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.

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.

Initial reaction between CaO and SO₂ under carbonating and non-carbonating conditions

DEFF Research Database (Denmark)

Rasmussen, Martin Hagsted; Wedel, Stig; Pedersen, Kim H.

2015-01-01

The initial kinetics of the CaO/SO2 reaction have been investigated for reaction times shorter than 1s and in the temperature interval between 450 and 600°C under both carbonating and non-carbonating conditions (0-20 vol% CO2) to clarify how recirculating CaO influences the emission of SO2 from...... showed that the CaO conversion with respect to SO2 declined when the CO2 concentration was increased. Under all conditions, larger specific surface areas of CaO gave higher reaction rates with SO2. Higher temperatures had a positive effect on the reaction between SO2 and CaO under non......-carbonating conditions, but no or even a negative effect under carbonating conditions. The results led to the conclusion that SO2 released from raw meal in the upper stages of the preheater does not to any significant extent react with CaO recirculating in the preheater tower....

Temperature dependence on sodium-water chemical reaction

International Nuclear Information System (INIS)

Tamura, Kenta; Deguchi, Yoshihiro; Suzuki, Koichi; Takata, Takashi; Yamaguchi, Akira; Kikuchi, Shin; Ohshima, Hiroyuki

2012-01-01

In a sodium-cooled fast reactor (SFR), liquid sodium is used as a heat transfer fluid because of its excellent heat transport capability. On the other hand, it has strong chemical reactivity with water vapor. One of the design basis accidents of the SFR is the water leakage into the liquid sodium flow by a breach of heat transfer tubes. This process ends up damages on the heat transport equipment in the SFR. Therefore, the study on sodium-water chemical reactions is of paramount importance for security reasons. This study aims to clarify the sodium-water reaction mechanisms using laser diagnostics. A quasi one-dimensional flame model is also applied to a sodium-water counter-flow reaction field. Temperature, H 2 , H 2 O, OH, Na and Particulate matter were measured using laser induced fluorescence and CARS in the counter-flow reaction field. The temperature of the reaction field was also modified to reduce the condensation of Na in the reaction zone. (author)

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.

Time-resolved studies of free radicals and laser-initiated chain reactions: Final report, 1 April 1979-31 March 1988

International Nuclear Information System (INIS)

Leone, S.R.

1988-03-01

Pulsed lasers were used in this work to photofragment molecules or to initiate chain reactions. One of the major advances was the availability of high-powered rare gas halide excimer lasers. In addition, pulsed Nd:YAG lasers and dye lasers were used throughout. Results include: generalized kinetic formulations of the problem of laser-initiated chain reactions. Several studies were carried out to explore the details of chain combustion phenomena, slow chain reactions, chain branching behavior, and vibrational temperatures of combusting mixtures. A method to determine the rotational temperature of nitrogen molecules by laser multiphoton ionization was shown. The chain reaction methodology was applied to complex polyatomic systems, in which complete infrared spectra of the emitting species were obtained. Systems studied included, chlorine + HBr, HI, methane, hydrogen, ethane, propane, butane, cyclopropane, and cyclohexane. Photofragmentation studies involved the production and analysis of radical species, such as methyl, CH 2 I, and CCH. Molecules studied included methylene iodide, methyl iodide, dimethyl mercury, acetone, acetylene, vinyl chloride, dichloroethylene, and fluorochloroethylene. The first infrared characterization of a highly vibrationally excited radical was shown. Reactions of methyl radicals were studied in detail, in which a new method for obtaining absolute values of the methyl radical reaction rates were obtained

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.

Adiabatic flame temperature of sodium combustion and sodium-water reaction

International Nuclear Information System (INIS)

Okano, Y.; Yamaguchi, A.

2001-01-01

In this paper, background information of sodium fire and sodium-water reaction accidents of LMFBR (liquid metal fast breeder reactor) is mentioned at first. Next, numerical analysis method of GENESYS is described in detail. Next, adiabatic flame temperature and composition of sodium combustion are analyzed, and affect of reactant composition, such oxygen and moisture, is discussed. Finally, adiabatic reaction zone temperature and composition of sodium-water reaction are calculated, and affects of reactant composition, sodium vaporization, and pressure are stated. Chemical equilibrium calculation program for generic chemical system (GENESYS) is developed in this study for the research on adiabatic flame temperature of sodium combustion and adiabatic reaction zone temperature of sodium-water reaction. The maximum flame temperature of the sodium combustion is 1,950 K at the standard atmospheric condition, and is not affected by the existence of moisture. The main reaction product is Na 2 O (l) , and in combustion in moist air, with NaOH (g) . The maximum reaction zone temperature of the sodium-water reaction is 1,600 K, and increases with the system pressure. The main products are NaOH (g) , NaOH (l) and H2 (g) . Sodium evaporation should be considered in the cases of sodium-rich and high pressure above 10 bar

Crack embryo formation before crack initiation and growth in high temperature water

International Nuclear Information System (INIS)

Arioka, Koji; Yamada, Takuyo; Terachi, Takumi; Miyamoto, Tomoki

2008-01-01

Crack growth measurements were performed in high temperature water and in air to examine the role of creep on IGSCC growth using cold rolled non-sensitized Type316(UNS S31600), TT690 alloy, MA600 alloy, and Carbon steel (STPT42). In addition, crack initiation tests were performed also in high temperature water and in air using specially designed CT specimen. The obtained major results are as follows: (1) TT690 did crack in intergranularly in hydrogenated high temperature water if material is cold worked in heavily. (2) Cold worked carbon steel also cracked in intergranularly in dearated high temperature water. (3) Intergranular crack growth was recognized on cold worked 316, TT690, MA600, and carbon steel even in air which might be crack embryo of IGSCC. (4) Simple Arrhenius type temperature dependence was observed on IGSCC in high temperature water and creep crack growth in air. This suggested that intergranular crack growth rate was determined by some thermal activated reaction. (5) Vacancy condensation was recognized at just ahead of the crack tips of IGSCC and creep crack of cold worked steel. This showed that IGSCC and creep crack growth was controlled by same mechanism. (6) Clear evidence of vacancies condensation was recognized at just beneath the surface before crack initiation. This proved that crack did initiate as the result of diffusion of vacancies in the solid. And the incubation time seems to be controlled by the required time for the condensation of vacancies to the stress concentrated zone. (7) Diffusion of subsituational atoms was also driven by stress gradient. This is the important knowledge to evaluate the SCC initiation after long term operation in LWR's. Based on the observed results, IGSCC initiation and growth mechanism were proposed considering the diffusion process of cold worked induced vacancies. (author)

Temperature escalation in PWR fuel rod simulators due to the zircaloy/steam reaction: Tests ESSI-1,2,3

International Nuclear Information System (INIS)

Hagen, S.; Malauschek, H.; Wallenfels, K.P.; Peck, S.O.

