueous and non-aqueous catholytes. Further, the molten Na alloy anode permits the decoupled design of power and energy since a large volume of the molten Na alloy can be used with a limited ion-exchange membrane size. In this proof-of-concept study, the feasibility of multi-electron transfer redox reactions per active ion and multiple active ions for catholytes has been demonstrated. The critical barriers to mature this new HNFBs have also been explored. PMID:26063629

Particle size effect of redox reactions for Co species supported on silica

International Nuclear Information System (INIS)

Chotiwan, Siwaruk; Tomiga, Hiroki; Katagiri, Masaki; Yamamoto, Yusaku; Yamashita, Shohei; Katayama, Misaki; Inada, Yasuhiro

2016-01-01

Conversions of chemical states during redox reactions of two silica-supported Co catalysts, which were prepared by the impregnation method, were evaluated by using an in situ XAFS technique. The addition of citric acid into the precursor solution led to the formation on silica of more homogeneous and smaller Co particles, with an average diameter of 4 nm. The supported Co 3 O 4 species were reduced to metallic Co via the divalent CoO species during a temperature-programmed reduction process. The reduced Co species were quantitatively oxidized with a temperature-programmed oxidation process. The higher observed reduction temperature of the smaller CoO particles and the lower observed oxidation temperature of the smaller metallic Co particles were induced by the higher dispersion of the Co oxide species, which apparently led to a stronger interaction with supporting silica. The redox temperature between CoO and Co 3 O 4 was found to be independent of the particle size. - Graphical abstract: Chemical state conversions of SiO 2 -supported Co species and the particle size effect have been analyzed by means of in situ XAFS technique. The small CoO particles have endurance against the reduction and exist in a wide temperature range. Display Omitted - Highlights: • The conversions of the chemical state of supported Co species during redox reaction are evaluated. • In operando XAFS technique were applied to measure redox properties of small Co particles. • A small particle size affects to the redox temperatures of cobalt catalysts.

Japanese HTTR program for demonstration of high temperature applications of nuclear energy

International Nuclear Information System (INIS)

Nishihara, T.; Hada, K.; Shiozawa, S.

1997-01-01

Construction works of the HTTR started in March 1991 in order to establish and upgrade the HTGR technology basis, to carry out innovative basic researches on high temperature engineering and to demonstrate high temperature heat utilization and application of nuclear heat. This report describes the demonstration program of high temperature heat utilization and application. (author). 2 refs, 4 figs, 3 tabs

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.

A general strategy for performing temperature-programming in high performance liquid chromatography--prediction of segmented temperature gradients.

Science.gov (United States)

Wiese, Steffen; Teutenberg, Thorsten; Schmidt, Torsten C

2011-09-28

In the present work it is shown that the linear elution strength (LES) model which was adapted from temperature-programming gas chromatography (GC) can also be employed to predict retention times for segmented-temperature gradients based on temperature-gradient input data in liquid chromatography (LC) with high accuracy. The LES model assumes that retention times for isothermal separations can be predicted based on two temperature gradients and is employed to calculate the retention factor of an analyte when changing the start temperature of the temperature gradient. In this study it was investigated whether this approach can also be employed in LC. It was shown that this approximation cannot be transferred to temperature-programmed LC where a temperature range from 60°C up to 180°C is investigated. Major relative errors up to 169.6% were observed for isothermal retention factor predictions. In order to predict retention times for temperature gradients with different start temperatures in LC, another relationship is required to describe the influence of temperature on retention. Therefore, retention times for isothermal separations based on isothermal input runs were predicted using a plot of the natural logarithm of the retention factor vs. the inverse temperature and a plot of the natural logarithm of the retention factor vs. temperature. It could be shown that a plot of lnk vs. T yields more reliable isothermal/isocratic retention time predictions than a plot of lnk vs. 1/T which is usually employed. Hence, in order to predict retention times for temperature-gradients with different start temperatures in LC, two temperature gradient and two isothermal measurements have been employed. In this case, retention times can be predicted with a maximal relative error of 5.5% (average relative error: 2.9%). In comparison, if the start temperature of the simulated temperature gradient is equal to the start temperature of the input data, only two temperature

The influence of temperature and reaction time in the degradation of natural rubber latex

International Nuclear Information System (INIS)

Siti Zaleha Isa; Rosiyah Yahya; Aziz Hassan; Mohd Tahir

2007-01-01

Liquid natural rubber (LNR /LENR) should be considered as a new material instead of a new type of rubber though they have the same configuration as the rubber used. In this work, thermal degradation of natural rubber latex was carried out to obtain LNR/LENR by varying the reaction time at different temperatures. The degraded polymers were characterized structurally using FTIR and NMR spectroscopies and the average molecular weights were determined by membrane-osmometry and viscometry. (author)

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)

Testing program for concrete at temperatures to 8940K

International Nuclear Information System (INIS)

Naus, D.J.; Oland, C.B.; Robinson, G.C.

1981-01-01

A test program was conducted to define the variations in mechanical properties of a limestone aggregate concrete and a lightweight insulating concrete exposed to elevated temperatures. Four test series were conducted: (1) unconfined compression; (2) shear; (3) rebar bond; and (4) sustained loading (creep). Tests results are presented

Summary of ORNL high-temperature gas-cooled reactor program

International Nuclear Information System (INIS)

Kasten, P.R.

1981-01-01

Oak Ridge National Laboratory (ORNL) efforts on the High-Temperature Gas-Cooled Reactor (HTGR) Program have been on HTGR fuel development, fission product and coolant chemistry, prestressed concrete reactor vessel (PCRV) studies, materials studies, graphite development, reactor physics and shielding studies, application assessments and evaluations and selected component testing

Low temperature thermal energy storage: a state-of-the-art survey

Energy Technology Data Exchange (ETDEWEB)

Baylin, F.

1979-07-01

The preliminary version of an analysis of activities in research, development, and demonstration of low temperature thermal energy storage (TES) technologies having applications in renewable energy systems is presented. Three major categories of thermal storage devices are considered: sensible heat; phase change materials (PCM); and reversible thermochemical reactions. Both short-term and annual thermal energy storage technologies based on prinicples of sensible heat are discussed. Storage media considered are water, earth, and rocks. Annual storage technologies include solar ponds, aquifers, and large tanks or beds of water, earth, or rocks. PCM storage devices considered employ salt hydrates and organic compounds. The sole application of reversible chemical reactions outlined is for the chemical heat pump. All program processes from basic research through commercialization efforts are investigated. Nongovernment-funded industrial programs and foreign efforts are outlined as well. Data describing low temperature TES activities are presented also as project descriptions. Projects for all these programs are grouped into seven categories: short-term sensible heat storage; annual sensible heat storage; PCM storage; heat transfer and exchange; industrial waste heat recovery and storage; reversible chemical reaction storage; and models, economic analyses, and support studies. Summary information about yearly funding and brief descriptions of project goals and accomplishments are included.

Influence of vegetable oils fatty acid composition on reaction temperature and glycerides conversion to biodiesel during transesterification.

Science.gov (United States)

Pinzi, S; Gandía, L M; Arzamendi, G; Ruiz, J J; Dorado, M P

2011-01-01

Presence of unreacted glycerides in biodiesel may reduce drastically its quality. This is why conversion of raw material in biodiesel through transesterification needs to readjust reaction parameter values to complete. In the present work, monitoring of glycerides transformation in biodiesel during the transesterification of vegetable oils was carried out. To check the influence of the chemical composition on glycerides conversion, selected vegetable oils covered a wide range of fatty acid composition. Reactions were carried out under alkali-transesterification in the presence of methanol. In addition, a multiple regression model was proposed. Results showed that kinetics depends on chemical and physical properties of the oils. It was found that the optimal reaction temperature depends on both length and unsaturation degree of vegetable oils fatty acid chains. Vegetable oils with higher degree of unsaturation exhibit faster monoglycerides conversion to biodiesel. It can be concluded that fatty acid composition influences reaction parameters and glycerides conversion, hence biodiesel yield and economic viability. Copyright © 2010 Elsevier Ltd. All rights reserved.

The effects of moisture on LiD single crystals studied by temperature-programmed decomposition

International Nuclear Information System (INIS)

Dinh, L.N.; Cecala, C.M.; Leckey, J.H.; Balooch, M.

2001-01-01

Temperature-programmed decomposition (TPD) technique was performed on LiOH powders and LiD single crystals previously exposed to different moisture levels. Our results show that the LiOH decomposition process is rate-limited by an inward moving reaction front mechanism with an activation energy barrier of ∼122-149 kJ/mol. The LiOH structure is stable even if kept at 320 K. However, LiOH structures formed on the surface of LiD single crystals during moisture exposure at low dosages may have multiple activation energy barriers, some of which may be much lower than 122 kJ/mol. The rate-limiting mechanism for the decomposition of LiOH structures with reduced activation energy barriers is consistent with a unimolecular nucleation model. We attribute the lowering of the activation energy barrier for the LiOH decomposition to the existence of sub-stoichiometric Li(OH) x with x 2 O formation is observed. The release of H 2 O molecules from LiOH · H 2 O structure has small activation energy barriers in the range of 48-69 kJ/mol and follows a unimolecular nucleation process. The loosely bonded H 2 O molecules in the LiOH · H 2 O structure can be easily pumped away at room temperature in a reasonable amount of time. Our experiments also suggest that handling LiD single crystals at an elevated temperature of 340 K or more reduces the growth rate of LiOH and LiOH · H 2 O significantly

High temperature reactions between molybdenum and metal halides

International Nuclear Information System (INIS)

Boeroeczki, A.; Dobos, G.; Josepovits, V.K.; Hars, Gy.

2006-01-01

Good colour rendering properties, high intensity and efficacy are of vital importance for high-end lighting applications. These requirements can be achieved by high intensity discharge lamps doped with different metal halide additives (metal halide lamps). To improve their reliability, it is very important to understand the different failure processes of the lamps. In this paper, the corrosion reactions between different metal halides and the molybdenum electrical feed-through electrode are discussed. The reactions were studied in the feed-through of real lamps and on model samples too. X-ray photoelectron spectroscopy (XPS) was used to establish the chemical states. In case of the model samples we have also used atomic absorption spectroscopy (AAS) to measure the reaction product amounts. Based on the measurement results we were able to determine the most corrosive metal halide components and to understand the mechanism of the reactions

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.

Qualitative and quantitative analysis of complex temperature-programmed desorption data by multivariate curve resolution

Science.gov (United States)

Rodríguez-Reyes, Juan Carlos F.; Teplyakov, Andrew V.; Brown, Steven D.

2010-10-01

The substantial amount of information carried in temperature-programmed desorption (TPD) experiments is often difficult to mine due to the occurrence of competing reaction pathways that produce compounds with similar mass spectrometric features. Multivariate curve resolution (MCR) is introduced as a tool capable of overcoming this problem by mathematically detecting spectral variations and correlations between several m/z traces, which is later translated into the extraction of the cracking pattern and the desorption profile for each desorbate. Different from the elegant (though complex) methods currently available to analyze TPD data, MCR analysis is applicable even when no information regarding the specific surface reaction/desorption process or the nature of the desorbing species is available. However, when available, any information can be used as constraints that guide the outcome, increasing the accuracy of the resolution. This approach is especially valuable when the compounds desorbing are different from what would be expected based on a chemical intuition, when the cracking pattern of the model test compound is difficult or impossible to obtain (because it could be unstable or very rare), and when knowing major components desorbing from the surface could in more traditional methods actually bias the quantification of minor components. The enhanced level of understanding of thermal processes achieved through MCR analysis is demonstrated by analyzing three phenomena: i) the cryogenic desorption of vinyltrimethylsilane from silicon, an introductory system where the known multilayer and monolayer components are resolved; ii) acrolein hydrogenation on a bimetallic Pt-Ni-Pt catalyst, where a rapid identification of hydrogenated products as well as other desorbing species is achieved, and iii) the thermal reaction of Ti[N(CH 3) 2] 4 on Si(100), where the products of surface decomposition are identified and an estimation of the surface composition after the

A development report on the inelastic analysis program for the high temperature structures

International Nuclear Information System (INIS)

Kim, Jong Bum; Lee, H. Y.; Lee, J. H.

2001-04-01

LMR high temperature structures such as reactor vessel and reactor internal structures are subject to high temperature operating loads thus they can undergo damage due to creep, creep-fatigue, and ratcheting behavior. In this project, NONSTA-EP program implementing combined isotropic and kinematic hardening behavior and NONSTA-VP program implementing Chaboche model, which is so called viscoplasticity model, have been developed and have been continuously improved. In the year of 2000, NONSTA-OW program implementing Ohno-Wang model which can simulate progressive plasticity (that is ratcheting) more precisely compared to other models. One of the characteristics of inelastic constitutive equations is to have various numbers of material parameters to simulate complex material behaviors realistically and it is very important to obtain these material parameters. In this project, the improved method to obtain these material parameters has been studied with the optimal technique and by conducting material characteristic tests under high temperature conditions. The feasibility of the developed program with Ohno-Wang model, which contains 9 isotropic constitutive equations, has been studied through the example problem

Temperature effects on waste glass performance

International Nuclear Information System (INIS)

Mazer, J.J.

1991-02-01

The temperature dependence of glass durability, particularly that of nuclear waste glasses, is assessed by reviewing past studies. The reaction mechanism for glass dissolution in water is complex and involves multiple simultaneous reaction proceeded, including molecular water diffusion, ion exchange, surface reaction, and precipitation. These processes can change in relative importance or dominance with time or changes in temperature. The temperature dependence of each reaction process has been shown to follow an Arrhenius relationship in studies where the reaction process has been isolated, but the overall temperature dependence for nuclear waste glass reaction mechanisms is less well understood, Nuclear waste glass studies have often neglected to identify and characterize the reaction mechanism because of difficulties in performing microanalyses; thus, it is unclear if such results can be extrapolated to other temperatures or reaction times. Recent developments in analytical capabilities suggest that investigations of nuclear waste glass reactions with water can lead to better understandings of their reaction mechanisms and their temperature dependences. Until a better understanding of glass reaction mechanisms is available, caution should be exercised in using temperature as an accelerating parameter. 76 refs., 1 tab

The reactions of magnesium and its alloys with moist gases at high temperatures

International Nuclear Information System (INIS)

Darras, R.

1963-02-01

The kinetics and mechanisms of the reaction of pure or low alloyed magnesium with various gas saturated by water vapor: oxygen, argon, nitrogen, air, carbon dioxide, have been studied and compared in the temperature range 350-600 deg C. After picturing the large chemical reactivity of magnesium surface, the more or less properties of the oxide film, always made of magnesia, have been shown depending on the nature of the gas carrying water vapor; in fact, metal sublimation occurs the more easily as the surrounding atmosphere is less oxidizing. Moreover, an activation energy change is systematic, but at a temperature which depends also on the latter. In the case of the alloys, the linear oxidation rate is generally obtained only after short induction periods, parabolic in nature. Two possibilities of corrosion inhibition of magnesium by water vapor are then demonstrated and explained: either by a partial superficial fluoridation, or when the carrier gas is carbon dioxide. Also, the extreme conditions of oxidation were studied, that is the ignition processes that occur at a particular temperature in every gas mixture. Finally, it is tried to evolve the fundamental and practical significance of all the results. (author) [fr

Spectral studies of intermediate species formed in one-electron reactions of bovine liver catalase at room and low temperatures. A comparison with peroxidase reactions

International Nuclear Information System (INIS)

Metodiewa, D.; Dunford, H.B.

1992-01-01

The reactions of native bovine catalase with superoxide and solvated electrons have been investigated using three different methods for generating these reducing substrates: γ-radiolysis of oxygenated or deaerated buffer solutions in the presence of an OH radical scavenger; either xanthine or acetaldehyde with xanthine oxidase; and low-temperature (77 K) γ-radiolysis of buffered ethylene glycol/water solutions with subsequent annealing of samples at 183 K. (Author)

Simultaneous catalytic conversion of cellulose and corncob xylan under temperature programming for enhanced sorbitol and xylitol production.

Science.gov (United States)

Ribeiro, Lucília Sousa; Órfão, José J de Melo; Pereira, Manuel Fernando Ribeiro

2017-11-01

Sorbitol and xylitol yields can be improved by converting cellulose and xylan simultaneously, due to a synergetic effect between both substrates. Furthermore, both yields can be greatly enhanced by simply adjusting the reaction conditions regarding the optimum for the production of each product, since xylitol (from xylan) and sorbitol (from cellulose) yields are maximized when the reaction is carried out at 170 and 205°C, respectively. Therefore, the combination of a simultaneous conversion of cellulose and xylan with a two-step temperature approach, which consists in the variation of the reaction temperature from 170 to 205°C after 2h, showed to be a good strategy for maximizing the production of sorbitol and xylitol directly from mixture of cellulose and xylan. Using this new and environmentally friendly approach, yields of sorbitol and xylitol of 75 and 77%, respectively, were obtained after 6h of reaction. Copyright © 2017 Elsevier Ltd. All rights reserved.

A temperature control method for shortening thermal cycling time to achieve rapid polymerase chain reaction (PCR) in a disposable polymer microfluidic device

DEFF Research Database (Denmark)

Bu, Minqiang; Perch-Nielsen, Ivan R.; Sørensen, Karen Skotte

2013-01-01

steps to achieve a rapid ramping between the temperature steps for DNA denaturation, annealing and extension. The temperature dynamics within the microfluidic PCR chamber was characterized and the overshooting and undershooting parameters were optimized using the temperature-dependent fluorescence......We present a temperature control method capable of effectively shortening the thermal cycling time of polymerase chain reaction (PCR) in a disposable polymer microfluidic device with an external heater and a temperature sensor. The method employs optimized temperature overshooting and undershooting...

1,3,5-Triethylbenzene Transformation Reactions Compared to Its Transalkylation Reaction with Ethylbenzene

KAUST Repository

Akhtar, M. Naseem; Sulaiman, Al Khattaf

2009-01-01

The transalkylation of 1,3,5-triethylbenzene (1,3,5-TEB) with ethylbenzene (EB) has been studied over USYtype catalysts using a riser simulator that mimics the operation of a fluidized-bed reactor. The reaction mixture EB and 1,3,5-TEB was used at a molar ratio of 1:1, which is equivalent to 40:60 wt % of EB/1,3,5-TEB, respectively. The reaction temperature was varied from 350 to 500 °C with a time on stream ranging from 3-15 s. The effect of reaction conditions on 1,3,5-TEB conversion, DEB selectivity, and isomerization of 1,3,5-TEB is reported. The transalkylation of 1,3,5-TEB with EB has been compared to the transformation reaction of pure 1,3,5-TEB and EB. The experimental results have revealed that reactivity of 1,3,5-TEB and selectivity of DEB is increased during the transalkylation reaction (EB + 1,3,5-TEB) as compared to the transformation reaction of pure EB or 1,3,5-TEB. The 1,3,5-TEB undergoes isomerization and a cracking reaction to produce DEB and EB but does not undergo any appreciable disproportionation reaction. The isomerization of 1,3,5-TEB is more active at low temperatures, while cracking is more active at high temperatures. © 2009 American Chemical Society.