1983-08-01

This report discusses the test conduct, results, and posttest appearance of three scoping tests (ESSI-1,2,3) investigating temperature escalation in zircaloy clad fuel rods. The experiments are part of an out-of-pile program using electrically heated fuel rod simulators to investigate PWR fuel element behavior up to temperatures of 2000 0 C. These experiments are part of the PNS Severe Fuel Damage Program. The temperature escalation is caused by the exothermal zircaloy/steam reaction, whose reaction rate increases exponentially with the temperature. The tests were performed using different initial oxide layers as a major parameter, obtained by varying the heatup rates and steam exposure times. (orig./RW) [de

Experimental evaluation of improved dual temperature hydrogen isotopic exchange reaction system

International Nuclear Information System (INIS)

Asakura, Yamato; Uchida, Shunsuke

1984-01-01

A proposed dual temperature hydrogen isotopic exchange reaction system between water and hydrogen gas is evaluated experimentally. The proposed system is composed of low temperature co-current reactors for reaction between water mists and hydrogen gas and high temperature co-current reactors for reaction between water vapor and hydrogen gas. Thus, operation is possible under atmospheric pressure with high reaction efficiency. Using the pilot test system which is composed of ten low temperature (30 0 C) reaction units and ten high temperature (200 0 C) reaction units, an experimental separation of deuterium from light water is carried out. The enrichment factor under steady state conditions, its dependency on operating time, and the reaction period necessary to obtain the steady state enrichment factor are determined experimentally and compared with calculations. It is shown that separation ability in a multistage reaction system can be estimated by numerical calculation using actual reaction efficiency in a unit reactor. (author)

Temperature effects on lithium-nitrogen reaction rates

International Nuclear Information System (INIS)

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

1985-08-01

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

Kinetics of chemical reactions initiated by hot atoms

International Nuclear Information System (INIS)

Firsova, L.P.

1977-01-01

Modern ideas about kinetics of chemical reactions of hot atoms are generalized. The main points of the phenomenological theories (''kinetic theory'' of Wolfgang-Estrup hot reactions and the theory of ''reactions integral probability'' of Porter) are given. Physico-chemical models of elastic and non-elastic collisions are considered which are used in solving Boltzmann integro-differential equations and stochastic equations in the Porter theory. The principal formulas are given describing probabilities or yields of chemical reactions, initiated with hot atoms, depending on the distribution functions of hot particles with respect to energy. Briefly described are the techniques and the results of applying the phenomenological theories for interpretation of the experimental data obtained during nuclear reactions with hot atoms, photochemical investigations, etc. 96 references are given

Study of n-Butyl Acrylate Self-Initiation Reaction Experimentally and via Macroscopic Mechanistic Modeling

Directory of Open Access Journals (Sweden)

Ahmad Arabi Shamsabadi

2016-04-01

Full Text Available This paper presents an experimental study of the self-initiation reaction of n-butyl acrylate (n-BA in free-radical polymerization. For the first time, the frequency factor and activation energy of the monomer self-initiation reaction are estimated from measurements of n-BA conversion in free-radical homo-polymerization initiated only by the monomer. The estimation was carried out using a macroscopic mechanistic mathematical model of the reactor. In addition to already-known reactions that contribute to the polymerization, the model considers a n-BA self-initiation reaction mechanism that is based on our previous electronic-level first-principles theoretical study of the self-initiation reaction. Reaction rate equations are derived using the method of moments. The reaction-rate parameter estimates obtained from conversion measurements agree well with estimates obtained via our purely-theoretical quantum chemical calculations.

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 muonium reaction rates in the gas phase

International Nuclear Information System (INIS)

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

1981-01-01

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

The similar hexheimer reaction during initial treatment of pulmonary tuberculosis: CT appearances

International Nuclear Information System (INIS)

Lu Yan; Zhou Xinhua; Xie Ruming; Xu Jinping

2009-01-01

Objective: To investigate CT features of similar Hexheimer's reaction during initial treatment of active pulmonary tuberculosis. Methods: The similar Hexheimer's reaction in 44 patients diagnosed by clinic and follow-up CT scans were retrospectively reviewed by three radiologists. Results: During initial treatment of active pulmonary tuberculosis, development of radiographic progression were observed in 57 foci, including 28 pulmonary lesions increased at the site of their original lesion or new opacities elsewhere, ipsilateral or contralateral to the original lesion or both, 10 lesions related to the pleura (pleural effusion, pleural tuberculoma), 15 lymphadenectasis, 3 thymus reactions, and 1 cardiac pericardium thickening, respectively. These reactions appeared from the 20 days to 3.5 months, then with continuation of the initial chemotherapy for 1.0-3.0 months, the radiographic response was excellent with the areas of progression and the original lesions demonstrating resolution or improvement. Conclusion: The CT appearances of similar Hexheimer's reaction during initial treatment of active tuberculosis are specific to a certainty. (authors)

Initiation of the microgene polymerization reaction with non-repetitive homo-duplexes

International Nuclear Information System (INIS)

Itsko, Mark; Zaritsky, Arieh; Rabinovitch, Avinoam; Ben-Dov, Eitan

2008-01-01

Microgene Polymerization Reaction (MPR) is used as an experimental system to artificially simulate evolution of short, non-repetitive homo-duplex DNA into multiply-repetitive products that can code for functional proteins. Blunt-end ligation by DNA polymerase is crucial in expansion of homo-duplexes (HDs) into head-to-tail multiple repeats in MPR. The propagation mechanism is known, but formation of the initial doublet (ID) by juxtaposing two HDs and polymerization through the gap has been ambiguous. Initiation events with pairs of HDs using Real-Time PCR were more frequent at higher HD concentrations and slightly below the melting temperature. A process molecularity of about 3.1, calculated from the amplification efficiency and the difference in PCR cycles at which propagation was detected at varying HD concentrations, led to a simple mechanism for ID formation: the gap between two HDs is bridged by a third. Considering thermodynamic aspects of the presumed intermediate 'nucleation complex' can predict relative propensity for the process with other HDs

Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study.

Science.gov (United States)

Zhou, Tingting; Lou, Jianfeng; Zhang, Yangeng; Song, Huajie; Huang, Fenglei

2016-07-14

We report million-atom reactive molecular dynamic simulations of shock initiation of β-cyclotetramethylene tetranitramine (β-HMX) single crystals containing nanometer-scale spherical voids. Shock induced void collapse and subsequent hot spot formation as well as chemical reaction initiation are observed which depend on the void size and impact strength. For an impact velocity of 1 km s(-1) and a void radius of 4 nm, the void collapse process includes three stages; the dominant mechanism is the convergence of upstream molecules toward the centerline and the downstream surface of the void forming flowing molecules. Hot spot formation also undergoes three stages, and the principal mechanism is kinetic energy transforming to thermal energy due to the collision of flowing molecules on the downstream surface. The high temperature of the hot spot initiates a local chemical reaction, and the breakage of the N-NO2 bond plays the key role in the initial reaction mechanism. The impact strength and void size have noticeable effects on the shock dynamical process, resulting in a variation of the predominant mechanisms leading to void collapse and hot spot formation. Larger voids or stronger shocks result in more intense hot spots and, thus, more violent chemical reactions, promoting more reaction channels and generating more reaction products in a shorter duration. The reaction products are mainly concentrated in the developed hot spot, indicating that the chemical reactivity of the hmx crystal is greatly enhanced by void collapse. The detailed information derived from this study can aid a thorough understanding of the role of void collapse in hot spot formation and the chemical reaction initiation of explosives.

The reaction of OH with H at elevated temperatures

DEFF Research Database (Denmark)

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

2002-01-01

The temperature dependence of the rate constant for the reaction between OH radicals and H atoms has been determined in Ar-saturated solutions at pH 2. The reaction was studied in the temperature range 5-233degreesC. The rate constants at 20degreesC and 200degreesC are 9.3 x 10(9) and 3.3 x 10...

Subsequent development of the normal temperature fusion reaction. Joon kakuyugo sonogo no shinten

Energy Technology Data Exchange (ETDEWEB)

Matsumoto, T. (Hokkaido University, Sapporo (Japan). Faculty of Engineering)

1991-04-24

This paper reports on a NATTOH model made public in May 1989 by T. Matsumoto who took notice of abnormality of the normal temperature fusion reaction. The NATTO model is based on a chain reaction by hydrogen with a hydrogen-catalyzed fusion reaction which is the normal temperature fusion reaction as an elementary process. If a high temperature fusion reaction is a small-size simulation of the fusion reaction rising on the surface of the sparkling star like the sun, the normal temperature fusion reaction can be a small-size simulation of the phenomena in the last years of the star in the far distance of the space. This gives reality to the normal temperature fusion reaction. The reaction mechanism of the normal temperature fusion reaction is almost being clarified by a NATTOH model. There remain problems on a possibility of generation of unknown radioactive rays and identification of radioactive wastes, but it seems that a prospect of commercialization can be talked about now. As for the utilization as energy, sea water may be used as it is. 10 ref., 5 figs.

Subgingival temperature and microbiota in initial periodontitis.

Science.gov (United States)

Maiden, M F; Tanner, A C; Macuch, P J; Murray, L; Kent, R L

1998-10-01

The association between subgingival temperature, other clinical characteristics, and the subgingival microbiota was examined in adult subjects with initial periodontitis and differing levels of gingival inflammation. 43 subjects were measured at 6 sites per tooth for pocket depth, attachment level, presence of plaque, gingival redness, bleeding on probing and subgingival temperature at 3-month intervals for 1 year. Subgingival plaque was sampled from 15 initial active periodontitis sites (10 subjects), 121 gingivitis, sites (20 subjects) and 202 healthy sites (13 subjects), and included the 5 hottest and 5 coldest sites in each subject. Plaque samples were analyzed for 13 subgingival species using whole-genomic DNA probes. The major influences on the subgingival microbiota were the clinical status of sites, pocket depth, and the presence of supragingival plaque. No significant association between species and site temperature was observed. Initial active sites were associated with Bacteroides forsythus and Campylobacter rectus, and had a higher mean subgingival temperature and deeper mean pocket depth than inactive sites. A weak association between pocket depth and site temperature was noted. The major influence on subgingival temperature of sites was the anterior to posterior anatomical temperature gradient in the mandible and maxilla.

A review of reaction rates in high temperature air

Science.gov (United States)

Park, Chul

1989-01-01

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

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)

Hydrothermal Liquefaction of Dried Distillers Grains with solubles: A reaction temperature study

DEFF Research Database (Denmark)

Mørup, Anders; Christensen, Per Runge; Aarup, David Friis

2012-01-01

provides rapid heating of biomass feeds and the option of performing multiple sequential repetitions. This bypasses long, uncontrollable temperature gradients and unintended changes in the reaction chemistry. The product, a crude bio-oil, was characterized in terms of yield, elemental composition......The effect of the reaction temperature on hydrothermal liquefaction of dried distillers grains with solubles (DDGS) was investigated using a novel stop-flow reactor system at varying temperatures (300–400 °C), fixed pressure (250 bar), and fixed reaction time (15 min). The stop-flow reactor......, and chemical composition. Higher reaction temperatures resulted in improved bio-oil yields, less char formation, and higher heating values of the bio-oil. A supercritical reaction temperature of 400 °C was found to produce bio-oil in the highest yields and of the best quality....