1,3,5-Triethylbenzene Transformation Reactions Compared to Its Transalkylation Reaction with Ethylbenzene

KAUST Repository

Akhtar, M. Naseem

2009-08-20

The transalkylation of 1,3,5-triethylbenzene (1,3,5-TEB) with ethylbenzene (EB) has been studied over USYtype catalysts using a riser simulator that mimics the operation of a fluidized-bed reactor. The reaction mixture EB and 1,3,5-TEB was used at a molar ratio of 1:1, which is equivalent to 40:60 wt % of EB/1,3,5-TEB, respectively. The reaction temperature was varied from 350 to 500 °C with a time on stream ranging from 3-15 s. The effect of reaction conditions on 1,3,5-TEB conversion, DEB selectivity, and isomerization of 1,3,5-TEB is reported. The transalkylation of 1,3,5-TEB with EB has been compared to the transformation reaction of pure 1,3,5-TEB and EB. The experimental results have revealed that reactivity of 1,3,5-TEB and selectivity of DEB is increased during the transalkylation reaction (EB + 1,3,5-TEB) as compared to the transformation reaction of pure EB or 1,3,5-TEB. The 1,3,5-TEB undergoes isomerization and a cracking reaction to produce DEB and EB but does not undergo any appreciable disproportionation reaction. The isomerization of 1,3,5-TEB is more active at low temperatures, while cracking is more active at high temperatures. © 2009 American Chemical Society.

Preparation of ultra-fine calcium carbonate by a solvent-free reaction using supersonic airflow and low temperatures

OpenAIRE

Cai, Yan-Hua; Ma, Dong-Mei; Peng, Ru-Fang; Chu, Shi-Jin

2008-01-01

The treatment of calcium chloride with sodium carbonate under solvent-free conditions with a supersonic airflow and at a low heating temperature leads to the synthesis of ultra-fine calcium carbonate. The reaction not only involves mild conditions, a simple operation, and high yields but also gives a high conversion rate.

A theoretical study of the mechanism of the atmospherically relevant reaction of chlorine atoms with methyl nitrate, and calculation of the reaction rate coefficients at temperatures relevant to the troposphere.

Science.gov (United States)

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

2015-03-21

The reaction between atomic chlorine (Cl) and methyl nitrate (CH3ONO2) is significant in the atmosphere, as Cl is a key oxidant, especially in the marine boundary layer, and alkyl nitrates are important nitrogen-containing organic compounds, which are temporary reservoirs of the reactive nitrogen oxides NO, NO2 and NO3 (NOx). Four reaction channels HCl + CH2ONO2, CH3OCl + NO2, CH3Cl + NO3 and CH3O + ClNO2 were considered. The major channel is found to be the H abstraction channel, to give the products HCl + CH2ONO2. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/6-31+G** level, while relative electronic energies were improved to the UCCSD(T*)-F12/CBS level. The reaction barrier (ΔE(‡)0K) and reaction enthalpy (ΔH(RX)298K) of the H abstraction channel were computed to be 0.61 and -2.30 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS//M06-2X/6-31+G** level. Reaction barriers (ΔE(‡)0K) for the other channels are more positive and these pathways do not contribute to the overall reaction rate coefficient in the temperature range considered (200-400 K). Rate coefficients were calculated for the H-abstraction channel at various levels of variational transition state theory (VTST) including tunnelling. Recommended ICVT/SCT rate coefficients in the temperature range 200-400 K are presented for the first time for this reaction. The values obtained in the 200-300 K region are particularly important as they will be valuable for atmospheric modelling calculations involving reactions with methyl nitrate. The implications of the results to atmospheric chemistry are discussed. Also, the enthalpies of formation, ΔHf,298K, of CH3ONO2 and CH2ONO2 were computed to be -29.7 and 19.3 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS level.

A novel rate of the reaction between NaOH with CO2 at low temperature in spray dryer

Directory of Open Access Journals (Sweden)

Yadollah Tavan

2017-03-01

Full Text Available Carbon dioxide (CO2 is an influential greenhouse gas that has a significant impact on global warming partly. Nowadays, many techniques are available to control and remove CO2 in different chemical processes. Since the spray dryer has high removal efficiency rate, a laboratory-scale spray dryer is used to absorb carbon dioxide from air in aqueous solution of NaOH. In the present study, the impact of NaOH concentration, operating temperature and nozzle diameter on removal efficiency of CO2 is explored through experimental study. Moreover, the reaction kinetic of NaOH with CO2 is studied over the temperature range of 50–100 °C in a laboratory-scale spray dryer absorber. In the present contribution, a simple reaction rate equation is proposed that shows the lowest deviation from the experimental data with error less than 2%.

Investigation of Na-CO{sub 2} Reaction with Initial Reaction in Various Reacting Surface

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of); Wi, Myung-Hwan [KAERI, Daejeon (Korea, Republic of)

2015-10-15

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO{sub 2} reaction according to various experimental parameter. Unlike SWR, Na-CO{sub 2} reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO{sub 2} reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO{sub 2} gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO{sub 2} interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO{sub 2} brayton cycle energy conversion system for Na-CO{sub 2} heat exchanger. And next parameter is sodium surface area which contact between sodium and CO{sub 2} when CO{sub 2} is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm{sup 2}. Additionally, it has been reported in recent years that CO{sub 2} Flow rate affects reactivity less significantly and CO{sub 2} flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO{sub 2} flow rate. Na-CO{sub 2} reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO{sub 2}. Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a

Uranium/water vapor reactions in gaseous atmospheres

International Nuclear Information System (INIS)

Jackson, R.L.; Condon, J.B.; Steckel, L.M.

1977-07-01

Experiments have been performed to determine the effect of varying humidities, gaseous atmospheres, and temperatures on the uranium/water vapor reaction. A balance, which allowed continuous in-system weighings, was used to determine the rates of the uranium/water vapor reactions at water vapor pressures of 383, 1586, and 2853 Pa and at temperatures of 80, 100, and 150 0 C in atmospheres of hydrogen, argon, or argon/oxygen mixtures. Based on rate data, the reactions were characterized as hydriding or nonhydriding. Hydriding reactions were found to be preferred in moist hydrogen systems at the higher temperatures and the lower humidities. The presence of hydrogen in hydriding systems was found to initially inhibit the reaction, but causes an acceleration of the rate in the final stages. In general, reaction rates of hydriding systems approached the hydriding rates calculated and observed in dry hydrogen. Hydriding and nonhydriding reaction rates showed a positive correlation to temperature and water vapor pressure. Final reaction rates in moist argon/oxygen mixtures of 1.93, 4.57, and 9.08 mole percent oxygen were greater than the rates observed in moist hydrogen or argon. Final reaction rates were negatively correlated to the oxygen concentration

High stereoselectivity on low temperature Diels-Alder reactions

Directory of Open Access Journals (Sweden)

Invernize Paulo

2005-12-01

Full Text Available Abstract We have found that some of the usually poor dienophiles (2-cycloenones can undergo Diels-Alder reaction at -78°C with unusually high stereoselectivity in the presence of niobium pentachloride as a Lewis acid catalyst. A remarkable difference in reaction rates for unsubstituted and α- or β-methyl substituted 2-cycloenones was also observed.

Development of Refractory Ceramics for The Oxygen Evolution Reaction (OER) Electrocatalyst Support for Water Electrolysis at elevated temperatures

DEFF Research Database (Denmark)

Nikiforov, Aleksey; Prag, Carsten Brorson; Polonsky, J.

2012-01-01

Commercial TaC and Si3N4 powders were tested as possible electrocatalyst support materials for the Oxygen Evolution Reaction (OER) for PEM water electrolysers, operating at elevated temperatures. TaC and Si3N4 were characterised by thermogravimmetric and differential thermal analysis...

Programming chemical kinetics: engineering dynamic reaction networks with DNA strand displacement

Science.gov (United States)

Srinivas, Niranjan

Over the last century, the silicon revolution has enabled us to build faster, smaller and more sophisticated computers. Today, these computers control phones, cars, satellites, assembly lines, and other electromechanical devices. Just as electrical wiring controls electromechanical devices, living organisms employ "chemical wiring" to make decisions about their environment and control physical processes. Currently, the big difference between these two substrates is that while we have the abstractions, design principles, verification and fabrication techniques in place for programming with silicon, we have no comparable understanding or expertise for programming chemistry. In this thesis we take a small step towards the goal of learning how to systematically engineer prescribed non-equilibrium dynamical behaviors in chemical systems. We use the formalism of chemical reaction networks (CRNs), combined with mass-action kinetics, as our programming language for specifying dynamical behaviors. Leveraging the tools of nucleic acid nanotechnology (introduced in Chapter 1), we employ synthetic DNA molecules as our molecular architecture and toehold-mediated DNA strand displacement as our reaction primitive. Abstraction, modular design and systematic fabrication can work only with well-understood and quantitatively characterized tools. Therefore, we embark on a detailed study of the "device physics" of DNA strand displacement (Chapter 2). We present a unified view of strand displacement biophysics and kinetics by studying the process at multiple levels of detail, using an intuitive model of a random walk on a 1-dimensional energy landscape, a secondary structure kinetics model with single base-pair steps, and a coarse-grained molecular model that incorporates three-dimensional geometric and steric effects. Further, we experimentally investigate the thermodynamics of three-way branch migration. Our findings are consistent with previously measured or inferred rates for

A novel temperature control method for shortening thermal cycling time to achieve rapid polymerase chain reaction (PCR) in a disposable polymer microfluidic device

DEFF Research Database (Denmark)

Bu, Minqiang; R. Perch-Nielsen, Ivan; Sørensen, Karen Skotte

steps to achieve a rapid ramping between the temperature steps for DNA denaturation, annealing and extension. The temperature dynamics within the microfluidic PCR chamber was characterized and the overshooting and undershooting parameters were optimized using the temperature dependent fluorescence......We present a new temperature control method capable of effectively shortening the thermal cycling time of polymerase chain reaction (PCR) in a disposable polymer microfluidic device with external heater and temperature sensor. The method employs optimized temperature overshooting and undershooting...

Research program of the high temperature engineering test reactor for upgrading the HTGR technology

International Nuclear Information System (INIS)

Kunitomi, Kazuhiko; Tachibana, Yukio; Takeda, Takeshi; Saikusa, Akio; Sawa, Kazuhiro

1997-07-01

The High Temperature Engineering Test Reactor (HTTR) is a graphite-moderated and helium-cooled reactor with an outlet power of 30 MW and outlet coolant temperature of 950degC, and its first criticality will be attained at the end of 1997. In the HTTR, researches establishing and upgrading the technology basis necessary for an HTGR and innovative basic researches for a high temperature engineering will be conducted. A research program of the HTTR for upgrading the technology basis for the HTGR was determined considering realization of future generation commercial HTGRs. This paper describes a research program of the HTTR. (author)

High-temperature shock tube and modeling studies on the reactions of methanol with D-atoms and CH3-radicals.

Science.gov (United States)

Peukert, S L; Michael, J V

2013-10-10

The shock tube technique has been used to study the hydrogen abstraction reactions D + CH3OH → CH2O + H + HD (A) and CH3 + CH3OH → CH2O + H + CH4 (B). For reaction A, the experiments span a T-range of 1016 K ≤ T ≤ 1325 K, at pressures 0.25 bar ≤ P ≤ 0.46 bar. The experiments on reaction B, CH3 + CH3OH, cover a T-range of 1138 K ≤ T ≤ 1270 K, at pressures around 0.40 bar. Reflected shock tube experiments, monitoring the depletion of D-atoms by applying D-atom atomic resonance absorption spectrometry (ARAS), were performed on reaction A using gas mixtures of C2D5I and CH3OH in Kr bath gas. C2D5I was used as precursor for D-atoms. For reaction B, reflected shock tube experiments monitoring H-atom formation with H-ARAS, were carried out using gas mixtures of diacetyl ((CH3CO)2) and CH3OH in Kr bath gas. (CH3CO)2 was used as the source of CH3-radicals. Detailed reaction models were assembled to fit the D-atom and H-atom time profiles in order to obtain experimental rate constants for reactions A and B. Total rate constants from the present experiments on D + CH3OH and CH3 + CH3OH can be represented by the Arrhenius equations kA(T) = 1.51 × 10(-10) exp(-3843 K/T) cm(3) molecules(-1) s(-1) (1016 K ≤ T ≤ 1325 K) and kB(T) = 9.62 × 10(-12) exp(-7477 K/T) cm(3) molecules(-1) s(-1) (1138 K ≤ T ≤ 1270 K). The experimentally obtained rate constants were compared with available rate data from the literature. The results from quantum chemical studies on reaction A were found to be in good agreement with the present results. The present work represents the first direct experimental study on these bimolecular reactions at combustion temperatures and is important to the high-temperature oxidation of CH3OH.

Temperature measurements in thermonuclear plasmas; Mesures des temperatures dans les plasmas thermonucleaires

Energy Technology Data Exchange (ETDEWEB)

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

1958-07-01

The temperatures needed to produce thermonuclear reactions are of the order of several million degrees Kelvin. Devising methods for measuring such temperatures has been the subject of research in many countries. In order to present the problem clearly and to demonstrate its importance, the author reviews the various conditions which must be fulfilled in order that reactions may be qualified as thermonuclear. The relationship between the temperature and the cross-section of the reactions is studied, and it is shown that the notion of temperature in the plasmas is complex, which leads to a consideration of the temperature of the ions and that of the electrons. None of the methods for the temperature measurements is completely satisfactory because of the hypotheses which must be made, and which are seldom fulfilled during high-intensity discharges in the plasmas. In practice it is necessary to use several methods simultaneously. (author) [French] Les temperatures necessaires pour produire des reactions thermonucleaires sont de l'ordre de plusieurs millions de degres Kelvin. Les methodes envisagees pour mesurer ces temperatures font l'objet de recherches dans de nombreux pays. Afin de preciser le probleme et de montrer son importance, l'auteur rappelle les conditions qui doivent etre reunies pour que des reactions puissent etre qualifiees thermonucleaires. Il etudie la relation entre la temperature et la section efficace des reactions et montre que la notion de temperature dans les plasmas est complexe, ce qui amene a considerer la temperature des ions et celle des electrons. Aucune des methodes de mesure des temperatures n'est completement satisfaisante en raison des hypotheses qu'elles exigent et qui sont rarement realisees lors des decharges a haute intensite dans les plasmas. En pratique, il est necessaire d'utiliser plusieurs methodes simultanement. (auteur)

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

Science.gov (United States)

Kaiser, E W; Jawad, Khadija M

2014-05-08

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

Influence of the Reaction Temperature on the Nature of the Active and Deactivating Species during Methanol to Olefins Conversion over H-SSZ-13

NARCIS (Netherlands)

Borodina, E.; Meirer, F.; Lezcano-Gonzalez, I.; Mokhtar, M.; Asiri, A. M.; Al-Thabaiti, S. A.; Basahel, S. N.; Ruiz-Martinez, J.; Weckhuysen, B. M.

The formation of hydrocarbon species during the methanol to olefins (MTO) reaction over zeolite H-SSZ-13 has been systematically studied at reaction temperatures between 573 and 723 K with a combination of operando UV-vis spectroscopy and online gas chromatography. It was found that the applied

Catalyst dispersion and activity under conditions of temperature-staged liquefaction

Energy Technology Data Exchange (ETDEWEB)

Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

1993-02-01

This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275[degrees]C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

Temperature field in concrete when in contact with hot liquids

International Nuclear Information System (INIS)

Andrade Lima, F.R. de.

1981-09-01

In an HCDA (Hypothetical Core Disruptive Accident) it is postulated that liquid metal coolants and core materials come in contact with the retaining concrete structure. A mathematical model and an associated computer program was previously developed to describle the transient heat and mass transfer in the concrete. Implementations on the original program-USINT- are included to consider the variations of the thermal conductivity as a function of the temperature. Also a subroutine - PLOTTI - is incorporated to the program for the plotting of the results. The new program - USINTG - is used to calculate the temperature and pressure fields and the water released from concrete structures during a sodium leak simulation and with the concrete structures in contact with liquid sodium. No consideration about chemical reactions involving the sodium when in contact with concrete is considered. (Author) [pt

Reaction of tellurium with Zircaloy-4

International Nuclear Information System (INIS)

Boer, R. de; Cordfunke, E.H.P.

1994-09-01

Interaction of tellurium vapour with Zircaloy during the initial stage of an accident will lead to retention of tellurium in the core. For reliable estimation of the release behaviour of tellurium, it is necessary to know which zirconium tellurides are formed during this interaction. In this work the reaction of tellurium with Zircaloy-4 has been studied, using various reaction temperatures and tellurium vapour pressures. The compound ZrTe 2-x is formed on the surface of the Zircaloy in a broad range of reaction temperatures and vapour pressures. It is found that the formation of the more zirconium-rich compound Zr 5 Te 4 is favoured at high reaction temperatures is combination with low tellurium vapour pressures. (orig.)

RBS investigations of high-temperature reactions on graphite substrates

Energy Technology Data Exchange (ETDEWEB)

Eloi, C.C. [Kentucky Univ., Lexington, KY (United States). Dept. of Chemistry]|[Center for Applied Energy Research, University of Kentucky, Lexington, KY 40506 (United States); Robertson, J.D. [Kentucky Univ., Lexington, KY (United States). Dept. of Chemistry]|[Center for Applied Energy Research, University of Kentucky, Lexington, KY 40506 (United States); Majidi, V. [Kentucky Univ., Lexington, KY (United States). Dept. of Chemistry

1995-05-01

While graphite furnace atomic absorption spectrometry (GFAAS) is one of the most powerful techniques for ultratrace analysis of Pb, it is often plagued by matrix interferences. These interferences are minimized by the addition of matrix modifiers which stabilize the analyte signal through unknown mechanisms. Using RBS, the high temperature reactions of nitrate salts of Pb were studied on pyrolytically coated graphite with and without matrix modifiers. The addition of an ammonium phosphate modifier was found to stabilize Pb through the formation of a metal oxy-phosphorus compound. Moreover, the depth profiles demonstrated that the pyrolytically coated graphite was not impervious as previously thought. Pre-treatment of the surface with O{sub 2} is also known to cause a delay in the vaporization of Pb. While a surface effect had previously been postulated, the 3.04 MeV resonance {sup 16}O({alpha}, {alpha}){sup 16}O elastic scattering measurements show that it proceeds through the formation of surface bound lead-oxygen species as the number of oxygen atoms chemisorbed and the number of lead atoms, present on the surface prior to vaporization, are nearly equal. (orig.).