Ozone initiated reactions and human comfort in indoor environments

DEFF Research Database (Denmark)

Tamas, Gyöngyi

2006-01-01

Chemical reactions between ozone and pollutants commonly found indoors have been suggested to cause adverse health and comfort effects among building occupants. Of special interest are reactions with terpenes and other pollutants containing unsaturated carbon-carbon bonds that are fast enough...... to occur under normal conditions in various indoor settings. These reactions are known to occur both in the gas phase (homogeneous reactions) and on the surfaces of building materials (heterogeneous reactions), producing a number of compounds that can be orders of magnitude more odorous and irritating than...... their precursors. The present thesis investigates the effects of ozone-initiated reactions with limonene and with various interior surfaces, including those associated with people, on short-term sensory responses. The evaluations were conducted using a perceived air quality (PAQ) method introduced by Fanger (1988...

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

Science.gov (United States)

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

2015-01-01

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

The 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)

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

Reaction enhancement of initially distant scalars by Lagrangian coherent structures

International Nuclear Information System (INIS)

Pratt, Kenneth R.; Crimaldi, John P.; Meiss, James D.

2015-01-01

Turbulent fluid flows have long been recognized as a superior means of diluting initial concentrations of scalars due to rapid stirring. Conversely, experiments have shown that the structures responsible for this rapid dilution can also aggregate initially distant reactive scalars and thereby greatly enhance reaction rates. Indeed, chaotic flows not only enhance dilution by shearing and stretching but also organize initially distant scalars along transiently attracting regions in the flow. To show the robustness of this phenomenon, a hierarchical set of three numerical flows is used: the periodic wake downstream of a stationary cylinder, a chaotic double gyre flow, and a chaotic, aperiodic flow consisting of interacting Taylor vortices. We demonstrate that Lagrangian coherent structures (LCS), as identified by ridges in finite time Lyapunov exponents, are directly responsible for this coalescence of reactive scalar filaments. When highly concentrated filaments coalesce, reaction rates can be orders of magnitude greater than would be predicted in a well-mixed system. This is further supported by an idealized, analytical model that was developed to quantify the competing effects of scalar dilution and coalescence. Chaotic flows, known for their ability to efficiently dilute scalars, therefore have the competing effect of organizing initially distant scalars along the LCS at timescales shorter than that required for dilution, resulting in reaction enhancement

Recovery of an initial temperature from discrete sampling

KAUST Repository

DeVore, Ronald

2014-11-01

The problem of recovering the initial temperature of a body from discrete temperature measurements made at later times is studied. While this problem has a general formulation, the results of this paper are only given in the simplest setting of a finite (one-dimensional), constant coefficient, linear rod. It is shown that with a judicious placement of a thermometer on this rod, the initial temperature profile of the rod can be completely determined by later time measurements. The paper then studies the number of measurements that are needed to recover the initial profile to a prescribed accuracy and provides an optimal reconstruction algorithm under the assumption that the initial profile is in a Sobolev class. © 2014 World Scientific Publishing Company.

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.

Chemiluminescence development after initiation of Maillard reaction in aqueous solutions of glycine and glucose: nonlinearity of the process and cooperative properties of the reaction system

Science.gov (United States)

Voeikov, Vladimir L.; Naletov, Vladimir I.

1998-06-01

Nonenzymatic glycation of free or peptide bound amino acids (Maillard reaction, MR) plays an important role in aging, diabetic complications and atherosclerosis. MR taking place at high temperatures is accompanied by chemiluminescence (CL). Here kinetics of CL development in MR proceeding in model systems at room temperature has been analyzed for the first time. Brief heating of glycine and D-glucose solutions to t greater than 93 degrees Celsius results in their browning and appearance of fluorescencent properties. Developed In solutions rapidly cooled down to 20 degrees Celsius a wave of CL. It reached maximum intensity around 40 min after the reaction mixture heating and cooling it down. CL intensity elevation was accompanied by certain decoloration of the solution. Appearance of light absorbing substances and development of CL depended critically upon the temperature of preincubation (greater than or equal to 93 degrees Celsius), initial pH (greater than or equal to 11,2), sample volume (greater than or equal to 0.5 ml) and reagents concentrations. Dependence of total counts accumulation on a system volume over the critical volume was non-monotonous. After reaching maximum values CL began to decline, though only small part of glucose and glycin had been consumed. Brief heating of such solutions to the critical temperature resulted in emergence of a new CL wave. This procedure could be repeated in one and the same reaction system for several times. Whole CL kinetic curve best fitted to lognormal distribution. Macrokinetic properties of the process are characteristic of chain reactions with delayed branching. Results imply also, that self-organization occurs in this system, and that the course of the process strongly depends upon boundary conditions and periodic interference in its course.

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.

Influence of initial temperature and heating method in the temperature profile during alkaline dissolution of Al for the production of Mo-99

Energy Technology Data Exchange (ETDEWEB)

Camilo, Ruth L.; Araujo, Izilda C.; Mindrisz, Ana C.; Forbicini, Christina A.L.G. de O., E-mail: rcamilo@ipen.br, E-mail: cruzaraujo22@gmail.com, E-mail: acmindri@ipen.br, E-mail: cforbici@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2013-07-01

Radionuclides in nuclear medicine can be used for diagnosis and therapy. The {sup 99m}Tc, son of {sup 99}Mo, is most often used in nuclear medicine as tracer element because of its favorable nuclear properties, accounting for about 80% of all diagnostic procedures in vivo. Aiming to resolve the dependency of Brazil with respect to the supply of {sup 99}Mo was created the Brazilian Multipurpose Reactor project (BMR), started in 2008, having as main objective to produce about 1000 Ci/week of {sup 99}Mo. This study is part of the project to obtain {sup 9}'9Mo by alkaline dissolution of UAl{sub x}-Al targets. The initial reaction temperature is an important parameter, since it has great influence on the value of the maximum temperature and dissolution time. According to literature, for security reasons the dissolution process must have its temperature controlled so that the maximum temperature has to be around 90 deg C. The behavior of the temperature during dissolution using three different methods of heating in order to minimize the fluctuation of temperature during dissolution, keeping its maximum value at around 90 deg C was studied. The three methods of heating chosen were: a) initial temperature of 85 deg C with continuous heating, b) heating water bath until it reaches the initial temperature (70 to 95 deg C), turning off after that, and c) external heating until it reached the starting temperature (60-95 deg C). The alkaline solution used was 3 mol.L{sup -1} NaOH{sub 3} and 2 mol.L{sup -1} NaNO{sub 3}. In the first study it was observed that after 1 minute of dissolution the solution temperature reached 100 deg C on average, up to a maximum of 109 deg C, ending with values around 95 deg C. In the second study after 3 minutes of dissolution the maximum temperature was 106 deg C and the minimum 100 deg C. In the third study the temperature rise during dissolution increased with increasing initial temperature which practically remains constant until the end

Self-reported adverse reactions among patients initiating antiretroviral therapy in Brazil

Directory of Open Access Journals (Sweden)

Cristiane A. Menezes de Pádua

Full Text Available A cross-sectional analysis was carried out to describe adverse reactions to antiretroviral therapy (ART reported by HIV-infected patients initiating treatment at two public health AIDS referral centers in Belo Horizonte, Brazil, 2001-2003 and to verify their association with selected variables. Adverse reactions were obtained through interview at the first follow-up visit (first month after the antiretroviral prescription. Socio-demographic and behavioral variables related to ART were obtained from baseline and follow-up interviews and clinical variables from medical charts. Patients with four or more reactions were compared to those with less than four. Odds ratio with 95% confidence interval were estimated using logistic regression model for both univariate and multivariate analyses. At least one adverse reaction was reported by 92.2% of the participants while 56.2% reported four or more different reactions. Antiretroviral regimens including indinavir/ritonavir, irregular use of antiretrovirals and switch in regimens were independently associated with four or more adverse reactions (OR=7.92, 5.73 and 2.03, respectively. The initial period of ARV treatment is crucial and patients´ perception of adverse reactions should be carefully taken into account. Strategies for monitoring and management of adverse reactions including the choice of regimens and the prevention of irregular ART should be developed in AIDS/HIV referral centers in Brazil to promote better adherence to antiretroviral therapy.

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.

Heat-Initiated Chemical Functionalization of Graphene

OpenAIRE

Gao, Guodong; Liu, Dandan; Tang, Shangcheng; Huang, Can; He, Mengci; Guo, Yu; Sun, Xiudong; Gao, Bo

2016-01-01

A heat-initiated chemical reaction was developed to functionalize CVD-grown graphene at wafer scale and the reaction was universally extended to carbon nanotubes, and other precursors that could be thermally converted to active radicals. The chemical reaction can occur in absence of oxygen and water vapor when the temperature is above the decomposition temperature of the reactants. The chemical reaction was also found to be substrate-dependent due to surface doping and inhomogeneity. A large-...

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...

Toluene pyrolysis studies and high temperature reactions of propargyl chloride

Energy Technology Data Exchange (ETDEWEB)

Kern, R.D.; Chen, H.; Qin, Z. [Univ. of New Orleans, LA (United States)

1993-12-01

The main focus of this program is to investigate the thermal decompositions of fuels that play an important role in the pre-particle soot formation process. It has been demonstrated that the condition of maximum soot yield is established when the reaction conditions of temperature and pressure are sufficient to establish a radical pool to support the production of polyaromatic hydrocarbon species and the subsequent formation of soot particles. However, elevated temperatures result in lower soot yields which are attributed to thermolyses of aromatic ring structures and result in the bell-shaped dependence of soot yield on temperature. The authors have selected several acyclic hydrocarbons to evaluate the chemical thermodynamic and kinetic effects attendant to benzene formation. To assess the thermal stability of the aromatic ring, the authors have studied the pyrolyses of benzene, toluene, ethylbenzene, chlorobenzene and pyridine. Time-of-flight mass spectrometry (TOF) is employed to analyze the reaction zone behind reflected shock waves. Reaction time histories of the reactants, products, and intermediates are constructed and mechanisms are formulated to model the experimental data. The TOF work is often performed with use of laser schlieren densitometry (LS) to measure density gradients resulting from the heats of various reactions involved in a particular pyrolytic system. The two techniques, TOF and LS, provide independent and complementary information about ring formation and ring rupture reactions.

Evaluation of the extent of initial Maillard reaction during cooking some vegetables by direct measurement of the Amadori compounds.

Science.gov (United States)

Yu, Jiahao; Zhang, Shuqin; Zhang, Lianfu

2018-01-01

During vegetable cooking, one of the most notable and common chemical reactions is the Maillard reaction, which occurs as a result of thermal treatment and dehydration. Amadori compound determination provides a very sensitive indicator for early detection of quality changes caused by the Maillard reaction, as well as to retrospectively assess the heat treatment or storage conditions to which the product has been subjected. In this paper, a hydrophilic interaction liquid chromatographic-electrospray ionization-tandem mass spectrometric method was developed for the analysis of eight Amadori compounds, and the initial steps of the Maillard reaction during cooking (steaming, frying and baking) bell pepper, red pepper, yellow onion, purple onion, tomato and carrot were also assessed by quantitative determination of these Amadori compounds. These culinary treatments reduced moisture and increased the total content of Amadori compounds, which was not dependent on the type of vegetable or cooking method. Moreover, the effect of steaming on Amadori compound content and water loss was less than that by baking and frying vegetables. Further studies showed that the combination of high temperature and short time may lead to lower formation of Amadori compounds when baking vegetables. Culinary methods differently affected the extent of initial Maillard reaction when vegetables were made into home-cooked products. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

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.

Temperature-dependent shock initiation of LX-17 explosive

Energy Technology Data Exchange (ETDEWEB)

Lee, R.S.; Chau, H.H.; Druce, R.L.; Moua, K.