High temperature magnetic properties of Co(FeY){sub 2}O{sub 4} synthesized by combustion reaction

Energy Technology Data Exchange (ETDEWEB)

Alves, Thiago Eduardo Pereira, E-mail: thiago.ifgo@gmail.com [Instituto Federal de Educacao, Ciencia e Tecnologia de Goias (IFGO), Goiania (Brazil); Franco Junior, Adolfo [Universidade Federal de Goias (UFG), Goiania (Brazil)

2016-07-01

Full text: Cobalt ferrite is widely studied due to its interesting magnetic behavior at room temperature. However, many technical applications require temperatures that are above that. Thus, it is necessary to understand how some magnetic properties, such as saturation magnetization (Ms), remanent magnetization (Mr), and coercivity (Hc), may behave at high temperatures [1]. Among several methods to synthesize cobalt ferrites, combustion reaction method is intensively used because it is inexpensive, fast and has good control on the stoichiometry. This method is based on the chemistry of propellants and explosives [2]. Therefore, we have prepared a series of nanoparticles of CoFe{sub (2-x)}Y{sub x}O{sub 4}, with x ranging from 0.00 to 0.04, by combustion reaction method. The crystal structure and morphology were characterized by X-ray diffraction (XRD) using Rietveld refinement and transmission electron microscopy (TEM), respectively. Nanocrystalline particles structures in the typical phase of spinel were observed on diffractograms. Micrographies showed high crystalline powders for the particles and particles size within nanoscale range. The magnetic properties were measured by vibrating sample magnetometry (VSM) in broad range of temperature (300-850K). Saturation magnetization (Ms) decreases with Y doping increase, while Hc increases, being about 1.8 higher than the undoped sample. Furthermore, Curie temperature increases with Y doping increase. These magnetic properties were discussed in terms of the particle interactions induced by the thermal fluctuations, cation distribution, and ions exchange between yttrium and cobalt atoms in A-B sites in the cubic structure [3]. References: [1] A. Franco, Jr. and F. C. e Silva, Applied Physics Letters 96, 172505, (2010). 525 [2] S.R. Jain, et al, Combustion and flame 40, 71-79, (1981). [3] A. Franco Jr. et al. Journal of Alloys and Compounds 680, 198-205, (2016). (author)

Enhancing chemical reactions

Science.gov (United States)

Morrey, John R.

1978-01-01

Methods of enhancing selected chemical reactions. The population of a selected high vibrational energy state of a reactant molecule is increased substantially above its population at thermal equilibrium by directing onto the molecule a beam of radiant energy from a laser having a combination of frequency and intensity selected to pump the selected energy state, and the reaction is carried out with the temperature, pressure, and concentrations of reactants maintained at a combination of values selected to optimize the reaction in preference to thermal degradation by transforming the absorbed energy into translational motion. The reaction temperature is selected to optimize the reaction. Typically a laser and a frequency doubler emit radiant energy at frequencies of .nu. and 2.nu. into an optical dye within an optical cavity capable of being tuned to a wanted frequency .delta. or a parametric oscillator comprising a non-centrosymmetric crystal having two indices of refraction, to emit radiant energy at the frequencies of .nu., 2.nu., and .delta. (and, with a parametric oscillator, also at 2.nu.-.delta.). Each unwanted frequency is filtered out, and each desired frequency is focused to the desired radiation flux within a reaction chamber and is reflected repeatedly through the chamber while reactants are fed into the chamber and reaction products are removed therefrom.

Development of Bi-phase sodium-oxygen-hydrogen chemical equilibrium calculation program (BISHOP) using Gibbs free energy minimization method

International Nuclear Information System (INIS)

Okano, Yasushi

1999-08-01

In order to analyze the reaction heat and compounds due to sodium combustion, the multiphase chemical equilibrium calculation program for chemical reaction among sodium, oxygen and hydrogen is developed in this study. The developed numerical program is named BISHOP; which denotes Bi-Phase, Sodium - Oxygen - Hydrogen, Chemical Equilibrium Calculation Program'. Gibbs free energy minimization method is used because of the special merits that easily add and change chemical species, and generally deal many thermochemical reaction systems in addition to constant temperature and pressure one. Three new methods are developed for solving multi-phase sodium reaction system in this study. One is to construct equation system by simplifying phase, and the other is to expand the Gibbs free energy minimization method into multi-phase system, and the last is to establish the effective searching method for the minimum value. Chemical compounds by the combustion of sodium in the air are calculated using BISHOP. The Calculated temperature and moisture conditions where sodium-oxide and hydroxide are formed qualitatively agree with the experiments. Deformation of sodium hydride is calculated by the program. The estimated result of the relationship between the deformation temperature and pressure closely agree with the well known experimental equation of Roy and Rodgers. It is concluded that BISHOP can be used for evaluated the combustion and deformation behaviors of sodium and its compounds. Hydrogen formation condition of the dump-tank room at the sodium leak event of FBR is quantitatively evaluated by BISHOP. It can be concluded that to keep the temperature of dump-tank room lower is effective method to suppress the formation of hydrogen. In case of choosing the lower inflammability limit of 4.1 mol% as the hydrogen concentration criterion, formation reaction of sodium hydride from sodium and hydrogen is facilitated below the room temperature of 800 K, and concentration of hydrogen

Development of a program for evaluating the temperature of SMART-P fuel rod

Energy Technology Data Exchange (ETDEWEB)

Cheon, Jin Sik; Lee, Byung Ho; Koo, Yang Hyun; Oh, Je Yong; Yim, Jeong Sik; Sohn, Dong Seong

2003-11-01

A code for evaluating the temperature of SMART-P fuel rod has been developed. Finite Element (FE) method is adopted for the developed code sharing the user subroutines which has been prepared for the ABAQUS commercial FE code. The developed program for SMART-P fuel rod corresponds to a nonlinear transient heat transfer problem, and uses a sparse matrix solver for FE equations during iterations at every time step. The verifications of the developed program were conducted using the ABAQUS code. Steady state and transient problems were analyzed for 1/8 rod model due to the symmetry of the fuel rod and full model. From the evaluation of temperature for the 1/8 rod model at steady state, maximal error of 0.18 % was present relative to the ABAQUS result. Analysis for the transient problem using the fuel rod model resulted in the same as the variation of centerline temperature from the ABAQUS code during a hypothetical power transient. Also, given a power depression in fuel meat as a function of burnup, its effect on the centerline temperature was more precisely evaluated by the developed program compared to the ABAQUS code. The distribution of heat flux for the entire cross section and surface was almost identical for the two codes.

Qualitative Assessment of a 3D Simulation Program: Faculty, Students, and Bio-Organic Reaction Animations

Science.gov (United States)

Günersel, Adalet B.; Fleming, Steven A.

2013-01-01

Research shows that computer-based simulations and animations are especially helpful in fields such as chemistry where concepts are abstract and cannot be directly observed. Bio-Organic Reaction Animations (BioORA) is a freely available 3D visualization software program developed to help students understand the chemistry of biomolecular events.…

General purpose nonlinear analysis program FINAS for elevated temperature design of FBR components

International Nuclear Information System (INIS)

Iwata, K.; Atsumo, H.; Kano, T.; Takeda, H.

1982-01-01

This paper presents currently available capabilities of a general purpose finite element nonlinear analysis program FINAS (FBR Inelastic Structural Analysis System) which has been developed at Power Reactor and Nuclear Fuel Development Corporation (PNC) since 1976 to support structural design of fast breeder reactor (FBR) components in Japan. This program is capable of treating inelastic responses of arbitrary complex structures subjected to static and dynamic load histories. Various types of finite element covering rods, beams, pipes, axisymmetric, two and three dimensional solids, plates and shells, are implemented in the program. The thermal elastic-plastic creep analysis is possible for each element type, with primary emphasis on the application to FBR components subjected to sustained or cyclic loads at elevated temperature. The program permits large deformation, buckling, fracture mechanics, and dynamic analyses for some of the element types and provides a number of options for automatic mesh generation and computer graphics. Some examples including elevated temperature effects are shown to demonstrate the accuracy and the efficiency of the program

Development of detailed analysis program for high-temperature crack growth evaluation

Energy Technology Data Exchange (ETDEWEB)

Takahashi, Yukio; Nakayama, Yasunari [Central Research Inst. of Electric Power Industry, Komae, Tokyo (Japan). Komae Research Lab

2001-04-01

Evaluation of crack growth as well as crack initiation is necessary to make realistic evaluation of structural integrity and life management of high-temperature plant components. Domain integral formulae for three kinds of nonlinear fracture mechanics parameters, i.e. J-integral, fatigue J-integral range and creep J-integral were derived for two-dimensional, three-dimensional and axi-symmetrical structures. Furthermore, methods for applying them to finite element results were derived and a computer program was developed for the general-purpose finite element program, MARC. The program was applied to various problems and its effectiveness was demonstrated. (author)

Multiyear Program Plan for the High Temperature Materials Laboratory

Energy Technology Data Exchange (ETDEWEB)

Arvid E. Pasto

2000-03-17

Recently, the U.S. Department of Energy's (DOE) Office of Heavy Vehicle Technologies (OHVT) prepared a Technology Roadmap describing the challenges facing development of higher fuel efficiency, less polluting sport utility vehicles, vans, and commercial trucks. Based on this roadmap, a multiyear program plan (MYPP) was also developed, in which approaches to solving the numerous challenges are enumerated. Additional planning has been performed by DOE and national laboratory staff, on approaches to solving the numerous challenges faced by heavy vehicle system improvements. Workshops and planning documents have been developed concerning advanced aerodynamics, frictional and other parasitic losses, and thermal management. Similarly, the Heavy Vehicle Propulsion Materials Program has developed its own multiyear program plan. The High Temperature Materials Laboratory, a major user facility sponsored by OHVT, has now developed its program plan, described herein. Information was gathered via participation in the development of OHVT's overall Technology Roadmap and MYPP, through personal contacts within the materials-user community, and from attendance at conferences and expositions. Major materials issues for the heavy vehicle industry currently center on trying to increase efficiency of (diesel) engines while at the same time reducing emissions (particularly NO{sub x} and particulates). These requirements dictate the use of increasingly stronger, higher-temperature capable and more corrosion-resistant materials of construction, as well as advanced catalysts, particulate traps, and other pollution-control devices. Exhaust gas recirculation (EGR) is a technique which will certainly be applied to diesel engines in the near future, and its use represents a formidable challenge, as will be described later. Energy-efficient, low cost materials processing methods and surface treatments to improve wear, fracture, and corrosion resistance are also required.

Temperature and excitation energy of hot nuclei in the reaction of 40Ar+197Au at 25 MeV/nucleon

International Nuclear Information System (INIS)

Wu, H.; Jin, G.; Li, Z.; Dai, G.; Qi, Y.; He, Z.; Luo, Q.; Duan, L.; Wen, W.; Zhang, B.

1997-01-01

The coincidence measurements between heavy fission fragments and light charged particles with Z ≤2 were carried out for the 40 Ar+ 197 Au reaction at 25 MeV/nucleon, to study the properties of hot nuclei in heavy ion induced reactions. The linear momentum transfers (LMTs) were deduced from the folding angle and the time-of-flight difference between two fission fragments of heavy residues. The relationship of the nuclear temperature (slope parameter of the energy spectrum) and the excitation energy was determined independently from the measurement of the kinetic energy spectra in the frames of the emitting sources and from the LMT analysis. Both the temperature and the excitation energy increase with decreasing impact parameter, which suggests that a plateau temperature of 5.5 MeV is reached at an excitation energy of 3.1 MeV/nucleon. The result was also compared with various statistical models that explain the plateau by the multifragmentation process, where the excitation energy is assumed to be stored in compression and expansion effects. (orig.)

Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C-Glycosylation Reactions at Room Temperature.

Science.gov (United States)

Hernan-Gomez, Alberto; Orr, Samantha; Uzelac, Marina; Kennedy, Alan; Barroso, Santiago; Jusseau, Xavier; Lemaire, Sebastien; Farina, Vittorio; Hevia, Eva

2018-06-01

Pairing a range of bis(aryl) zinc reagents ZnAr2 with the stronger Lewis acidic [(ZnArF2)] (ArF = C6F5), enables highly stereoselective cross-coupling between glycosyl bromides and ZnAr2 without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnArF2 acts as a non-coupling partner although its presence is crucial for the execution of the C(sp2)-C(sp3) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition-metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases vs. diarylzinc compounds (e.g. THF. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Wide temperature range (T = 295 K and 770-1305 K) study of the kinetics of the reactions HCO + NO and HCO + NO2 using frequency modulation spectroscopy.

Science.gov (United States)

Dammeier, J; Colberg, M; Friedrichs, G

2007-08-21

The rate constants for , HCO + NO --> HNO + CO, and , HCO + NO(2)--> products, have been measured at temperatures between 770 K modulation (FM) absorption spectroscopy. Kinetic simulations based on a comprehensive reaction mechanism showed that the rate constants for the title reactions could be sensitively extracted from the measured HCO profiles. The determined high temperature rate constants are k(1)(769-1307 K) = (7.1 +/- 2.7) x 10(12) cm(3) mol(-1) s(-1) and k(2)(804-1186 K) = (3.3 +/- 1.8) x 10(13) cm(3) mol(-1) s(-1). The room temperature values were found to be in very good agreement with existing literature data and show that both reactions are essentially temperature independent. The weak temperature dependence of can be explained by the interplay of a dominating direct abstraction pathway and a complex-forming mechanism. Both pathways yield the products HNO + CO. In contrast to , no evidence for a significant contribution of a direct high temperature abstraction channel was found for . Here, the observed temperature independent overall rate constant can be described by a complex-forming mechanism with several product channels. Detailed information on the strongly temperature dependent channel branching ratios is provided. Moreover, the high temperature rate constant of , OH + (CHO)(2), has been determined to be k(7) approximately 1.1 x 10(13) cm(3) mol(-1) s(-1).

Sensor programming and concept implementation of a temperature monitoring system, using Arduino as prototyping platform

DEFF Research Database (Denmark)

Sbîrnă, Sebastian; Søberg, Peder Veng; Sbîrnă, Liana Simona

2016-01-01

The present work reports the programming paradigms that have been developed for a temperature monitoring system able to provide accurate data regarding food temperatures inside refrigerated vehicles and alert the driver accordingly, in relation to which temperature states are encountered. The men...

High-pressure modulation of the structure of the bacterial photochemical reaction center at physiological and cryogenic temperatures

Science.gov (United States)

Timpmann, Kõu; Kangur, Liina; Lõhmus, Ants; Freiberg, Arvi

2017-07-01

The optical absorption and fluorescence response to external high pressure of the reaction center membrane chromoprotein complex from the wild-type non-sulfur photosynthetic bacterium Rhodobacter sphaeroides was investigated using the native pigment cofactors as local molecular probes of the reaction center structure at physiological (ambient) and cryogenic (79 K) temperatures. In detergent-purified complexes at ambient temperature, abrupt blue shift and accompanied broadening of the special pair band was observed at about 265 MPa. These reversible in pressure features were assigned to a pressure-induced rupture of a lone hydrogen bond that binds the photo-chemically active L-branch primary electron donor bacteriochlorophyll cofactor to the surrounding protein scaffold. In native membrane-protected complexes the hydrogen bond rupture appeared significantly restricted and occurred close to about 500 MPa. The free energy change associated with the rupture of the special pair hydrogen bond in isolate complexes was estimated to be equal to about 12 kJ mol-1. In frozen samples at cryogenic temperatures the hydrogen bond remained apparently intact up to the maximum utilized pressure of 600 MPa. In this case, however, heterogeneous spectral response of the cofactors from the L-and M-branches was observed due to anisotropic build-up of the protein structure. While in solid phase, the special pair fluorescence as a function of pressure exactly followed the respective absorption spectrum at a constant Stokes shift, at ambient temperature, the two paths began to deviate strongly from one other at the hydrogen bond rupture pressure. This effect was tentatively interpreted by different emission properties of hydrogen-bound and hydrogen-unbound special pair exciton states.

Detailed Reaction Kinetics for CFD Modeling of Nuclear Fuel Pellet Coating for High Temperature Gas-Cooled Reactors

International Nuclear Information System (INIS)

Battaglia, Francine

2008-01-01

The research project was related to the Advanced Fuel Cycle Initiative and was in direct alignment with advancing knowledge in the area of Nuclear Fuel Development related to the use of TRISO fuels for high-temperature reactors. The importance of properly coating nuclear fuel pellets received a renewed interest for the safe production of nuclear power to help meet the energy requirements of the United States. High-temperature gas-cooled nuclear reactors use fuel in the form of coated uranium particles, and it is the coating process that was of importance to this project. The coating process requires four coating layers to retain radioactive fission products from escaping into the environment. The first layer consists of porous carbon and serves as a buffer layer to attenuate the fission and accommodate the fuel kernel swelling. The second (inner) layer is of pyrocarbon and provides protection from fission products and supports the third layer, which is silicon carbide. The final (outer) layer is also pyrocarbon and provides a bonding surface and protective barrier for the entire pellet. The coating procedures for the silicon carbide and the outer pyrocarbon layers require knowledge of the detailed kinetics of the reaction processes in the gas phase and at the surfaces where the particles interact with the reactor walls. The intent of this project was to acquire detailed information on the reaction kinetics for the chemical vapor deposition (CVD) of carbon and silicon carbine on uranium fuel pellets, including the location of transition state structures, evaluation of the associated activation energies, and the use of these activation energies in the prediction of reaction rate constants. After the detailed reaction kinetics were determined, the reactions were implemented and tested in a computational fluid dynamics model, MFIX. The intention was to find a reduced mechanism set to reduce the computational time for a simulation, while still providing accurate results

Possibilities and limitations of fast temperature programming as a route towards fast GC

NARCIS (Netherlands)

Deursen, van M.M.; Beens, J.; Cramers, C.A.M.G.; Janssen, J.G.M.

1999-01-01

One possible way to speed up a gas chromatographic analysis is the application of fast temperature programming by using resistive heating techniques. With this heating technique programming rates up to 20° per second can be reached. A relative standard deviation of retention times better than 0.2%

Optimization Models for Reaction Networks: Information Divergence, Quadratic Programming and Kirchhoff’s Laws

Directory of Open Access Journals (Sweden)

Julio Michael Stern

2014-03-01

Full Text Available This article presents a simple derivation of optimization models for reaction networks leading to a generalized form of the mass-action law, and compares the formal structure of Minimum Information Divergence, Quadratic Programming and Kirchhoff type network models. These optimization models are used in related articles to develop and illustrate the operation of ontology alignment algorithms and to discuss closely connected issues concerning the epistemological and statistical significance of sharp or precise hypotheses in empirical science.

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.

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,

Hydrogenolysis reactions characteristics of deashed coal under low temperature; Teionka ni okeru dakkai shoritan no suisoka bunkai hanno tokusei

Energy Technology Data Exchange (ETDEWEB)

Owada, T.; Mashimo, K.; Wainai, T. [Nihon University, Tokyo (Japan). College of Science and Technology

1996-10-28

In relation to coal liquefaction, the effect of inorganic minerals on liquefaction reactivity and the effect of hydrofluoric acid (HF) treatment on organic molecular structure of coals were studied by demineralization of low-rank coals in HCl or HF solution. In experiment, Taiheiyo coal specimen was deashed in HCl solution at 25-70{degree}C for 6 hours while agitating, and in addition, deashed in HF solution. Hydrogenolysis of the deashed coal specimen was conducted using tetralin or methylnaphthalene as solvent under initial hydrogen pressure of 1.96MPa at reaction temperature of 693K for 60min. The experimental results are as follows. The ash content of Taiheiyo coal hardly offers catalysis in hydrogenolysis reaction. Carboxyl group increases in demineralization of coal because of breakage of bridged bonds. Organic structure of coal changes by demineralization in dense HF solution. Change in organic structure of coal by demineralization in dense HF solution is dependent on treatment temperature. 2 refs., 4 figs., 1 tab.