1995-02-01

LX-17 samples, heated to temperatures up to 250 C, were impacted by 3 to 10-mm-wide, 50.8-mm-long strips of 0.13-mm-thick Kapton polyimide film at velocities up to 7.7 km/s. The Kapton strips were laminated onto a thin aluminum bridge foil and were launched to the desired velocity by discharging a capacitor bank through the foil, causing the foil to explode. The LX-17 samples were confined in a steel holder and heated in an oven to the desired temperature. After the capacitor bank was charged, the LX-17 sample in its steel holder was remotely drawn out of the oven on rails and positioned over the bridge-foil/Kapton-strip laminate. When the sample was in position, the bank was discharged, launching the Kapton strip against the LX-17 surface. The shock initiation threshold was measured for 3, 7, and 10-mm-wide strips at room temperature, 200 C and 250 C. The authors found a significant reduction in the velocity threshold and in the critical area for initiation when the samples were heated. The authors compare the results with the earlier data of Bloom, who measured the initiation threshold of LX-17 over the density range 1.8--1.91 g/cm{sup 3} at room temperature and {minus}54 C. LX-17 has a large coefficient of thermal expansion, as reported by Urtiew, et al., which reduces its density significantly t elevated temperatures. They find that the change of shock initiation threshold with temperature is consistent with the change in sample density, using the relation between threshold and density reported by Bloom.

Errors in Postural Preparation Lead to Increased Choice Reaction Times for Step Initiation in Older Adults

Science.gov (United States)

Nutt, John G.; Horak, Fay B.

2011-01-01

Background. This study asked whether older adults were more likely than younger adults to err in the initial direction of their anticipatory postural adjustment (APA) prior to a step (indicating a motor program error), whether initial motor program errors accounted for reaction time differences for step initiation, and whether initial motor program errors were linked to inhibitory failure. Methods. In a stepping task with choice reaction time and simple reaction time conditions, we measured forces under the feet to quantify APA onset and step latency and we used body kinematics to quantify forward movement of center of mass and length of first step. Results. Trials with APA errors were almost three times as common for older adults as for younger adults, and they were nine times more likely in choice reaction time trials than in simple reaction time trials. In trials with APA errors, step latency was delayed, correlation between APA onset and step latency was diminished, and forward motion of the center of mass prior to the step was increased. Participants with more APA errors tended to have worse Stroop interference scores, regardless of age. Conclusions. The results support the hypothesis that findings of slow choice reaction time step initiation in older adults are attributable to inclusion of trials with incorrect initial motor preparation and that these errors are caused by deficits in response inhibition. By extension, the results also suggest that mixing of trials with correct and incorrect initial motor preparation might explain apparent choice reaction time slowing with age in upper limb tasks. PMID:21498431

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)

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)

Recovery of an initial temperature from discrete sampling

KAUST Repository

DeVore, Ronald; Zuazua, Enrique

2014-01-01

The problem of recovering the initial temperature of a body from discrete temperature measurements made at later times is studied. While this problem has a general formulation, the results of this paper are only given in the simplest setting of a

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.)

The international surface temperature initiative

Science.gov (United States)

Thorne, P. W.; Lawrimore, J. H.; Willett, K. M.; Allan, R.; Chandler, R. E.; Mhanda, A.; de Podesta, M.; Possolo, A.; Revadekar, J.; Rusticucci, M.; Stott, P. A.; Strouse, G. F.; Trewin, B.; Wang, X. L.; Yatagai, A.; Merchant, C.; Merlone, A.; Peterson, T. C.; Scott, E. M.

2013-09-01

The aim of International Surface Temperature Initiative is to create an end-to-end process for analysis of air temperature data taken over the land surface of the Earth. The foundation of any analysis is the source data. Land surface air temperature records have traditionally been stored in local, organizational, national and international holdings, some of which have been available digitally but many of which are available solely on paper or as imaged files. Further, economic and geopolitical realities have often precluded open sharing of these data. The necessary first step therefore is to collate readily available holdings and augment these over time either through gaining access to previously unavailable digital data or through data rescue and digitization activities. Next, it must be recognized that these historical measurements were made primarily in support of real-time weather applications where timeliness and coverage are key. At almost every long-term station it is virtually certain that changes in instrumentation, siting or observing practices have occurred. Because none of the historical measures were made in a metrologically traceable manner there is no unambiguous way to retrieve the true climate evolution from the heterogeneous raw data holdings. Therefore it is desirable for multiple independent groups to produce adjusted data sets (so-called homogenized data) to adequately understand the data characteristics and estimate uncertainties. Then it is necessary to benchmark the performance of the contributed algorithms (equivalent to metrological software validation) through development of realistic benchmark datasets. In support of this, a series of successive benchmarking and assessment cycles are envisaged, allowing continual improvement while avoiding over-tuning of algorithms. Finally, a portal is proposed giving access to related data-products, utilizing the assessment results to provide guidance to end-users on which product is the most suited to

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

Science.gov (United States)

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

2016-11-05

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

Does increasing pressure always accelerate the condensed material decay initiated through bimolecular reactions? A case of the thermal decomposition of TKX-50 at high pressures.

Science.gov (United States)

Lu, Zhipeng; Zeng, Qun; Xue, Xianggui; Zhang, Zengming; Nie, Fude; Zhang, Chaoyang

2017-08-30

Performances and behaviors under high temperature-high pressure conditions are fundamentals for many materials. We study in the present work the pressure effect on the thermal decomposition of a new energetic ionic salt (EIS), TKX-50, by confining samples in a diamond anvil cell, using Raman spectroscopy measurements and ab initio simulations. As a result, we find a quadratic increase in decomposition temperature (T d ) of TKX-50 with increasing pressure (P) (T d = 6.28P 2 + 12.94P + 493.33, T d and P in K and GPa, respectively, and R 2 = 0.995) and the decomposition under various pressures initiated by an intermolecular H-transfer reaction (a bimolecular reaction). Surprisingly, this finding is contrary to a general observation about the pressure effect on the decomposition of common energetic materials (EMs) composed of neutral molecules: increasing pressure will impede the decomposition if it starts from a bimolecular reaction. Our results also demonstrate that increasing pressure impedes the H-transfer via the enhanced long-range electrostatic repulsion of H +δ H +δ of neighboring NH 3 OH + , with blue shifts of the intermolecular H-bonds. And the subsequent decomposition of the H-transferred intermediates is also suppressed, because the decomposition proceeds from a bimolecular reaction to a unimolecular one, which is generally prevented by compression. These two factors are the basic root for which the decomposition retarded with increasing pressure of TKX-50. Therefore, our finding breaks through the previously proposed concept that, for the condensed materials, increasing pressure will accelerate the thermal decomposition initiated by bimolecular reactions, and reveals a distinct mechanism of the pressure effect on thermal decomposition. That is to say, increasing pressure does not always promote the condensed material decay initiated through bimolecular reactions. Moreover, such a mechanism may be feasible to other EISs due to the similar intermolecular

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).

Self-reported adverse reactions among patients initiating antiretroviral therapy in Brazil

OpenAIRE

Pádua,Cristiane A. Menezes de; César,Cibele C.; Bonolo,Palmira F.; Acurcio,Francisco A.; Guimarães,Mark Drew C.

2007-01-01

A cross-sectional analysis was carried out to describe adverse reactions to antiretroviral therapy (ART) reported by HIV-infected patients initiating treatment at two public health AIDS referral centers in Belo Horizonte, Brazil, 2001-2003 and to verify their association with selected variables. Adverse reactions were obtained through interview at the first follow-up visit (first month) after the antiretroviral prescription. Socio-demographic and behavioral variables related to ART were obtai...

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.

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.

Optimal control of the initiation of a pericyclic reaction in the ...

Indian Academy of Sciences (India)

Abstract. Pericyclic reactions in the electronic ground state may be initiated by down-chirped pump-dump ... Figure 1. Cope rearrangement of semibullvalene, with pincer-motion-type ... investigations which have centred attention on the simp-.

Degradation of quinoline by wet oxidation - kinetic aspects and reaction mechanisms

DEFF Research Database (Denmark)

Thomsen, A.B.

1998-01-01

The high temperature, high pressure wet oxidation reaction of quinoline has been studied as a function of initial concentration, pH and temperature. At neutral to acidic pH, it is effective in the oxidation of quinoline at 240 degrees C and above, whereas under alkaline conditions the reaction...... is markedly slowed down. The results indicate that the reaction is an auto-catalysed, free radical chain reaction transforming 99% of quinoline to other substances. Of the quinoline. 30-50% was oxidised to CO2 and H2O depending on the initial concentration. Wet oxidation of deuterium-labelled quinoline...

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.

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

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).

Reflood behavior at low initial clad temperature in Slab Core Test Facility Core-II

International Nuclear Information System (INIS)

Akimoto, Hajime; Sobajima, Makoto; Abe, Yutaka; Iwamura, Takamichi; Ohnuki, Akira; Okubo, Tsutomu; Murao, Yoshio; Okabe, Kazuharu; Adachi, Hiromichi.

1990-07-01

In order to study the reflood behavior with low initial clad temperature, a reflood test was performed using the Slab Core Test Facility (SCTF) with initial clad temperature of 573 K. The test conditions of the test are identical with those of SCTF base case test S2-SH1 (initial clad temperature 1073 K) except the initial clad temperature. Through the comparison of results from these two tests, the following conclusions were obtained. (1) The low initial clad temperature resulted in the low differential pressures through the primary loops due to smaller steam generation in the core. (2) The low initial clad temperature caused the accumulated mass in the core to be increased and the accumulated mass in the downcomer to be decreased in the period of the lower plenum injection with accumulator (before 50s). In the later period of the cold leg injection with LPCI (after 100s), the water accumulation rates in the core and the downcomer were almost the same between both tests. (3) The low initial clad temperature resulted in the increase of the core inlet mass flow rate in the lower plenum injection period. However, the core inlet mass flow rate was almost the same regardless of the initial clad temperature in the later period of the cold leg injection period. (4) The low initial clad temperature resulted in the low turnaround temperature, high temperature rise and fast bottom quench front propagation. (5) In the region apart from the quench front, low initial clad temperature resulted in the lower heat transfer. In the region near the quench front, almost the same heat transfer coefficient was observed between both tests. (6) No flow oscillation with a long period was observed in the SCTF test with low initial clad temperature of 573 K, while it was remarkable in the Cylindrical Core Test Facility (CCTF) test which was performed with the same initial clad temperature. (J.P.N.)

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....

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

SCC Initiation Testing of Alloy 600 in High Temperature Water

Science.gov (United States)

Etien, Robert A.; Richey, Edward; Morton, David S.; Eager, Julie

Stress corrosion cracking (SCC) initiation tests have been conducted on Alloy 600 at temperatures from 304 to 367°C. Tests were conducted with in-situ monitored smooth tensile specimens under a constant load in hydrogenated environments. A reversing direct current electric potential drop (EPD) system was used for all of the tests to detect SCC initiation. Tests were conducted to examine the effects of stress (and strain), coolant hydrogen, and temperature on SCC initiation time. The thermal activation energy of SCC initiation was measured as 103 ± 18 kJ/mol in hydrogenated water, which is similar to the thermal activation energy for SCC growth. Results suggest that the fundamental mechanical parameter which controls SCC initiation is plastic strain not stress. SCC initiation was shown to have a different sensitivity than SCC growth to dissolved hydrogen level. Specifically, SCC initiation time appears to be relatively insensitive to hydrogen level in the nickel stability region.

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

Temperatures of fragment kinetic energy spectra

International Nuclear Information System (INIS)

Bauer, W.

1995-01-01

Multifragmentation reactions without large compression in the initial state (proton-induced reactions, reverse kinematics, projectile fragmentation) are examined, and it is verified quantitatively that the high temperatures obtained from fragment kinetic energy spectra and lower temperatures obtained from observables such as level population or isotope ratios can be understood in a common framework

Quantum wave packet study of D+OF reaction

International Nuclear Information System (INIS)

Kurban, M.; Karabulut, E.; Tutuk, R.; Goektas, F.