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.

Surface modification of highly oriented pyrolytic graphite by reaction with atomic nitrogen at high temperatures

International Nuclear Information System (INIS)

Zhang Luning; Pejakovic, Dusan A.; Geng Baisong; Marschall, Jochen

2011-01-01

Dry etching of {0 0 0 1} basal planes of highly oriented pyrolytic graphite (HOPG) using active nitridation by nitrogen atoms was investigated at low pressures and high temperatures. The etching process produces channels at grain boundaries and pits whose shapes depend on the reaction temperature. For temperatures below 600 deg. C, the majority of pits are nearly circular, with a small fraction of hexagonal pits with rounded edges. For temperatures above 600 deg. C, the pits are almost exclusively hexagonal with straight edges. The Raman spectra of samples etched at 1000 deg. C show the D mode near 1360 cm -1 , which is absent in pristine HOPG. For deep hexagonal pits that penetrate many graphene layers, neither the surface number density of pits nor the width of pit size distribution changes substantially with the nitridation time, suggesting that these pits are initiated at a fixed number of extended defects intersecting {0 0 0 1} planes. Shallow pits that penetrate 1-2 graphene layers have a wide size distribution, which suggests that these pits are initiated on pristine graphene surfaces from lattice vacancies continually formed by N atoms. A similar wide size distribution of shallow hexagonal pits is observed in an n-layer graphene sample after N-atom etching.

Reactor for exothermic reactions

Science.gov (United States)

Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

1993-03-02

A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

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

Science.gov (United States)

Gupta, Shikha; Basant, Nikita

2017-11-01

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

High-temperature gas-cooled reactor safety-reliability program plan

Energy Technology Data Exchange (ETDEWEB)

1981-03-01

The purpose of this document is to present a safety plan as part of an overall program plan for the design and development of the High Temperature Gas-Cooled Reactor (HTGR). This plan is intended to establish a logical framework for identifying the technology necessary to demonstrate that the requisite degree of public risk safety can be achieved economically. This plan provides a coherent system safety approach together with goals and success criterion as part of a unifying strategy for licensing a lead reactor plant in the near term. It is intended to provide guidance to program participants involved in producing a technology base for the HTGR that is fully responsive to safety consideration in the design, evaluation, licensing, public acceptance, and economic optimization of reactor systems.

Investigation of reactions and species dominating low temperature combustion - Final report

Energy Technology Data Exchange (ETDEWEB)

Radi, P.; Knopp, G.; Johnson, M.; Boedi, A.; Gerber, T.

2009-12-15

This report for the Swiss Federal Office of Energy (SFOE) presents the results of work done at the Paul Scherrer Institute (PSI) in Switzerland. The project 'Investigation of reactions and species dominating low temperature combustion' involves the characterisation of species that govern ignition. A base established for the spectroscopic investigation of peroxy radicals is discussed. The two-fold aim of this project is discussed which includes the measurement of molecular features such as binding energies and dissociation patterns of well-studied and spectroscopically accessible molecules and radicals as well as the application of the measurement techniques to alkyl peroxy radicals. This was done in order to improve the database of a class of molecules playing a dominant role in combustion and atmospheric chemistry. Several experimental techniques that are to be developed to achieve these aims are looked at. Achievements made are discussed and future work to be carried out is noted.

Temperature-programmed desorption for membrane inlet mass spectrometry

DEFF Research Database (Denmark)

Ketola, R.A.; Grøn, C.; Lauritsen, F.R.

1998-01-01

We present a novel technique for analyzing volatile organic compounds in air samples using a solid adsorbent together with temperature-programmed desorption and subsequent detection by membrane inlet mass spectrometry (TPD-MIMS). The new system has the advantage of a fast separation of compounds...... to diffuse through the membrane into the mass spectrometer in a few seconds. In this fashion we could completely separate many similar volatile compounds, for example toluene from xylene and trichloroethene from tetrachloroethene. Typical detection limits were at low or sub-nanogram levels, the dynamic range...

Gibbs free energy of reactions involving SiC, Si3N4, H2, and H2O as a function of temperature and pressure

Science.gov (United States)

Isham, M. A.

1992-01-01

Silicon carbide and silicon nitride are considered for application as structural materials and coating in advanced propulsion systems including nuclear thermal. Three-dimensional Gibbs free energy were constructed for reactions involving these materials in H2 and H2/H2O. Free energy plots are functions of temperature and pressure. Calculations used the definition of Gibbs free energy where the spontaneity of reactions is calculated as a function of temperature and pressure. Silicon carbide decomposes to Si and CH4 in pure H2 and forms a SiO2 scale in a wet atmosphere. Silicon nitride remains stable under all conditions. There was no apparent difference in reaction thermodynamics between ideal and Van der Waals treatment of gaseous species.

The reaction of hydrazine nitrate with nitric acid

International Nuclear Information System (INIS)

Kida, Takashi; Sugikawa, Susumu

2004-03-01

It is known that hydrazine nitrate used in nuclear fuel reprocessing plants is an unstable substance thermochemically like hydroxylamine nitrate. In order to take the basic data regarding the reaction of hydrazine nitrate with nitric acid, initiation temperatures and heats of this reaction, effect of impurity on initiation temperature and self-accelerating reaction when it holds at constant temperature for a long time were measured by the pressure vessel type reaction calorimeter etc. In this paper, the experimental data and evaluation of the safe handling of hydrazine nitrate in nuclear fuel reprocessing plants are described. (author)

Fast Neutral reactions in cold interstellar clouds

International Nuclear Information System (INIS)

Graff, M.M.

1989-01-01

The dynamics of exothermic neutral reactions between radical species have been examined, with particular attention to reactivity at the very low energies characteristic of cold interstellar clouds. Long-range interactions (electrostatic and spin-orbit) were considered within in the adiabatic capture-infinite order sudden approximation (ACIOSA). Analytic expressions have been developed for cross sections and rate constants of exothermic reactions between atoms and dipolar radicals at low temperatures. A method for approximating the adiabatic potential surface for the reactive state will be presented. The reaction systems O+OH and O+CH are both predicted to be fast at low temperatures. The systems C+CH and C+OH are expected to be nonreactive at low temperatures, and upper limits of rate constants for these reactions have been estimated. General predictions are made for other reaction systems. Implications for interstellar chemistry will be discussed

Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry and quantum chemical methods.

Science.gov (United States)

Kulik, Tetiana V; Lipkovska, Natalia O; Barvinchenko, Valentyna M; Palyanytsya, Borys B; Kazakova, Olga A; Dudik, Olesia O; Menyhárd, Alfréd; László, Krisztina

2016-05-15

Thermochemical studies of hydroxycinnamic acid derivatives and their surface complexes are important for the pharmaceutical industry, medicine and for the development of technologies of heterogeneous biomass pyrolysis. In this study, structural and thermal transformations of caffeic acid complexes on silica surfaces were studied by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry (TPD MS) and quantum chemical methods. Two types of caffeic acid surface complexes are found to form through phenolic or carboxyl groups. The kinetic parameters of the chemical reactions of caffeic acid on silica surface are calculated. The mechanisms of thermal transformations of the caffeic chemisorbed surface complexes are proposed. Thermal decomposition of caffeic acid complex chemisorbed through grafted ester group proceeds via three parallel reactions, producing ketene, vinyl and acetylene derivatives of 1,2-dihydroxybenzene. Immobilization of phenolic acids on the silica surface improves greatly their thermal stability. Copyright © 2016 Elsevier Inc. All rights reserved.

A low temperature investigation of the gas-phase N(2D) + NO reaction. Towards a viable source of N(2D) atoms for kinetic studies in astrochemistry.

Science.gov (United States)

Nuñez-Reyes, Dianailys; Hickson, Kevin M

2018-06-18

The gas-phase reaction of metastable atomic nitrogen N(2D) with nitric oxide has been investigated over the 296-50 K temperature range using a supersonic flow reactor. As N(2D) could not be produced photolytically in the present work, these excited state atoms were generated instead through the C(3P) + NO → N(2D) + CO reaction while C(3P) atoms were created in situ by the 266 nm pulsed laser photolysis of CBr4 precursor molecules. The kinetics of N(2D) atoms were followed on-resonance by vacuum ultraviolet laser induced fluorescence at 116.7 nm. The measured rate constants for the N(2D) + NO reaction are in excellent agreement with most of the earlier work at room temperature and represent the only available kinetic data for this process below 296 K. The rate constants are seen to increase slightly as the temperature falls to 100 K with a more substantial increase at even lower temperature; a finding which is not reproduced by theoretical work. The prospects for using this chemical source of N(2D) atoms in future studies of a wide range of N(2D) atom reactions are discussed.

Catalyst dispersion and activity under conditions of temperature-staged liquefaction. Final report

Energy Technology Data Exchange (ETDEWEB)

Davis, A.; Schobert, H.H.; Mitchell, G.D.; Artok, L.

1993-02-01

This research program involves the investigation of the use of highly dispersed catalyst precursors for the pretreatment of coals by mild hydrogenation. During the course of this effort solvent preswelling of the coal was evaluated as a means of deeply impregnating catalysts into coal, active phases of catalysts under reaction conditions were studied and the impact of these techniques were evaluated during pretreatment and temperature-staged liquefaction. Two coals, a Texas subbituminous and a Utah high volatile A bituminous, were used to examine the effects of solvent swelling pretreatment and catalyst impregnation on conversion behavior at 275{degrees}C, representative of the first, low-temperature stage in a temperature-staged liquefaction reaction. Ferrous sulfate, iron pentacarbonyl, ammonium tetrathiomolybdate, and molybdenum hexacarbonyl were used as catalyst precursors. Without swelling pretreatment, impregnation of both coals increased conversion, mainly through increased yields of preasphaltenes.

Peak capacity, peak-capacity production rate, and boiling point resolution for temperature-programmed GC with very high programming rates

Science.gov (United States)

Grall; Leonard; Sacks

2000-02-01

Recent advances in column heating technology have made possible very fast linear temperature programming for high-speed gas chromatography. A fused-silica capillary column is contained in a tubular metal jacket, which is resistively heated by a precision power supply. With very rapid column heating, the rate of peak-capacity production is significantly enhanced, but the total peak capacity and the boiling-point resolution (minimum boiling-point difference required for the separation of two nonpolar compounds on a nonpolar column) are reduced relative to more conventional heating rates used with convection-oven instruments. As temperature-programming rates increase, elution temperatures also increase with the result that retention may become insignificant prior to elution. This results in inefficient utilization of the down-stream end of the column and causes a loss in the rate of peak-capacity production. The rate of peak-capacity production is increased by the use of shorter columns and higher carrier gas velocities. With high programming rates (100-600 degrees C/min), column lengths of 6-12 m and average linear carrier gas velocities in the 100-150 cm/s range are satisfactory. In this study, the rate of peak-capacity production, the total peak capacity, and the boiling point resolution are determined for C10-C28 n-alkanes using 6-18 m long columns, 50-200 cm/s average carrier gas velocities, and 60-600 degrees C/min programming rates. It was found that with a 6-meter-long, 0.25-mm i.d. column programmed at a rate of 600 degrees C/min, a maximum peak-capacity production rate of 6.1 peaks/s was obtained. A total peak capacity of about 75 peaks was produced in a 37-s long separation spanning a boiling-point range from n-C10 (174 degrees C) to n-C28 (432 degrees C).

Multiyear Program Plan for the High Temperature Materials Laboratory; FINAL

International Nuclear Information System (INIS)

Arvid E. Pasto

2000-01-01

Recently, the U.S. Department of Energy's (DOE) Office of Heavy Vehicle Technologies (OHVT) prepared a Technology Roadmap describing the challenges facing development of higher fuel efficiency, less polluting sport utility vehicles, vans, and commercial trucks. Based on this roadmap, a multiyear program plan (MYPP) was also developed, in which approaches to solving the numerous challenges are enumerated. Additional planning has been performed by DOE and national laboratory staff, on approaches to solving the numerous challenges faced by heavy vehicle system improvements. Workshops and planning documents have been developed concerning advanced aerodynamics, frictional and other parasitic losses, and thermal management. Similarly, the Heavy Vehicle Propulsion Materials Program has developed its own multiyear program plan. The High Temperature Materials Laboratory, a major user facility sponsored by OHVT, has now developed its program plan, described herein. Information was gathered via participation in the development of OHVT's overall Technology Roadmap and MYPP, through personal contacts within the materials-user community, and from attendance at conferences and expositions. Major materials issues for the heavy vehicle industry currently center on trying to increase efficiency of (diesel) engines while at the same time reducing emissions (particularly NO(sub x) and particulates). These requirements dictate the use of increasingly stronger, higher-temperature capable and more corrosion-resistant materials of construction, as well as advanced catalysts, particulate traps, and other pollution-control devices. Exhaust gas recirculation (EGR) is a technique which will certainly be applied to diesel engines in the near future, and its use represents a formidable challenge, as will be described later. Energy-efficient, low cost materials processing methods and surface treatments to improve wear, fracture, and corrosion resistance are also required

Evaluation of the effect of the acetic anhydride concentration, temperature and time in the acetylation reaction for chemical modification of Calophyllum brasiliense and Enterolobium cyclocarpum

International Nuclear Information System (INIS)

Blanco Arias, Ernesto

2013-01-01

A treatment is performed to increase the life of wood in Costa Rica. The effect of acetic anhydride concentration, temperature and time have been studied in the reaction of acetylation for the chemical modification of tropical species Calophyllum brasiliense (Cedar Maria) and Enterolobium cyclocarpum (Guanacaste). Species have been characterized for quantifying the amount of OH groups available for the acetylation reaction. An important aspect is that the temperature conditions, the ratio of acetic anhydride with has dry wood mass and initial acetic acid concentration were assessed using a factorial design and have determined the conditions with which has obtained greater weight gain in the acetylation reaction. Furthermore, the acetylation reaction was conducted for times of 2 hours, 4,5 hours and 7 hours. The ATR infrared spectroscopy was used to verify the replacement of the OH group by acetyl groups and the increase in the different reaction time. The characteristics obtained from the OH groups have been 13,23 mmol and 13,85 mmol of OH per gram of wood of the Guanacaste species and Cedar Maria respectively. The temperature has been 90 degrees Celsius, one relationship acetic anhydride/dry wood 1,75 mL/g without the initial presence of acetic acid in the reaction medium. Also, percentages of profit of weight (WPG) have been obtained; maximums of 12,20% and 12,44% for Guanacaste for Cedar Maria in reaction time of 7 hours, 4,5 hours respectively. A decrease in the band has performed in the 3300 cm -1 characteristic of the OH group and the presence of bands at 1700 cm -1 characteristic of C=O. One of the main conclusions is that the acetylated wood has been an increase in resistance to biological degradation by white rot fungus Trametes versicolor of about 87% efficiency for both species [es

Low-temperature (75 °C) solid-state reaction enhanced by less-crystallized nanoporous PbI2 films for efficient CH3NH3PbI3 perovskite solar cells

International Nuclear Information System (INIS)

Zheng, Huifeng; Liu, Yangqiao; Sun, Jing

2017-01-01

Highlights: • Efficient perovskite solar cells were prepared with solid-state reaction at 75 °C. • Ln-PbI 2 is superior to c-PbI 2 when applied in low-temperature solid-state reaction. • A higher champion PCE was obtained at 75 °C (13.8%) than that of 140 °C (11.8%). • Non-radiative defects increase significantly when annealed at high temperature. - Abstract: Organohalide perovskite films are usually prepared with the solid-state reaction at a high temperature ≥100 °C, which causes the increase of non-radiative defects and decomposition of perovskite films. Here, we demonstrate it’s feasible to prepare high-quality perovskite films with the solid-state reaction method even at a temperature of 75 °C, when enhanced by less-crystallized nanoporous PbI 2 (ln-PbI 2 ) films. The replacement of compact PbI 2 (c-PbI 2 ) by ln-PbI 2 , results in a significant improvement of crystallinity of perovskite films, besides the elimination of remnant PbI 2 . As a result, ln-PbI 2 based perovskite solar cells display much higher power conversion efficiency (PCE) and better stability. Moreover, annealing duration was found to be critical for high PCE and was optimized as 60 min. Finally, with the optimal process, the champion device displayed a PCE of 13.8% and the average PCE reached 10.1% with a satisfactory deviation. Furthermore, we found annealing at high temperature (140 °C) led to a lower PCE compared with that annealed at 75 °C, because non-radiative defects increased significantly during high-temperature annealing. This work may open up a promising avenue for preparing high-quality perovskite films with the low-temperature solid-state reaction method, which is desirable for real application.

Optimization of basic parameters in temperature-programmed gas chromatographic separations of multi-component samples within a given time

NARCIS (Netherlands)

Repka, D.; Krupcik, J.; Brunovska, A.; Leclercq, P.A.; Rijks, J.A.

1989-01-01

A new procedure is introduced for the optimization of column peak capacity in a given time. The opitmization focuses on temperature-programmed operating conditions, notably the initial temperature and hold time, and the programming rate. Based conceptually upon Lagrange functions, experiments were

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

Science.gov (United States)

Hickson, Kevin M; Suleimanov, Yury V

2017-03-09

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

Fluorination reaction uranium dioxide by fluorine

International Nuclear Information System (INIS)

Ogata, Shinji; Homma, Shunji; Koga, Jiro; Matsumoto, Shiro; Sasahira, Akira; Kawamura, Fumio

2004-01-01

Kinetics of the fluorination reaction of uranium dioxide is studied using un-reacted core model with shrinking particles. The model includes the film mass transfer of fluorine gas and its diffusion in the particle. The rate constants of the model are determined by fitting the experimental data for 370-450degC. The model successfully represents the fluorination in this temperature range. The rate control step is identified by examining the rate constants of the model for 300-1,800degC. For temperature range up to 900degC, the fluorination reaction is rate controlling. For over 900degC, both mechanisms of the mass transfer of fluorine and the fluorination reaction control the rate of the fluorination. With further increase of the temperature, however, the fluorination reaction becomes so fast that the mass transfer of fluorine eventually controls the rate of the fluorination. (author)

Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-107 K).

Science.gov (United States)

Ocaña, A J; Blázquez, S; Ballesteros, B; Canosa, A; Antiñolo, M; Albaladejo, J; Jiménez, E

2018-02-21

Ethanol, CH 3 CH 2 OH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CH 3 CH 2 OH (k(T)) between 21 and 107 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(107 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10 -11 (T/300 K) -(0.71±0.10) cm 3 molecule -1 s -1 . In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (∼10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10 -11 cm 3 molecule -1 s -1 at 100 K and around 1 × 10 -10 cm 3 molecule -1 s -1 at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

Mathematical Model of Synthesis Catalyst with Local Reaction Centers

Directory of Open Access Journals (Sweden)

I. V. Derevich

2017-01-01

Full Text Available The article considers a catalyst granule with a porous ceramic passive substrate and point active centers on which an exothermic synthesis reaction occurs. A rate of the chemical reaction depends on the temperature according to the Arrhenius law. Heat is removed from the pellet surface in products of synthesis due to heat transfer. In our work we first proposed a model for calculating the steady-state temperature of a catalyst pellet with local reaction centers. Calculation of active centers temperature is based on the idea of self-consistent field (mean-field theory. At first, it is considered that powers of the reaction heat release at the centers are known. On the basis of the found analytical solution, which describes temperature distribution inside the granule, the average temperature of the reaction centers is calculated, which then is inserted in the formula for heat release. The resulting system of transcendental algebraic equations is transformed into a system of ordinary differential equations of relaxation type and solved numerically to achieve a steady-state value. As a practical application, the article considers a Fischer-Tropsch synthesis catalyst granule with active cobalt metallic micro-particles. Cobalt micro-particles are the centers of the exothermic reaction of hydrocarbons macromolecular synthesis. Synthesis occurs as a result of absorption of the components of the synthesis gas on metallic cobalt. The temperature distribution inside the granule for a single local center and reaction centers located on the same granule diameter is found. It was found that there is a critical temperature of reactor exceeding of which leads to significant local overheating of the centers - thermal explosion. The temperature distribution with the local reaction centers is qualitatively different from the granule temperature, calculated in the homogeneous approximation. It is shown that, in contrast to the homogeneous approximation, the

Rate coefficients of the CF3CHFCF3 + H → CF3CFCF3 + H2 reaction at different temperatures calculated by transition state theory with ab initio and DFT reaction paths.

Science.gov (United States)

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

2013-03-15

The minimum energy path (MEP) of the reaction, CF(3)CHFCF(3) + H → transition state (TS) → CF(3)CFCF(3) + H(2), has been computed at different ab initio levels and with density functional theory (DFT) using different functionals. The computed B3LYP/6-31++G**, BH&HLYP/cc-pVDZ, BMK/6-31++G**, M05/6-31+G**, M05-2X/6-31+G**, UMP2/6-31++G**, PUMP2/6-31++G**//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVDZ//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVTZ(spd,sp)//UMP2//6-31++G**, RCCSD(T)/CBS//M05/6-31+G**, and RCCSD(T)/CBS//UMP2/6-31++G** MEPs, and associated gradients and Hessians, were used in reaction rate coefficient calculations based on the transition state theory (TST). Reaction rate coefficients were computed between 300 and 1500 K at various levels of TST, which include conventional TST, canonical variational TST (CVT) and improved CVT (ICVT), and with different tunneling corrections, namely, Wigner, zero-curvature, and small-curvature (SCT). The computed rate coefficients obtained at different ab initio, DFT and TST levels are compared with experimental values available in the 1000-1200 K temperature range. Based on the rate coefficients computed at the ICVT/SCT level, the highest TST level used in this study, the BH&HLYP functional performs best among all the functionals used, while the RCCSD(T)/CBS//MP2/6-31++G** level is the best among all the ab initio levels used. Comparing computed reaction rate coefficients obtained at different levels of theory shows that, the computed barrier height has the strongest effect on the computed reaction rate coefficients as expected. Variational effects on the computed rate coefficients are found to be negligibly small. Although tunneling effects are relatively small at high temperatures (~1500 K), SCT corrections are significant at low temperatures (~300 K), and both barrier heights and the magnitudes of the imaginary frequencies affect SCT corrections. Copyright © 2012 Wiley Periodicals, Inc.

Atomic-Scale View on the H₂O Formation Reaction from H₂ on O-Rich RuO₂(110)

DEFF Research Database (Denmark)

Wei, Yinying; Martinez, Umberto; Lammich, Lutz

2014-01-01

The H2O formation reaction from H-2 on O-rich RuO2(110) was studied by temperature-programmed desorption and reaction (TPD/TPR) and scanning tunneling microscopy (STM) measurements and density functional theory (DFT) calculations. On the one hand, following H-2 adsorption at 270 K, our TPD/TPR me...

Fusion chain reaction - a chain reaction with charged particles

International Nuclear Information System (INIS)

Peres, A.; Shvarts, D.

1975-01-01

When a DT-plasma is compressed to very high density, the particles resulting from nuclear reactions give their energy mostly to D and T ions, by nuclear collisions, rather than to electrons as usual. Fusion can thus proceed as a chain reaction, without the need of thermonuclear temperatures. In this paper, we derive relations for the suprathermal ion population created by a fusion reaction. Numerical integration of these equations shows that a chain reaction can proceed in a cold infinite DT-plasma at densities above 8.4x10 27 ions.cm -3 . Seeding the plasma with a small amount of 6 Li reduces the critical density to 7.2x10 27 ions.cm -3 (140000times the normal solid density). (author)

Research programs in adsorption carried out in the low temperature laboratory of UFRJ (Brazil)

International Nuclear Information System (INIS)

Rapp, R.E.

1981-01-01

Research programs of gas adsorption in thin films carried out by the low temperature laboratory of UFRJ (Brazil) are reported. These programs were divided in two parts: 1) experiments of adsorption isotherm measurements by the volumetric method and 2) specific heat measurements of adsorbed gases. (L.C.) [pt

Reactions of Ground State Nitrogen Atoms N(4S) with Astrochemically-Relevant Molecules on Interstellar Dusts

Science.gov (United States)

Krim, Lahouari; Nourry, Sendres

2015-06-01

In the last few years, ambitious programs were launched to probe the interstellar medium always more accurately. One of the major challenges of these missions remains the detection of prebiotic compounds and the understanding of reaction pathways leading to their formation. These complex heterogeneous reactions mainly occur on icy dust grains, and their studies require the coupling of laboratory experiments mimicking the extreme conditions of extreme cold and dilute media. For that purpose, we have developed an original experimental approach that combine the study of heterogeneous reactions (by exposing neutral molecules adsorbed on ice to non-energetic radicals H, OH, N...) and a neon matrix isolation study at very low temperatures, which is of paramount importance to isolate and characterize highly reactive reaction intermediates. Such experimental approach has already provided answers to many questions raised about some astrochemically-relevant reactions occurring in the ground state on the surface of dust grain ices in dense molecular clouds. The aim of this new present work is to show the implication of ground state atomic nitrogen on hydrogen atom abstraction reactions from some astrochemically-relevant species, at very low temperatures (3K-20K), without providing any external energy. Under cryogenic temperatures and with high barrier heights, such reactions involving N(4S) nitrogen atoms should not occur spontaneously and require an initiating energy. However, the detection of some radicals species as byproducts, in our solid samples left in the dark for hours at 10K, proves that hydrogen abstraction reactions involving ground state N(4S) nitrogen atoms may occur in solid phase at cryogenic temperatures. Our results show the efficiency of radical species formation stemming from non-energetic N-atoms and astrochemically-relevant molecules. We will then discuss how such reactions, involving nitrogen atoms in their ground states, might be the first key step

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

Science.gov (United States)

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

2014-08-21

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

Unveiling the uncatalyzed reaction of alkynes with 1,2-dipoles for the room temperature synthesis of cyclobutenes.

Science.gov (United States)

Alcaide, Benito; Almendros, Pedro; Fernández, Israel; Lázaro-Milla, Carlos

2015-02-25

2-(Pyridinium-1-yl)-1,1-bis(triflyl)ethanides have been used as 1,2-dipole precursors in a metal-free direct [2+2] cycloaddition reaction of alkynes. Starting from stable zwitterionic pyridinium salts, the electron deficient olefin 1,1-bis(trifluoromethylsulfonyl)ethene is generated in situ and immediately reacted at room temperature with an alkyne to afford substituted cyclobutenes. Remarkably, this mild and facile uncatalyzed protocol requires neither irradiation nor heating.

GENGTC-JB: a computer program to calculate temperature distribution for cylindrical geometry capsule

International Nuclear Information System (INIS)

Someya, Hiroyuki; Kobayashi, Toshiki; Niimi, Motoji; Hoshiya, Taiji; Harayama, Yasuo

1987-09-01

In design of JMTR irradiation capsules contained specimens, a program (named GENGTC) has been generally used to evaluate temperature distributions in the capsules. The program was originally compiled by ORNL(U.S.A.) and consisted of very simple calculation methods. From the incorporated calculation methods, the program is easy to use, and has many applications to the capsule design. However, it was considered to replace original computing methods with advanced ones, when the program was checked from a standpoint of the recent computer abilities, and also to be complicated in data input. Therefore, the program was versioned up as aim to make better calculations and improve input method. The present report describes revised calculation methods and input/output guide of the version-up program. (author)

Experimental Study of Na based Titanium Nanofluid-Water Reaction

Energy Technology Data Exchange (ETDEWEB)

Park, Gunyeop; Kim, Soo Jae; Baek, Jehyun; Kim, Hyun Soo; Oh, Sun Ryung; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of)

2015-10-15

In KALIMER-600, a sodium-cooled fast reactor designed by KAERI, thermal energy is transported from high-temperature liquid Na (526 .deg. C at 0.1 MPa) to low temperature water (230 .deg. C at - 19.5 MPa) through a heat exchanger. If any leakage or rupture occurs during the operation of this heat exchanger, highly pressurized liquid water can penetrate into the liquid Na channels; this contact should instantly cause SWR. As reaction continues, liquid water is soon vaporized by pressure drop and huge amount of reaction heat. This generated water vapor expands large reaction area and increases sodium-water vapor reaction process. Therefore, the rapid generation of reaction product (like H{sub 2}) and water vapor increases the system pressure that can cause the system failure in SFR. To reduce this strong chemical reaction phenomena between Na and water, some we have focused on suppressing the chemical reactivity of liquid Na by dispersing nanoparticles (NPs). For the real application of NaTiNF, the pressure change induced by NaTiNF-water reaction is compared with Na-water reaction in the present study. NaTiNF contains 100nm of Ti NPs at 0.2 vol. %. The reaction rate of NaTiNF-water reaction is also investigated as reaction temperature increases. Sodium-water vapor reaction (SVR) will occur when an SWR accident occurs in SFR. In this manner, NaTiNF-water vapor reaction is experimentally performed for ensuring the suppression of chemical reactivity of NaTiNF in contact with water vapor. In the basic step for reducing risk of an SWR in SFR, we have experimentally verified the suppressed chemical reactivity of liquid sodium using Ti NPs through SWR and SVR experiments. In SWR, Na based titanium nanofluid (NaTiNF) shows lower pressure change than Na. As T{sub R} increases, P{sub max} in Na-water reaction increases while NaTiNF does not. The reaction rate of NaTiNF shows twice slower than that of Na. In SVR, NaTiNF shows slower temperature increase than Na. The distinct

Intrinsic reaction kinetics of coal char combustion by direct measurement of ignition temperature

International Nuclear Information System (INIS)

Kim, Ryang-Gyoon; Jeon, Chung-Hwan

2014-01-01

A wire heating reactor that can use a synchronized experimental method was developed to obtain the intrinsic kinetics of large coal char particles ranging in size from 0.4 to 1 mm. This synchronization system consists of three parts: a thermocouple wire for both heating and direct measurement of the particle temperature, a photodetector sensor for determining ignition/burnout points by measuring the intensity of luminous emission from burning particles, and a high-speed camera–long-distance microscope for observing and recording the movement of luminous zone directly. Coal char ignition was found to begin at a spot on the particle's external surface and then moved across the entire particle. Moreover, the ignition point determined according to the minimum of dT/dt is a spot point and not a full growth point. The ignition temperature of the spot point rises as the particle diameter increases. A spot ignition model, which describes the ignition in terms of the internal conduction and external/internal oxygen diffusion, was then developed to evaluate the intrinsic kinetics and predict the ignition temperature of the coal char. Internal conduction was found to be important in large coal char particles because its effect becomes greater than that of oxygen diffusion as the particle diameter increases. In addition, the intrinsic kinetics of coal char obtained from the spot ignition model for two types of coal does not differ significantly from the results of previous investigators. -- Highlights: • A novel technique was used to measure the coal char particle temperature. • The ignition point determined from a dT/dt minimum is a spot ignition point. • A spot ignition model was suggested to analyze the intrinsic reaction kinetics of coal char. • Internal conduction has to be considered in order to evaluate the intrinsic kinetics for larger particle (above 1 mm)

Impact parameter selected nuclear temperatures of hot nuclei from excited state populations for 40Ar+197Au reactions at E/A=25MeV

International Nuclear Information System (INIS)

Li Zuyu; He Zhiyong; Duan Limin; Jin Genming; Wu Heyu; Zhang Baoguo; Wen Wanxin; Qi Yujin; Luo Qingzheng; Dai Guangxi; Wang Hongwei

1997-01-01

Nuclear temperatures extracted from excited state populations were measured as a function of linear momentum transfer (LMT) for 40 Ar+ 197 Au reactions at 25MeV/nucleon. The emission temperatures increased slightly with increasing linear momentum transfer or decreasing impact parameter. Taking into account the corrections of detection efficiency and sequential feeding from higher-lying states, a temperature of T∼4MeV was deduced for central collisions. For peripheral collisions the extracted temperatures increased with the energy of the particles. (orig.)

Determining Annealing Temperatures for Polymerase Chain Reaction

Science.gov (United States)

Porta, Angela R.; Enners, Edward

2012-01-01

The polymerase chain reaction (PCR) is a common technique used in high school and undergraduate science teaching. Students often do not fully comprehend the underlying principles of the technique and how optimization of the protocol affects the outcome and analysis. In this molecular biology laboratory, students learn the steps of PCR with an…

Kinetics of iron redox reaction in silicate melts: A high temperature Xanes study on an alkali basalt

Energy Technology Data Exchange (ETDEWEB)

Cochain, B; Neuville, D R; Roux, J; Strukelj, E; Richet, P [Physique des Mineraux et Magmas, Geochimie-Cosmochimie, CNRS-IPGP, 4 place Jussieu, 75005 Paris (France); Ligny, D de [Universite Claude Bernard Lyon 1, LPCML, F-69622 Villeurbanne (France); Baudelet, F, E-mail: cochain@ipgp.jussieu.f [Synchrotron SOLEIL, L' Orme des Merisiers, Saint Aubin (France)

2009-11-15

In Earth and Materials sciences, iron is the most important transition element. Glass and melt properties are strongly affected by iron content and redox state with the consequence that some properties (i.e. viscosity, heat capacity, crystallization...) depend not only on the amounts of Fe{sup 2+} and Fe{sup 3+}, but also on the coordination state of these ions. In this work we investigate iron redox reactions through XANES experiments at the K-edge of iron. Using a high-temperature heating device, pre-edge of XANES spectra exhibits definite advantages to make in-situ measurements and to determine the evolution of redox state with time, temperature and composition of synthetic silicate melts. In this study, new kinetics measurements are presented for a basalt melt from the 31,000-BC eruption of the Puy de Lemptegy Volcano in France. These measurements have been made between 773 K and at superliquidus temperatures up to 1923 K.

Kinetics of iron redox reaction in silicate melts: A high temperature Xanes study on an alkali basalt

International Nuclear Information System (INIS)

Cochain, B; Neuville, D R; Roux, J; Strukelj, E; Richet, P; Ligny, D de; Baudelet, F

2009-01-01

In Earth and Materials sciences, iron is the most important transition element. Glass and melt properties are strongly affected by iron content and redox state with the consequence that some properties (i.e. viscosity, heat capacity, crystallization...) depend not only on the amounts of Fe 2+ and Fe 3+ , but also on the coordination state of these ions. In this work we investigate iron redox reactions through XANES experiments at the K-edge of iron. Using a high-temperature heating device, pre-edge of XANES spectra exhibits definite advantages to make in-situ measurements and to determine the evolution of redox state with time, temperature and composition of synthetic silicate melts. In this study, new kinetics measurements are presented for a basalt melt from the 31,000-BC eruption of the Puy de Lemptegy Volcano in France. These measurements have been made between 773 K and at superliquidus temperatures up to 1923 K.

A shock tube study of the reactions of the hydroxyl radical with combustion species

Energy Technology Data Exchange (ETDEWEB)

Cohen, N.; Koffend, J.B. [The Aerospace Corporation, Los Angeles, CA (United States)

1993-12-01

To extend the semi-empirical techniques of Benson and coworkers, and to extend the database of reliable high temperature measurements of OH radicals with hydrocarbons and other fuels and their decomposition products, the authors undertook a research program with both experimental and computational tasks. The experimental goal was to design a procedure for measuring, at combustion temperatures, the reaction rate coefficients of OH radicals with fuels and other species of importance in combustion or propulsion systems. The computational effort was intended to refine the semi-empirical transition-state-theory procedures for extrapolating rate coefficients of reactions of OH with combustion species of interest, for predicting rate coefficients for species not studied in the laboratory, and to examine the ability of the theory to predict rate coefficients for different pathways in the case the reagent possessed more than one nonequivalent H atoms.

Effect of Ti and C particle sizes on reaction behavior of thermal explosion reaction of Cu−Ti−C system under Ar and air atmospheres

Energy Technology Data Exchange (ETDEWEB)

Liang, Yunhong; Zhao, Qian; Li, Xiujuan; Zhang, Zhihui, E-mail: zhzh@jlu.edu.cn; Ren, Luquan

2016-09-15

The thermal explosion (TE) reaction behavior of Cu−Ti−C systems with different Ti and C particle sizes was investigated under air and Ar atmospheres. It was found that increasing the Ti and C particle sizes leads to higher ignition temperatures under both atmospheres and that the maximum combustion temperature decreases with increasing C particle size. The TE reaction is much easier to activate (i.e., it has a lower ignition temperature) in air because of the heat released from Ti oxidation and nitridation and Cu oxidation reactions on the Cu−Ti−C compact surface. TiC ceramic particles are successfully prepared in the bulk Cu−Ti−C compacts under both air and Ar atmospheres through a dissolution-diffusion-precipitation mechanism. Differential thermal and thermodynamic analyses show that the TE reaction ignition process in air is mainly controlled by the Ti particle size. - Highlights: • Variation of Ti and C particle sizes affects thermal reaction (TE) behaviors. • Ignition temperature under air is much lower than that under Ar atmosphere. • Heat of oxidation and nitridation reactions reduces ignition temperature under air.

EQUILGAS: Program to estimate temperatures and in situ two-phase conditions in geothermal reservoirs using three combined FT-HSH gas equilibria models

Science.gov (United States)

Barragán, Rosa María; Núñez, José; Arellano, Víctor Manuel; Nieva, David

2016-03-01

Exploration and exploitation of geothermal resources require the estimation of important physical characteristics of reservoirs including temperatures, pressures and in situ two-phase conditions, in order to evaluate possible uses and/or investigate changes due to exploitation. As at relatively high temperatures (>150 °C) reservoir fluids usually attain chemical equilibrium in contact with hot rocks, different models based on the chemistry of fluids have been developed that allow deep conditions to be estimated. Currently either in water-dominated or steam-dominated reservoirs the chemistry of steam has been useful for working out reservoir conditions. In this context, three methods based on the Fischer-Tropsch (FT) and combined H2S-H2 (HSH) mineral-gas reactions have been developed for estimating temperatures and the quality of the in situ two-phase mixture prevailing in the reservoir. For these methods the mineral buffers considered to be controlling H2S-H2 composition of fluids are as follows. The pyrite-magnetite buffer (FT-HSH1); the pyrite-hematite buffer (FT-HSH2) and the pyrite-pyrrhotite buffer (FT-HSH3). Currently from such models the estimations of both, temperature and steam fraction in the two-phase fluid are obtained graphically by using a blank diagram with a background theoretical solution as reference. Thus large errors are involved since the isotherms are highly nonlinear functions while reservoir steam fractions are taken from a logarithmic scale. In order to facilitate the use of the three FT-HSH methods and minimize visual interpolation errors, the EQUILGAS program that numerically solves the equations of the FT-HSH methods was developed. In this work the FT-HSH methods and the EQUILGAS program are described. Illustrative examples for Mexican fields are also given in order to help the users in deciding which method could be more suitable for every specific data set.

The use of on-line ion chromatography for high temperature and high pressure reaction studies

International Nuclear Information System (INIS)

Lynch, G.J.

1993-10-01

This paper describes the use of on-line ion chromatography as a tool for chemistry reaction studies in small volume systems. The technique was used to study chemistry behavior in a high temperature and high pressure autoclave system. A dual analyzer, multi-channel on-line ion chromatograph (IC) was configured to automate the sampling and analysis. Analytical channels were set up for analysis of inorganic anions, monovalent cations, conductivity, and pH. Conductivity and pH were measured using the IC as a flow injection analyzer. Use of the IC system provides significant advantages over conventional sampling and analysis techniques: Reduction in sample volume, a closed sampling system that protects air or light sensitive analytes from breakdown, around-the-clock test performance combined with automatic calibration and quality control checking, and detection and tracking of reaction products or unexpected contaminants. Methods used to correct measured concentrations for the effects of sampling and for calculation of control chemical loss half-lives are presented. A limited evaluation of the flow injection analysis methods for conductivity and pH is provided

Minimization of steam requirements and enhancement of water-gas shift reaction with warm gas temperature CO2 removal

Science.gov (United States)

Siriwardane, Ranjani V; Fisher, II, James C

2013-12-31

The disclosure utilizes a hydroxide sorbent for humidification and CO.sub.2 removal from a gaseous stream comprised of CO and CO.sub.2 prior to entry into a water-gas-shift reactor, in order to decrease CO.sub.2 concentration and increase H.sub.2O concentration and shift the water-gas shift reaction toward the forward reaction products CO.sub.2 and H.sub.2. The hydroxide sorbent may be utilized for absorbtion of CO.sub.2 exiting the water-gas shift reactor, producing an enriched H.sub.2 stream. The disclosure further provides for regeneration of the hydroxide sorbent at temperature approximating water-gas shift conditions, and for utilizing H.sub.2O product liberated as a result of the CO.sub.2 absorption.

Hydrogen Temperature-Programmed Desorption (H2 TPD) of Supported Platinum Catalysts.

NARCIS (Netherlands)

Koningsberger, D.C.; Miller, J.T.; Meyers, B.L.; Modica, F.S.; Lane, G.S.; Vaarkamp, M.

1993-01-01

Hydrogen temperature-programmed desorption (TPD) of supported platinum catalysts, Pt/KLTL, Pt/H-LTL, Pt/K-MAZ, Pt/H-MAZ, Pt/-Al2O3, and Pt/SiO2, was performed after hydrogen reduction at 300, 450, or 650°C. For all catalysts, reversible desorption of chemisorbed hydrogen occurred at approximately

THE HIGH-TEMPERATURE ELECTROLYSIS PROGRAM AT THE IDAHO NATIONAL LABORATORY: OBSERVATIONS ON PERFORMANCE DEGRADATION

Energy Technology Data Exchange (ETDEWEB)

J. E. O' Brien; C. M. Stoots; J. S. Herring; K. G. Condie; G. K. Housley

2009-06-01

This paper presents an overview of the high-temperature electrolysis research and development program at the Idaho National Laboratory, with selected observations of electrolysis cell degradation at the single-cell, small stack and large facility scales. The objective of the INL program is to address the technical and scale-up issues associated with the implementation of solid-oxide electrolysis cell technology for hydrogen production from steam. In the envisioned application, high-temperature electrolysis would be coupled to an advanced nuclear reactor for efficient large-scale non-fossil non-greenhouse-gas hydrogen production. The program supports a broad range of activities including small bench-scale experiments, larger scale technology demonstrations, detailed computational fluid dynamic modeling, and system modeling. A summary of the current status of these activities and future plans will be provided, with a focus on the problem of cell and stack degradation.

KINETICS OF THE REACTION OF ELEMENTAL FLUORINE WITH ZIRCONIUM CARBIDE AND ZIRCONIUM DIBORIDE AT HIGH TEMPERATURES

Energy Technology Data Exchange (ETDEWEB)

Kuriakose, A. K.; Margrave, J. L.

1963-09-15

The reaction between ZrC and F/sub 2/ was investigated at 278 to 410 deg C, using 31 mm HgF/syb 2/. The reaction was found to be linear with time, and linear rate constants were computed. The activation energy was determined to be 22.1 plus or minus 1.6 kcal/mole. ZrB/sub 2/ is not attacked by 31 mm HgF/sub 2/ below 500 deg C. The weight losses from reaction of ZrB/sub 2/ with F/sub 2/ at 600 to 900 deg C and of ZrC with F/sub 2/ at 700 to 950 deg C, were rneasured for a F/sub 2/ pressure of 2.7 mm Hg. Zero-time linear rate constants were calculated and found not to be strongly temperature-dependent above 600 deg C, and the activation energies are essentially zero for both ZrB/sub 2/ and ZrC. For ZrC at 350 deg C and for ZrB/sub 2/ at 700 deg C, the rate is approximately proportional to the square root of F/sub 2/ partial pressure, while for ZrC at 700 deg C, it is proportional to the 1.5 power of F/sub 2/ partial pressure. (D.L.C.)

Sugarcane bagasse gasification: Global reaction mechanism of syngas evolution

International Nuclear Information System (INIS)

Ahmed, I.I.; Gupta, A.K.

2012-01-01

Highlights: ► Gasification of sugarcane bagasse has been investigated using a semi batch reactor. ► Global reaction mechanism combining pyrolysis and gasification reactions is presented. ► High flow rates of syngas supported fragmentation and secondary reactions. ► CO flow rate increased at higher heating rates at the expense of CO 2 production. ► At high temperatures merger between pyrolysis and char gasification occurs. -- Abstract: Steam gasification of sugarcane bagasse has been investigated. A semi batch reactor with a fixed amount of sugarcane bagasse sample placed in steady flow of high temperature steam at atmospheric pressure has been used. The gasification of bagasse was examined at reactor and steam temperatures of 800, 900 and 1000 °C. The evolution of syngas flow rate and chemical composition has been monitored. The evolution of chemical composition and total flow rate of the syngas has been used to formulate a global reaction mechanism. The mechanism combines pyrolysis reaction mechanisms from the literature and steam gasification/reforming reactions. Steam gasification steps include steam–hydrocarbons reforming, char gasification and water gas shift reactions. Evidence of fragmentation, secondary ring opening reactions and tertiary reactions resulting in formation of gaseous hydrocarbons is supported by higher flow rates of syngas and hydrogen at high heating rates and high reactor temperatures. Increase in carbon monoxide flow rate at the expense of carbon dioxide flow rate with the increase in reactor temperature has been observed. This increase in the ratio of CO/CO 2 flow rate confirms the production of CO and CO 2 from the competing reaction routes. At 1000 °C gasification a total merging between the pyrolysis step and the char gasification step has been observed. This is attributed to acceleration of char gasification reactions and acceleration of steam–hydrocarbons reforming reactions. These hydrocarbons are the precursors to

The effects of temperature and pH on the kinetics of reactions between catalase and its suicide substrate hydrogen peroxide.

Science.gov (United States)

Ghadermarzi, M; Moosavi-Movahedi, A A

1997-12-01

Variation of initial (intact) activity (ai), inactivation rate constant (ki) and the partition ratio (r) of bovine liver catalase in the reaction with its suicide substrate, hydrogen peroxide, were determined in workable ranges of temperature (17-42 degrees C) or pH (5-10.5), using the data of progress curves. The changes of temperature had a slight effect on ai, giving a Q10 of 1.15 for the enzymatic breakdown of H2O2, corresponding to an improved value for its activation energy of 8.8 +/- l kJ.mol-1. In contrast, the ki was greatly increased by elevation of temperature, giving a Q10 of 2.1 for the suicide inactivation reaction of catalase. Consequently, a significant decrease of r was observed by increasing of temperature. In pH studies, decreasing of pH from 7.0 to 5.0 led to reduction of ai whereas the ki value was not effected significantly, possibly due to the parallel changes in affinities to free catalase and compound I for H2O2. Reduction of ki and alpha i were observed at pH > 9.5, where reversible dissociation of tetrameric enzyme into catalytically inactive subunits is possible. The r had a maximum value at pH around 7.5, similar to that of catalase activity. The effect of ionic strength on the above kinetic parameters was studied. There was not an observable influence when the ammonium sulfate concentration was below l M.

Reactions and reaction intermediates on iron surfaces--1. Methanol, ethanol, and isopropanol on Fe(100). 2. Hydrocarbons and carboxylic acids

Energy Technology Data Exchange (ETDEWEB)

Benziger, J.B.; Madix, R.J.

1980-09-01

Temperature-programed desorption and ESCA showed that the alcohols formed alkoxy intermediates on Fe(100) surfaces at room temperature, but that the methoxy and ethoxy species were much more stable than the isopropoxy intermediate. The alkoxy species reacted above 400/sup 0/K by decomposing into carbon monoxide and hydrogen, hydrogenation to alcohol, and scission of C-C and C-O bonds with hydrogenation of the hydrocarbon fragments. Ethylene, acetylene, and cis-2-butene formed stable, unidentified surface species. Methyl chloride formed stable surface methyl groups which decomposed into hydrogen and surface carbide at 475/sup 0/K. Formic and acetic acids yielded stable carboxylate intermediates which decomposed above 490/sup 0/K to hydrogen, carbon monoxide, and carbon dioxide. The studies suggested that the alkoxy surface species may be important intermediates in the Fischer-Tropsch reaction on iron.

The Effect of MHD on Free Convection with Periodic Temperature and Concentration in the Presence of Thermal Radiation and Chemical Reaction

Directory of Open Access Journals (Sweden)

Zigta B.

2017-12-01

Full Text Available This paper studies the effect of magneto hydrodynamics on unsteady free convection between a pair of infinite vertical Couette plates. The temperature of the plates and concentration between the plates vary with time. Convection between the plates is considered in the presence of thermal radiation and chemical reaction. The solution is obtained using perturbation techniques. These techniques are used to transform nonlinear coupled partial differential equations to a system of ordinary differential equations. The resulting equations are solved analytically. The solution is expressed in terms of power series with some small parameter. The effect of various parameters, viz., velocity, temperature and concentration, has been discussed. Mat lab code simulation study is carried out to support the theoretical results. The result shows that as the thermal radiation parameter R increases, the temperature decreases near the moving porous plate while it approaches to a zero in the region close to the boundary layer of the stationary plate. Moreover, as the modified Grashof number, i.e., based on concentration difference, increases, the velocity of the fluid flow increases hence the concentration decreases. An increase in both the chemical reaction parameter and Schmidt number results in decreased concentration.

The Effect of MHD on Free Convection with Periodic Temperature and Concentration in the Presence of Thermal Radiation and Chemical Reaction

Science.gov (United States)

Zigta, B.; Koya, P. R.

2017-12-01

This paper studies the effect of magneto hydrodynamics on unsteady free convection between a pair of infinite vertical Couette plates. The temperature of the plates and concentration between the plates vary with time. Convection between the plates is considered in the presence of thermal radiation and chemical reaction. The solution is obtained using perturbation techniques. These techniques are used to transform nonlinear coupled partial differential equations to a system of ordinary differential equations. The resulting equations are solved analytically. The solution is expressed in terms of power series with some small parameter. The effect of various parameters, viz., velocity, temperature and concentration, has been discussed. Mat lab code simulation study is carried out to support the theoretical results. The result shows that as the thermal radiation parameter R increases, the temperature decreases near the moving porous plate while it approaches to a zero in the region close to the boundary layer of the stationary plate. Moreover, as the modified Grashof number, i.e., based on concentration difference, increases, the velocity of the fluid flow increases hence the concentration decreases. An increase in both the chemical reaction parameter and Schmidt number results in decreased concentration.

Thermochemistry of ionic liquid-catalysed reactions. Isomerisation and transalkylation of tert-alkyl-benzenes. Are these systems ideal?

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Emel'yanenko, Vladimir N.; Hopmann, Elisabeth; Arlt, Wolfgang

2010-01-01

The chemical equilibrium of mutual interconversions of tert-alkyl-benzenes was studied in the temperature range (286 to 423) K using chloroaluminate ionic liquids as a catalyst. The knowledge of the activity coefficients is required in order to obtain the thermodynamic equilibrium constants K a . A well established procedure, COSMO-RS, has been used to assess activity coefficients of the reaction participants in the liquid phase. Enthalpies of five reactions of isomerisation and transalkylation of tert-alkyl-benzenes were obtained from temperature dependences of the corresponding equilibrium constants in the liquid phase. For the sake of comparison, high-level ab initio calculations of the reaction participants have been performed using the Gaussian-03 program package. Absolute electronic energy values of the molecules have been obtained using B3LYP and G3MP2 level. Using these results enthalpies of reaction of isomerisation and transalkylation of tert-alkyl-benzenes in the liquid phase based on the first principles are found to be in good agreement with the data obtained from the thermochemical measurements.

Method for conducting exothermic reactions

Science.gov (United States)

Smith, L. Jr.; Hearn, D.; Jones, E.M. Jr.

1993-01-05

A liquid phase process for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

Reaction of uranium and the fluorocarbon FC-75

Science.gov (United States)

Young, R. H.

1985-04-01

Because of criticality concerns with water cooling in enriched uranium upgrading, a fluorocarbon has been evaluated as a replacement coolant for internal module components in the Plasma Separation Process (PSP). The interaction of bulk uranium and of powdered uranium with FC-75 has been investigated at temperatures between 200 and 700 C. The gas pressure and the metal temperature were monitored as a function of time. Modest temperature changes of 50 to 100 C were observed for the bulk uranium/fluorocarbon reaction. Much larger changes (up to 1000 C) were noted for the reaction involving high surface area uranium powder. These temperature transients, particularly for the powdered uranium reaction, were short-lived ( 10 seconds) and indicative of the formation of a protective layer of reaction products. Analysis of residual gas products by infrared spectroscopy indicated that one potentially serious hazard, UF6, was not present; however, several small toxic fluorocarbons were produced by thermolysis and/or reaction. X-ray diffraction analysis of the residual solids indicated UF4 and UO2 were the major solid products.

Analysis of pellet center temperatures measured in HALDEN IFA-224 using program FREG-3

International Nuclear Information System (INIS)

Harayama, Yasuo; Izumi, Fumio

1977-01-01

To verify the program FREG-3, we compared the calculations by FREG-3 with those by measurement in a HALDEN instrumented fuel assembly, IFA-224. FREG-3 generally gives higher pellet center temperatures than the measurement. The temperature distribution calculated by FREG-3 to estimate the stored energy in fuel rods results in safety side. (auth.)

Hydrogen production via thermochemical water-splitting by lithium redox reaction

International Nuclear Information System (INIS)

Nakamura, Naoya; Miyaoka, Hiroki; Ichikawa, Takayuki; Kojima, Yoshitsugu

2013-01-01

Highlights: •Hydrogen production via water-splitting by lithium redox reactions possibly proceeds below 800 °C. •Entropy control by using nonequilibrium technique successfully reduces the reaction temperature. •The operating temperature should be further reduced by optimizing the nonequilibrium condition to control the cycle. -- Abstracts: Hydrogen production via thermochemical water-splitting by lithium redox reactions was investigated as energy conversion technique. The reaction system consists of three reactions, which are hydrogen generation by the reaction of lithium and lithium hydroxide, metal separation by thermolysis of lithium oxide, and oxygen generation by hydrolysis of lithium peroxide. The hydrogen generation reaction completed at 500 °C. The metal separation reaction is thermodynamically difficult because it requires about 3400 °C in equilibrium condition. However, it was indicated from experimental results that the reaction temperature was drastically reduced to 800 °C by using nonequilibrium technique. The hydrolysis reaction was exothermic reaction, and completed by heating up to 300 °C. Therefore, it was expected that the water-splitting by lithium redox reactions was possibly operated below 800 °C under nonequilibrium condition

Kinetics of liquid lithium reaction with oxygen-nitrogen mixtures

International Nuclear Information System (INIS)

Gil, T.K.; Kazimi, M.S.

1986-01-01

A series of experiments have been conducted in order to characterize the kinetics of lithium chemical reaction with a mixture of oxygen and nitrogen. Three mixed gas compositions were used; 80% N 2 and 20% O 2 , 90% N 2 and 10% O 2 , and 95% N 2 and 5% O 2 . The reaction rate was obtained as a function of lithium temperature and the oxygen fraction. Liquid lithium temperature varied from 400 to 1100 0 C. By varying the composition, the degree of inhibition of the lithium-nitrogen reaction rate due to the presence of oxygen was observed. The results indicate that the lithium-nitrogen reaction rate depended on both the fraction of oxygen present and lithium temperature. The lithium nitride layer formed from the reaction also had a significant inhibition effect on the lithium-nitrogen reaction rate while the lithium-oxygen reaction rate was not as greatly hindered. LITFIRE, a computer code which simulates temperature and pressure history in a containment building following lithium spills, was modified by including (1) an improved model for the lithium-nitrogen reaction rate and (2) a model for the lithium-CO 2 reaction. LITFIRE was used to simulate HEDL's LC-2 and LA-5 experiments, and the predicted temperatures and pressures were in a reasonable agreement. Furthermore, LITFIRE was applied to a prototypical fusion reactor containment in order to simulate the consequences of a lithium spill accident. The result indicated that if nitrogen was used as containment building gas during the accident, the consequences of the accident would be less severe than those with air. The pressure rise in the building was found to be reduced by 50% and the maximum temperature of the combustion zone was limited to 900 0 C instead of 1200 0 C in the case of air

Degradation reactions in SONY-type Li-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Roth, E.P.; Nagasubramanian, G.

2000-07-01

Thermal instabilities were identified in SONY-type lithium-ion cells and correlated with interactions of cell constituents and reaction products. Three temperature regions of interaction were identified and associated with the state of charge (degree of Li intercalation) of the cell. Anodes were shown to undergo exothermic reactions as low as 100 C involving the solid electrolyte interface (SEI) layer and the LiPF{sub 6} salt in the electrolyte (EC:PC:DEC/LiPF{sub 6}). These reactions could account for the thermal runaway observed in these cells beginning at 100 C. Exothermic reactions were also observed in the 200 C--300 C region between the intercalated lithium anodes, the LiPF{sub 6} salt, and the PVDF. These reactions were followed by a high-temperature reaction region, 300 C--400 C, also involving the PVDF binder and the intercalated lithium anodes. The solvent was not directly involved in these reactions but served as a moderator and transport medium. Cathode exothermic reactions with the PVDF binder were observed above 200 C and increased with the state of charge (decreasing Li content). This offers an explanation for the observed lower thermal runaway temperatures for charged cells.

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.)

Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-10^7 K)

Science.gov (United States)

Ocaña, A. J.; Blázquez, S.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejoab, J.; Jiménez, E.

2018-02-01

Ethanol, CH3CH2OH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CH3CH2OH (k(T)) between 21 and 10^7 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(10^7 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10^-11 (T/300 K)-(0.71±0.10) cm^3 molecule^-1 s^-1. In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (˜10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10^-11 cm^3 molecule^-1 s^-1 at 100 K and around 1 × 10^-10 cm^3 molecule^-1 s^-1 at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

Dechlorinating reaction of organic chlorides

Energy Technology Data Exchange (ETDEWEB)

Yahata, Taneaki; Kihara, Shinji [Japan Atomic Energy Research Inst., Oarai, Ibaraki (Japan). Oarai Research Establishment; Ohuchi, Misao

1996-06-01

Dechlorination has been examined by the reaction between iron, aluminum powder or CaO and organic chlorides such as C{sub 2}HCl{sub 3} and CH{sub 2}Cl{sub 2}. Progress of the reaction was analyzed with mass spectrometer. The reaction between iron and organic chloride was rapidly occurred at the temperature between 350 and 440degC in an atmosphere of argon. Above 380degC, more than 99.5% of C{sub 2}HCl{sub 3} was decomposed within approximately 100 minutes. At 440degC, approximately 60% of C{sub 2}HCl{sub 3} was decomposed by the reaction with aluminium powder within approximately 100 minutes. At 440degC, reaction between C{sub 2}HCl{sub 3} and CaO powder were occurred rapidly in an atmosphere of argon to form CaCl{sub 2} and free carbon. Also in an atmosphere of air, nearly the same result was obtained. In this reaction, CaCl{sub 2}, CO and CO{sub 2} were formed. CH{sub 2}Cl{sub 2} was also decomposed by the reaction with iron at the temperature between 380 and 440degC. In the reaction, FeCl{sub 2}, carbon and hydrogen were formed. CH{sub 3}{sup +} and CH{sub 4} were observed during the dechlorinating reaction of CH{sub 2}Cl{sub 2}. Variation in particle size of iron powder such as 100, 150 and 250 mesh did not affect the reaction rate. (author)

Development of program for evaluating the temperature of Zr-U metallic fuel rod

International Nuclear Information System (INIS)

Chun, J. S.; Lee, B. H.; Ku, Y. H.; Oh, J. Y.; Im, J. S.; Sohn, D. S.

2003-01-01

A code for evaluating the temperature of Zr-U metallic rod has been developed. Finite element (FE) method is adopted for the developed code sharing the user subroutines which has been prepared for the ABAQUS commercial FE code. The developed program for the Zr-U metallic fuel rod corresponds to a nonlinear transient heat transfer problem, and uses a sparse matrix solver for FE equations during iterations at every time step. The verifications of the developed program were conducted using the ABAQUS code. Steady state and transient problems were analyzed for 1/8 rod model due to the symmetry of the fuel rod and full model. From the evaluation of temperature for the 1/8 rod model at steady state, maximal error of 0.18 % was present relative to the ABAQUS result. Analysis for the transient problem using the fuel rod model resulted in the same as the variation of centerline temperature from the ABAQUS code during a hypothetical power transient. The distribution of heat flux for the entire cross section and surface was almost identical for the two codes

A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

KAUST Repository

Khaled, Fathi; Giri, Binod; Szőri, Milá n; Mai, Tam V.-T.; Huynh, Lam K.; Farooq, Aamir

2017-01-01

The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

In-operando elucidation of bimetallic CoNi nanoparticles during high-temperature CH 4 /CO 2 reaction

KAUST Repository

Al-Sabban, Bedour

2017-05-02

Dry reforming of methane (DRM) proceeds via CH4 decomposition to leave surface carbon species, followed by their removal with CO2-derived species. Reactivity tuning for stoichiometric CH4/CO2 reactants was attempted by alloying the non-noble metals Co and Ni, which have high affinity with CO2 and high activity for CH4 decomposition, respectively. This study was focused on providing evidence of the capturing surface coverage of the reactive intermediates and the associated structural changes of the metals during DRM at high temperature using in-operando X-ray absorption spectroscopy (XAS). On the Co catalysts, the first-order effects with respect to CH4 pressure and negative-order effects with respect to CO2 pressure on the DRM rate are consistent with the competitive adsorption of the surface oxygen species on the same sites as the CH4 decomposition reaction. The Ni surface provides comparatively higher rates of CH4 decomposition and the resultant DRM than the Co catalyst but leaves some deposited carbon on the catalyst surface. In contrast, the bimetallic CoNi catalyst exhibits reactivity towards the DRM but with kinetic orders resembling Co catalyst, producing negligible carbon deposition by balancing CH4 and CO2 activation. The in-operando X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements confirmed that the Co catalyst was progressively oxidized from the surface to the bulk with reaction time, whereas CoNi and Ni remained relatively reduced during DRM. Density functional theory (DFT) calculation considering the high reaction temperature for DRM confirmed the unselective site arrangement between Co and Ni atoms in both the surface and bulk of the alloy nanoparticle (NP). The calculated heat of oxygen chemisorption became more exothermic in the order of Ni, CoNi, Co, consistent with the catalytic behavior. The comprehensive experimental and theoretical evidence provided herein clearly suggests

Iron based superconductors and related compounds synthesized by solid state metathesis and high temperature reactions

International Nuclear Information System (INIS)

Frankovsky, Rainer

2013-01-01

The results of this thesis can be divided into three major topics, which can also be seen as different approaches of solid state chemistry to reveal interesting features of known and unknown compounds and to develop alternative synthesis routes. Firstly, known compounds with related structural motifs to the superconducting iron-arsenides were investigated regarding their structural and physical properties. In case of La 3 Pd 4 Ge 4 the influence of Fe doping on the properties was studied, whereas in the series ZrMAs (M=Ti,V) the physical properties have not yet been reported at all and were investigated for the first time. Secondly, an alternative synthesis route has been developed for the synthesis of superconducting LaFeAsO 1-x F x . This solid state metathesis reaction distinctly increased the quality of the samples compared to conventionally prepared products. Furthermore, the reaction pathway was investigated and clarified, which helps to understand the processes during high temperature solid state metathesis reactions in general. Thirdly, this alternative synthesis route was expanded to other systems and new compounds like co-substituted LaFe 1-x Mn x AsO 1-y F y were prepared and thoroughly investigated. This led to a complex study of the interplay of magnetism, electronic and structural conditions and the occurrence of superconducting properties. The investigation and understanding of such complex coherences will probably be decisive for the further understanding of the superconducting mechanism in iron based superconductors.

A high-temperature shock tube kinetic study for the branching ratios of isobutene+OH reaction

KAUST Repository

Khaled, Fathi; Giri, Binod; Farooq, Aamir

2016-01-01

Isobutene is an important intermediate formed during the oxidation of branched alkanes. It also appears as a byproduct during the combustion of methyl-tert-butyl-ether (MTBE) which is used as octane enhancer in gasolines. To understand better the oxidation kinetics of isobutene, we have measured the rate coefficients for the reaction of OH radicals with isobutene (HCC(CH)) behind reflected shock waves over the temperature range of 830-1289K and pressures near 1.5atm. The reaction progress was followed by measuring mole fraction of OH radicals near 306.7nm using UV laser absorption technique. Three deuterated isotopes, isobutene-1-d2 (DCC(CH)), isobutene-3-d6 (HCC(CD)) and isobutene-d8 (DCC(CD)) were employed to elucidate branching ratios of the allylic and vinylic H-abstraction from isobutene by OH radicals. H-abstraction from the allylic sites was found to be dominant and constituted about 75% of the total rate in the entire temperature range of the current work. The derived three-parameter Arrhenius expressions for site-specific H- and D- abstraction rates over 830-1289K are (units:cm mol s):k3,H=6.98×106(TK)1.77exp(-136.6KT) k3,D=4.42×106(TK)1.8exp(-361.7KT) k1,H=6.25×105(TK)2.16exp(-711.6KT) k1,D=3.13×107(TK)1.67exp(-1814KT) The subscript of . k identifies the position of H or D atom in isobutene according to the IUPAC nomenclature of alkenes.

A high-temperature shock tube kinetic study for the branching ratios of isobutene+OH reaction

KAUST Repository

Khaled, Fathi

2016-10-11

Isobutene is an important intermediate formed during the oxidation of branched alkanes. It also appears as a byproduct during the combustion of methyl-tert-butyl-ether (MTBE) which is used as octane enhancer in gasolines. To understand better the oxidation kinetics of isobutene, we have measured the rate coefficients for the reaction of OH radicals with isobutene (HCC(CH)) behind reflected shock waves over the temperature range of 830-1289K and pressures near 1.5atm. The reaction progress was followed by measuring mole fraction of OH radicals near 306.7nm using UV laser absorption technique. Three deuterated isotopes, isobutene-1-d2 (DCC(CH)), isobutene-3-d6 (HCC(CD)) and isobutene-d8 (DCC(CD)) were employed to elucidate branching ratios of the allylic and vinylic H-abstraction from isobutene by OH radicals. H-abstraction from the allylic sites was found to be dominant and constituted about 75% of the total rate in the entire temperature range of the current work. The derived three-parameter Arrhenius expressions for site-specific H- and D- abstraction rates over 830-1289K are (units:cm mol s):k3,H=6.98×106(TK)1.77exp(-136.6KT) k3,D=4.42×106(TK)1.8exp(-361.7KT) k1,H=6.25×105(TK)2.16exp(-711.6KT) k1,D=3.13×107(TK)1.67exp(-1814KT) The subscript of . k identifies the position of H or D atom in isobutene according to the IUPAC nomenclature of alkenes.

Computational study of chain transfer to monomer reactions in high-temperature polymerization of alkyl acrylates.

Science.gov (United States)

Moghadam, Nazanin; Liu, Shi; Srinivasan, Sriraj; Grady, Michael C; Soroush, Masoud; Rappe, Andrew M

2013-03-28

This article presents a computational study of chain transfer to monomer (CTM) reactions in self-initiated high-temperature homopolymerization of alkyl acrylates (methyl, ethyl, and n-butyl acrylate). Several mechanisms of CTM are studied. The effects of the length of live polymer chains and the type of monoradical that initiated the live polymer chains on the energy barriers and rate constants of the involved reaction steps are investigated theoretically. All calculations are carried out using density functional theory. Three types of hybrid functionals (B3LYP, X3LYP, and M06-2X) and four basis sets (6-31G(d), 6-31G(d,p), 6-311G(d), and 6-311G(d,p)) are applied to predict the molecular geometries of the reactants, products and transition sates, and energy barriers. Transition state theory is used to estimate rate constants. The results indicate that abstraction of a hydrogen atom (by live polymer chains) from the methyl group in methyl acrylate, the methylene group in ethyl acrylate, and methylene groups in n-butyl acrylate are the most likely mechanisms of CTM. Also, the rate constants of CTM reactions calculated using M06-2X are in good agreement with those estimated from polymer sample measurements using macroscopic mechanistic models. The rate constant values do not change significantly with the length of live polymer chains. Abstraction of a hydrogen atom by a tertiary radical has a higher energy barrier than abstraction by a secondary radical, which agrees with experimental findings. The calculated and experimental NMR spectra of dead polymer chains produced by CTM reactions are comparable. This theoretical/computational study reveals that CTM occurs most likely via hydrogen abstraction by live polymer chains from the methyl group of methyl acrylate and methylene group(s) of ethyl (n-butyl) acrylate.

Effect of olive mill wastewater phenol compounds on reactive carbonyl species and Maillard reaction end-products in ultrahigh-temperature-treated milk

NARCIS (Netherlands)

Troise, A.D.; Fiore, A.; Colantuono, A.; Kokkinidou, S.; Peterson, D.G.; Fogliano, V.

2014-01-01

Thermal processing and Maillard reaction (MR) affect the nutritional and sensorial qualities of milk. In this paper an olive mill wastewater phenolic powder (OMW) was tested as a functional ingredient for inhibiting MR development in ultrahigh-temperature (UHT)-treated milk. OMW was added to milk at

An integrated high temperature environmental cell for atom probe tomography studies of gas-surface reactions: Instrumentation and results

International Nuclear Information System (INIS)

Dumpala, S.; Broderick, S.R.; Bagot, P.A.J.; Rajan, K.

2014-01-01

An integrated environmental cell has been designed and developed for the latest generation of Atom Probe Tomography LEAP™ instruments, allowing controlled exposure of samples to gases at high temperatures. Following treatment, samples can be transferred through the LEAP vacuum system for subsequent APT analysis, which provides detailed information on changes to chemical microstructures following the reactions with near-atomic resolution. A full description of the cell is presented, along with some sample results on the oxidation of aluminum and two platinum-group alloys, demonstrating the capability of combining exposure/characterization functionality in a single instrument. - Highlights: • Designed and built atom probe environmental cell for in situ reactions. • Investigated Al oxidation, and demonstrated improvement with new cell. • in situ APT analysis of Pt-alloys showed surface segregation of Rh and Ir

Review of the sodium fire experiments including sodium-concrete-reactions and summary of the results

International Nuclear Information System (INIS)

Cherdron, W.

1996-01-01

In the technical and design concept of containment systems of sodium cooled breeder reactors it has to be considered, that leakages in sodium pipes lead to sodium fires. The temperature and pressure rise caused by sodium fires makes it indispensable to analyse these accidents to be able to assess the safety of the whole system. Generally sodium leakages may lead to three different types of fires with different consequences. The main influences are the geometry of the leakage, shape, size, location, and the sodium conditions, such as temperature, flow rate and velocity. It must be also considered the reaction of sodium with surfaces like concrete. The paper gives an overview over all the sodium fire experiments performed in the FAUNA-facility (220 m 3 ) of the Forschungszentrum Karlsruhe in the years 1979 to 1993. The experimental program started with the investigation of pool fires on burning areas between 2 and 12 m 2 with up to 500 kg of Sodium. The experiments had been continued with 3 combined fires and 40 experiments on spray fires. 7 experiments on sodium-concrete reactions completed the program. (author)

Temperature escalation in PWR fuel rod simulator bundles due to the zircaloy/steam reaction: Test ESBU-1

International Nuclear Information System (INIS)

Hagen, S.; Malauschek, H.; Peck, S.O.; Wallenfels, K.P.

1983-12-01

This report describes the test conduct and results of the bundle test ESBU-1. The test objective was the investigation of temperature escalation of zircaloy clad fuel rods. The investigation of the temperature escalation is part of a program of out-of-pile experiments, performed within the framework of the PNS Several Fuel Damage Program. The bundle was composed of a 3x3 array of fuel rod simulators surrounded by a zircaloy shroud which was insulated with a ZrO 2 fiber ceramic wrap. The fuel rod simulators comprised a tungsten heater, UO 2 annular pellets, and zircaloy cladding over a 0.4 m heated length. A steam flow of 1 g/s was inlet to the bundle. The most pronounced temperature escalation was found on the central rod. The initial heatup rate of 2 0 C/s at 1100 0 C increased to approximately 6 0 C/s. The maximum temperature reached was 2250 0 C. The following fast temperature decrease was caused by runoff of molten zircaloy. Molten zircaloy swept down the thin cladding oxide layer formed during heatup. The melt dissolved the surface of the UO 2 pellets and refroze as a coherent lump in the lower part of the bundle. The remaining pellets fragmented during cooldown and formed a powdery layer on the refrozen lump. The lump was sectioned posttest at several elevations: Dissolution of UO 2 by the molten zircaloy, interaction between the melt and previously oxidized zircaloy, and oxidation of the melt had occurred. (orig.) [de

Temperature-controlled cross-linking of silver nanoparticles with diels-alder reaction and its application on antibacterial property

Science.gov (United States)

Liu, Lian; Yang, Pengfei; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling

2017-05-01

Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV-vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.

PENGARUH SORPSI AIR DAN SUHU TRANSISI GELAS TERHADAP LAJU PENCOKLATAN NON-ENZIMATIS PADA PANGAN MODEL [The Effect of Water Sorption and Glass Transition Temperature on Non-Enzymatic Browning Reaction of Food Models

Directory of Open Access Journals (Sweden)

Dede R Adawiyah1

2005-12-01

Full Text Available This research was aimer/ to study the extend of non enzymatic browning reaction in food models containing the mixture of tapioca starch, casein, sucrose and oh at different moisture contents (2.55%, 5.26%, 7.54%, 15.20%. 15.93% and 23.99% and storage temperatures (30, 55 and 700C. The non-enzymatic browning reaction was detected from brown color intensity measured by spechtrophotometer and colorimetric methods. The non-enzymatic browning reaction or food model follow pseudo-zero order reaction, suggesting that browning reaction occurred at moisture content above monolayer zone. T-Tg (T storage - Tg prediction and reaction rate constant (k plots showed that browning reaction occurred at temperature around glass transition and increased significantly at 150 above Tg of casein. Tapioca starch in the food model was under glassy condition. The mobility of substrate increased and diffused at amorphous matrix.

Temperature measurements in thermonuclear plasmas

International Nuclear Information System (INIS)

Breton, D.

1958-01-01

The temperatures needed to produce thermonuclear reactions are of the order of several million degrees Kelvin. Devising methods for measuring such temperatures has been the subject of research in many countries. In order to present the problem clearly and to demonstrate its importance, the author reviews the various conditions which must be fulfilled in order that reactions may be qualified as thermonuclear. The relationship between the temperature and the cross-section of the reactions is studied, and it is shown that the notion of temperature in the plasmas is complex, which leads to a consideration of the temperature of the ions and that of the electrons. None of the methods for the temperature measurements is completely satisfactory because of the hypotheses which must be made, and which are seldom fulfilled during high-intensity discharges in the plasmas. In practice it is necessary to use several methods simultaneously. (author) [fr

Experimental program to determine maximum temperatures for dry storage of spent fuel

International Nuclear Information System (INIS)

Knox, C.A.; Gilbert, E.R.; White, G.D.

1985-02-01

Although air is used as a cover gas in some dry storage facilities, other facilities use inert cover gases which must be monitored to assure inertness of the atmosphere. Thus qualifying air as a cover gas is attractive for the dry storage of spent fuels. At sufficiently high temperatures, air can react with spent fuel (UO 2 ) at the site of cladding breaches that formed during reactor irradiation or during dry storage. The reaction rate is temperature dependent; hence the rates can be maintained at acceptable levels if temperatures are low. Tests with spent fuel are being conducted at Pacific Northwest Laboratory (PNL) to determine the allowable temperatures for storage of spent fuel in air. Tests performed with nonirradiated UO 2 pellets indicated that moisture, surface condition, gamma radiation, gadolinia content of the fuel pellet, and temperature are important variables. Tests were then initiated on spent fuel to develop design data under simulated dry storage conditions. Tests have been conducted at 200 and 230 0 C on spent fuel in air and 275 0 C in moist nitrogen. The results for nonirradiated UO 2 and published data for irradiated fuel indicate that above 230 0 C, oxidation rates are unacceptably high for extended storage in air. The tests with spent fuel will be continued for approximately three years to enable reliable extrapolations to be made for extended storage in air and inert gases with oxidizing constituents. 6 refs., 6 figs., 3 tabs

Influence of refreshment/activation cycles and temperature rise on the reaction rate of sodium hypochlorite with bovine dentine during ultrasonic activated irrigation

NARCIS (Netherlands)

Macedo, R.G.; Verhaagen, B.; Wesselink, P.R.; Versluis, Michel; van der Sluis, L.W.M.

2014-01-01

Aim To evaluate the effect of multiple refreshment/activation cycles and temperature on the reaction rate of sodium hypochlorite (NaOCl) with bovine dentine during ultrasonic activated irrigation (UAI) under laboratory conditions. Methodology The root canal walls of 24 standardized root canals in

High Temperature Degradation Mechanisms in Polymer Matrix Composites

Science.gov (United States)

Cunningham, Ronan A.

1996-01-01

Polymer matrix composites are increasingly used in demanding structural applications in which they may be exposed to harsh environments. The durability of such materials is a major concern, potentially limiting both the integrity of the structures and their useful lifetimes. The goal of the current investigation is to develop a mechanism-based model of the chemical degradation which occurs, such that given the external chemical environment and temperatures throughout the laminate, laminate geometry, and ply and/or constituent material properties, we can calculate the concentration of diffusing substances and extent of chemical degradation as functions of time and position throughout the laminate. This objective is met through the development and use of analytical models, coupled to an analysis-driven experimental program which offers both quantitative and qualitative information on the degradation mechanism. Preliminary analyses using a coupled diffusion/reaction model are used to gain insight into the physics of the degradation mechanisms and to identify crucial material parameters. An experimental program is defined based on the results of the preliminary analysis which allows the determination of the necessary material coefficients. Thermogravimetric analyses are carried out in nitrogen, air, and oxygen to provide quantitative information on thermal and oxidative reactions. Powdered samples are used to eliminate diffusion effects. Tests in both inert and oxidative environments allow the separation of thermal and oxidative contributions to specimen mass loss. The concentration dependency of the oxidative reactions is determined from the tests in pure oxygen. Short term isothermal tests at different temperatures are carried out on neat resin and unidirectional macroscopic specimens to identify diffusion effects. Mass loss, specimen shrinkage, the formation of degraded surface layers and surface cracking are recorded as functions of exposure time. Geometry effects

On the use temperature parameterized rate coefficients in the estimation of non-equilibrium reaction rates

Science.gov (United States)

Shizgal, Bernie D.; Chikhaoui, Aziz

2006-06-01

The present paper considers a detailed analysis of the nonequilibrium effects for a model reactive system with the Chapman-Eskog (CE) solution of the Boltzmann equation as well as an explicit time dependent solution. The elastic cross sections employed are a hard sphere cross section and the Maxwell molecule cross section. Reactive cross sections which model reactions with and without activation energy are used. A detailed comparison is carried out with these solutions of the Boltzmann equation and the approximation introduced by Cukrowski and coworkers [J. Chem. Phys. 97 (1992) 9086; Chem. Phys. 89 (1992) 159; Physica A 188 (1992) 344; Chem. Phys. Lett. A 297 (1998) 402; Physica A 275 (2000) 134; Chem. Phys. Lett. 341 (2001) 585; Acta Phys. Polonica B 334 (2003) 3607.] based on the temperature of the reactive particles. We show that the Cukrowski approximation has limited applicability for the large class of reactive systems studied in this paper. The explicit time dependent solutions of the Boltzmann equation demonstrate that the CE approach is valid only for very slow reactions for which the corrections to the equilibrium rate coefficient are very small.

Application of room temperature ionic liquids in advanced fuel cycles RIAR research concept program users

International Nuclear Information System (INIS)

Bychkov, Alexander V.; Kormilitsyn, Michael V.; Savochkin, Yuri P.; Osipenko, Alexander G.; Smolensky, Valeri V.; Shadrin, Alexander Yu.; Babain, Vladimir A.

2005-01-01

The paper reviews briefly the research program on application of Room Temperature Ionic Liquids (RTILs) in some processes of the nuclear fuel reprocessing, particularly in the uranium-aluminum fuel reprocessing and separation of TPEs and REEs from the PUREX process liquid waste, and approaches to implementation of this program. (author)

DETERMINING THE COMPOSITION OF HIGH TEMPERATURE COMBUSTION PRODUCTS OF FOSSIL FUEL BASED ON VARIATIONAL PRINCIPLES AND GEOMETRIC PROGRAMMING

Directory of Open Access Journals (Sweden)

Velibor V Vujović

2011-01-01

Full Text Available This paper presents the algorithm and results of a computer program for calculation of complex equilibrium composition for the high temperature fossil fuel combustion products. The method of determining the composition of high temperatures combustion products at the temperatures appearing in the open cycle MHD power generation is given. The determination of combustion product composition is based on minimization of the Gibbs free energy. The number of equations to be solved is reduced by using variational principles and a method of geometric programming and is equal to the sum of the numbers of elements and phases. A short description of the computer program for the calculation of the composition and an example of the results are also given.

Hydrogen desorption reactions of Li-N-H hydrogen storage system: Estimation of activation free energy

International Nuclear Information System (INIS)

Matsumoto, Mitsuru; Haga, Tetsuya; Kawai, Yasuaki; Kojima, Yoshitsugu

2007-01-01

The dehydrogenation reactions of the mixtures of lithium amide (LiNH 2 ) and lithium hydride (LiH) were studied under an Ar atmosphere by means of temperature programmed desorption (TPD) technique. The dehydrogenation reaction of the LiNH 2 /LiH mixture was accelerated by addition of 1 mol% Ti(III) species (k = 3.1 x 10 -4 s -1 at 493 K), and prolonged ball-milling time (16 h) further enhanced reaction rate (k = 1.1 x 10 -3 s -1 at 493 K). For the hydrogen desorption reaction of Ti(III) doped samples, the activation energies estimated by Kissinger plot (95 kJ mol -1 ) and Arrhenius plot (110 kJ mol -1 ) were in reasonable agreement. The LiNH 2 /LiH mixture without Ti(III) species, exhibited slower hydrogen desorption process and the kinetic traces deviated from single exponential behavior. The results indicated the Ti(III) additives change the hydrogen desorption reaction mechanism of the LiNH 2 /LiH mixture

Status of the INL high-temperature electrolysis research program –experimental and modeling

Energy Technology Data Exchange (ETDEWEB)

J. E. O' Brien; C. M. Stoots; M. G. McKellar; E. A. Harvego; K. G. Condie; G. K. Housley; J. S. Herring; J. J. Hartvigsen

2009-04-01

This paper provides a status update on the high-temperature electrolysis (HTE) research and development program at the Idaho National Laboratory (INL), with an overview of recent large-scale system modeling results and the status of the experimental program. System analysis results have been obtained using the commercial code UniSim, augmented with a custom high-temperature electrolyzer module. The process flow diagrams for the system simulations include an advanced nuclear reactor as a source of high-temperature process heat, a power cycle and a coupled steam electrolysis loop. Several reactor types and power cycles have been considered, over a range of reactor coolant outlet temperatures. In terms of experimental research, the INL has recently completed an Integrated Laboratory Scale (ILS) HTE test at the 15 kW level. The initial hydrogen production rate for the ILS test was in excess of 5000 liters per hour. Details of the ILS design and operation will be presented. Current small-scale experimental research is focused on improving the degradation characteristics of the electrolysis cells and stacks. Small-scale testing ranges from single cells to multiple-cell stacks. The INL is currently in the process of testing several state-of-the-art anode-supported cells and is working to broaden its relationship with industry in order to improve the long-term performance of the cells.

Photoluminescence and self-assembly of cesium lead halide perovskite nanocrystals: Effects of chain length of organic amines and reaction temperature

International Nuclear Information System (INIS)

Yuan, Yi; Liu, Zheming; Liu, Zhenyang; Peng, Lan; Li, Yongjie; Tang, Aiwei

2017-01-01

Highlights: • CsPbBr_3 perovskite nanocrystals have been synthesized in the presence of organic amines with different hydrocarbon length. • The photoluminescence of the CsPbBr_3 nanocrystals is affected by the varying the carbon length of the organic amines. • The lower reaction temperature and hydrocarbon chain length of the organic ligands play a significant role in the self-assembly of CsPbBr_3 nanocrystals. - Abstract: All-inorganic halide perovskites have become one of the most prospective materials for lightening and display technology due to their color-tunable and narrow-band emission. Herein, we have systematically studied the effects of organic amines with different hydrocarbon chain length on the optical properties and morphology as well as the crystal structure of colloidal CsPbBr_3 nanocrystals (NCs), which were synthesized in the presence of oleic acid (OA) and organic amines by using a simple hot-injection approach. The hydrocarbon chain length has shown an independent correlation to the morphology and crystal structure of the as-obtained CsPbBr_3 NCs at 160 °C, but their optical properties can be affected to some extent. The photoluminescence quantum yields (PLQYs) of the CsPbBr_3 NCs synthesized in the presence of organic amines with long carbon chain length are generally in the range of 55–80% for different reaction time, but the PLQYs of less than 20% are obtained for the products synthesized in the presence of octylamine (OTAm) with short carbon chain length. The effects of the reaction temperature on the optical properties, size and crystal structure of the CsPbBr_3 NCs synthesized in the presence of cetylamine (CTAm) are studied. Interestingly, some nanoplates also appear in these CsPbBr_3 NCs obtained at relatively low temperatures (120 and 140 °C), which have a strong tendency to self-assemble into face-to-face nanostructures. Such a similar self-assembly behavior is also observed in the product synthesized in the presence of

Photoluminescence and self-assembly of cesium lead halide perovskite nanocrystals: Effects of chain length of organic amines and reaction temperature

Energy Technology Data Exchange (ETDEWEB)

Yuan, Yi; Liu, Zheming; Liu, Zhenyang; Peng, Lan; Li, Yongjie; Tang, Aiwei, E-mail: awtang@bjtu.edu.cn

2017-05-31

Highlights: • CsPbBr{sub 3} perovskite nanocrystals have been synthesized in the presence of organic amines with different hydrocarbon length. • The photoluminescence of the CsPbBr{sub 3} nanocrystals is affected by the varying the carbon length of the organic amines. • The lower reaction temperature and hydrocarbon chain length of the organic ligands play a significant role in the self-assembly of CsPbBr{sub 3} nanocrystals. - Abstract: All-inorganic halide perovskites have become one of the most prospective materials for lightening and display technology due to their color-tunable and narrow-band emission. Herein, we have systematically studied the effects of organic amines with different hydrocarbon chain length on the optical properties and morphology as well as the crystal structure of colloidal CsPbBr{sub 3} nanocrystals (NCs), which were synthesized in the presence of oleic acid (OA) and organic amines by using a simple hot-injection approach. The hydrocarbon chain length has shown an independent correlation to the morphology and crystal structure of the as-obtained CsPbBr{sub 3} NCs at 160 °C, but their optical properties can be affected to some extent. The photoluminescence quantum yields (PLQYs) of the CsPbBr{sub 3} NCs synthesized in the presence of organic amines with long carbon chain length are generally in the range of 55–80% for different reaction time, but the PLQYs of less than 20% are obtained for the products synthesized in the presence of octylamine (OTAm) with short carbon chain length. The effects of the reaction temperature on the optical properties, size and crystal structure of the CsPbBr{sub 3} NCs synthesized in the presence of cetylamine (CTAm) are studied. Interestingly, some nanoplates also appear in these CsPbBr{sub 3} NCs obtained at relatively low temperatures (120 and 140 °C), which have a strong tendency to self-assemble into face-to-face nanostructures. Such a similar self-assembly behavior is also observed in the

Supramolecular engineering through temperature-induced chemical modification of 2H-tetraphenylporphyrin on Ag(111): flat phenyl conformation and possible dehydrogenation reactions.

Science.gov (United States)

Di Santo, Giovanni; Blankenburg, Stephan; Castellarin-Cudia, Carla; Fanetti, Mattia; Borghetti, Patrizia; Sangaletti, Luigi; Floreano, Luca; Verdini, Alberto; Magnano, Elena; Bondino, Federica; Pignedoli, Carlo A; Nguyen, Manh-Thuong; Gaspari, Roberto; Passerone, Daniele; Goldoni, Andrea

2011-12-16

Scratching the surface: Formation of a monolayer of 2H-tetraphenylporphyrins (2H-TPP) on Ag(111), either by sublimation of a multilayer in the range 525-600 K or by annealing (at the same temperature) a monolayer deposited at room temperature, induces a chemical modification of the molecules. Rotation of the phenyl rings into a flat conformation is observed and tentatively explained, by using DFT calculations, as a peculiar reaction due to molecular dehydrogenation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nuclear Astrophysics and Neutron Induced Reactions: Quasi-Free Reactions and RIBs

International Nuclear Information System (INIS)

Cherubini, S.; Spitaleri, C.; Crucilla, V.; Gulino, M.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Puglia, S.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Coc, A.; Kubono, S.; Binh, D. N.; Hayakawa, S.; Wakabayashi, Y.; Yamaguchi, H.; Burjan, V.; Kroha, V.; De Sereville, N.

2010-01-01

The use of quasi-free reactions in studying nuclear reactions between charged particles of astrophysical interest has received much attention over the last two decades. The Trojan Horse Method is based on this approach and it has been used to study a number of reactions relevant for Nuclear Astrophysics. Recently we applied this method to the study of nuclear reactions that involve radioactive species, namely to the study of the 18 F+p→ 15 O+α process at temperatures corresponding to the energies available in the classical novae scenario. Quasi-free reactions can also be exploited to study processes induced by neutrons. This technique is particularly interesting when applied to reaction induced by neutrons on unstable short-lived nuclei. Such processes are very important in the nucleosynthesis of elements in the sand r-processes scenarios and this technique can give hints for solving key questions in nuclear astrophysics where direct measurements are practically impossible.

A temperature dependence kinetics study of the reactions of Cl/2-P-3/2/ with O3, CH4, and H2O2

Science.gov (United States)

Watson, R.; Machado, G.; Fischer, S.; Davis, D. D.

1976-01-01

The temperature dependence of two chlorine atom reactions of considerable fundamental importance to stratospheric chemistry was studied using the technique of flash photolysis-resonance fluorescence. The reactions of interest were: (1) Cl + O3 yields ClO + O2 studied at 220-350 K, and (2) Cl + CH4 yields CH3 + HCl studied at 218-401 K. In addition, the reaction Cl + H2O2 yields HCl + HO2 was studied at 300 K. The corresponding rate constants are provided for the three reactions. The new rate data implies the need to revise downward by a factor of 2.4-3 the magnitude of the ozone perturbation due to the presence of ClO/x/ species in the stratosphere, predicted by earlier model calculations.

[Reaction mechanism studies of heavy ion induced nuclear reactions]: Annual progress report, October 1987

International Nuclear Information System (INIS)

Mignerey, A.C.

1987-10-01

The experiments which this group has been working on seek to define the reaction mechanisms responsible for complex fragment emission in heavy ion reactions. The reactions studied are La + La, La + Al, and La + Cu at 46.8 MeV/u; and Ne + Ag and Ne + Au reactions at 250 MeV/u. Another experimental program at the Oak Ridge Hollifield Heavy Ion Research Facility (HHIRF) is designed to measure the excitation energy division between reaction products in asymmetric deep inelastic reactions. A brief description is given of progress to date, the scientific goals of this experiment and the plastic phoswich detectors developed for this experiment

CONTEMPT-LT/028: a computer program for predicting containment pressure-temperature response to a loss-of-coolant accident

International Nuclear Information System (INIS)

Hargroves, D.W.; Metcalfe, L.J.; Wheat, L.L.; Niederauer, G.F.; Obenchain, C.F.

1979-03-01

CONTEMPT-LT is a digital computer program, written in FORTRAN IV, developed to describe the long-term behavior of water-cooled nuclear reactor containment systems subjected to postulated loss-of-coolant accident (LOCA) conditions. The program calculates the time variation of compartment pressures, temperatures, mass and energy inventories, heat structure temperature distributions, and energy exchange with adjacent compartments. The program is capable of describing the effects of leakage on containment response. Models are provided to describe fan cooler and cooling spray engineered safety systems. An annular fan model is also provided to model pressure control in the annular region of dual containment systems. Up to four compartments can be modeled with CONTEMPT-LT, and any compartment except the reactor system may have both a liquid pool region and an air--vapor atmosphere region above the pool. Each region is assumed to have a uniform temperature, but the temperatures of the two regions may be different

Understanding the Oxygen Reduction Reaction on a Y/Pt(111) Single Crystal

DEFF Research Database (Denmark)

Ulrikkeholm, Elisabeth Therese; Johansson, Tobias Peter; Malacrida, Paolo

2014-01-01

Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation of this tec......Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation...... using electrochemical measurements, low energy electron diffraction, ion scattering spectroscopy, angle resolved X-ray photoelectron spectroscopy, temperature programmed desorption of CO, and synchrotron based X-ray absorption spectroscopy and surface sensitive X-ray diffraction. These measurements were...

OPEM3-program for calculating pion differential spectra in pp → npπ+ reaction at energies up to 1 GeV. Physical model

International Nuclear Information System (INIS)

Suslenko, V.K.; Gajsak, I.I.

1982-01-01

Theoretical basis for the program to calcUlate the denSjties of differential criss sections of the third order (spectra) for pions produced in the reaction pp → npπ + at enerajes up to 1 GeV is presented. A variant of one pion exchange model (OPEM), im which precise account of all contributions from four polar Feynman diagrams is made is selected as a a physical model of the reaction pp → npπ + . The model apparatus is presented in correspondence with the scheme of the structure of OPEM 3 program for computer realized in Fortran language

The influence of temperature on the distribution and intensity of the reaction product in rat muscle fibers obtained with the histochemical method for myosin ATPase