2010-01-01

The quantum dynamics of the D+OF reaction on the adiabatic potential energy surface of the ground 1 3 A ' state has been studied by using a time-dependent quantum real wave packet method. The state-to-state and state-to-all reaction probabilities for total angular momentum J = 0 have been calculated. The probabilities for J > 0 have been calculated by J-shifting the J = 0 results by means of capture model. Then, the integral cross sections and initial state selected rate constants have been calculated. The initial state-selected reaction probabilities and reaction cross section show threshold but not manifest any resonances and the initial state selected rate constants are sensitive to the temperature.

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

Ion-molecular reactions initiated by β-decay of tritium in tritiated compounds

International Nuclear Information System (INIS)

Akulov, G.P.

1976-01-01

Ion-molecular reactions initiated by β-decay of tritium and tritiated hydrocarbons have been systematized. The review describes the theoretical and experimental foundation of the radiochemical method of this important type of chemical interactions investigation. The reactions of the molecular ions of HeT + with methane, ethane, propane, butane and also with cycloalkanes from C 3 to C 6 are discussed. The reactions under consideration have been united into two groups: reactions involving HeT + ions and those involving carbonic ions. From the experimental results available, the conclusions have been drawn about the reactivity of these intermediate formations, about the mechanism of their interaction with organic substances, and also about the perspectives of using the radiochemical method in studies of ion-molecular reactions. The experimental results published before May 1974 are examined. The bibliography includes 162 references

Kinetics of the glucose/glycine Maillard reaction pathways: influences of pH and reactant initial concentrations

NARCIS (Netherlands)

Martins, S.I.F.S.; Boekel, van M.A.J.S.

2005-01-01

A previously proposed kinetic model for the glucose/glycine Maillard reaction pathways has been validated by changing the initial pH (4.8, 5.5, 6.0, 6.8 and 7.5) of the reaction and reactant initial concentrations (1:2 and 2:1 molar ratios were compared to the 1:1 ratio). The model consists of 10

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.

Exchange reaction between tritiated hydrogen and water vapor

International Nuclear Information System (INIS)

Yamada, Koichi; Takano, Kenichi; Watanabe, Tamaki.

1979-01-01

Exchange reaction of tritiated hydrogen to water vapor under the condition of tritium gas concentration between 1 μCi/l and 1 mCi/l was studied. Tritium gas with hydrogen gas of 5 Torr and water of 20 mg were enclosed in a Pyrex glass ampule with volume of about 100 ml. The mixed gas with water vapor was heated with electric furnace. The heating time was between 2 and 100 hr, and the temperature was 776, 725, 675, 621, and 570.5 0 K. After heating, tritiated water was trapped with liquid nitrogen, and counted with a liquid scintillation counter. The radioactive concentration of initial tritiated hydrogen was measured with a calibrated ionization chamber. The main results obtained are as follows; 1) the concentration of produced tritiated water is well proportioned to that of initial tritiated hydrogen, 2) the activation energy of exchange reaction from tritiated hydrogen to tritiated water is 26.2 kcal/mol and that of inverse reaction is 27.4 kcal/mol, 3) the reaction rate at room temperature which calculated with activation energy is 1.04 x 10 -13 day -1 , and then exchange reaction at room temperature is negligible. (author)

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.

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.

Mix and Inject: Reaction Initiation by Diffusion for Time-Resolved Macromolecular Crystallography

Directory of Open Access Journals (Sweden)

Marius Schmidt

2013-01-01

Full Text Available Time-resolved macromolecular crystallography unifies structure determination with chemical kinetics, since the structures of transient states and chemical and kinetic mechanisms can be determined simultaneously from the same data. To start a reaction in an enzyme, typically, an initially inactive substrate present in the crystal is activated. This has particular disadvantages that are circumvented when active substrate is directly provided by diffusion. However, then it is prohibitive to use macroscopic crystals because diffusion times become too long. With small micro- and nanocrystals diffusion times are adequately short for most enzymes and the reaction can be swiftly initiated. We demonstrate here that a time-resolved crystallographic experiment becomes feasible by mixing substrate with enzyme nanocrystals which are subsequently injected into the X-ray beam of a pulsed X-ray source.

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.

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.

Becoming the denigrated other: Group relations perspectives on initial reactions to a bipolar disorder diagnosis

Directory of Open Access Journals (Sweden)

Susan G. Goldberg

2012-09-01

Full Text Available The initial reactions to a bipolar disorder diagnosis of research participants in a small, qualitative study consisted of astonishment, dread of being mad, and extremely negative associations. All had prior mental health diagnoses, including episodes of severe depression (all but one and alcoholism (one. All participants reported mental health histories prediagnosis and most had spent years contending with mental health labels, medications, symptoms, and hospitalizations. In addition, most participants were highly educated health professionals, quite familiar with the behaviors that the medical system considered to comprise bipolar disorder. Their negative associations to the initial bipolar disorder diagnosis, therefore, appeared inconsistent with their mental health histories and professional knowledge. This article contextualizes these initial reactions of shock and distress and proposes interpretations of these findings from societal and psychodynamic group relations perspectives. The participants’ initial negative reactions are conceptualized as involving the terror of being transported from the group of normal people into the group of mad or crazy people, i.e., people with mental illnesses, who may constitute a societal denigrated other.

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.)

Experimental study of effect of initial clad temperature on reflood phenomena during PWR-LOCA

International Nuclear Information System (INIS)

Sugimoto, Jun; Murao, Yoshio

1983-01-01

Integral system tests with the Cylindrical Core Test Facility (CCTF) were performed to investigate the effect of the initial clad temperature on the reflood phenomena in a PWR-LOCA. The initial peak clad temperatures in these three tests were 871, 968 and 1,047K, respectively. The feedback of the system on the core inlet mass flow rate was estimated to be little influenced by the variation of the initial clad temperature except for the first 20s in the transient. The observed temperature rise from the reflood initiation was lower with the higher initial clad temperature. This qualitatively agreed with the results of the small scale forced feed reflood experiments. However, the magnitude of the temperature rise in CCTF was significantly low due to the high initial core inlet mass flow rate. Also observed were the multi-dimensional thermal behaviors for the three cases in the CCTF wide core. The analysis codes REFLA and TRAC reasonably predicted the effect of the initial clad temperature on the core thermo-hydraulics under the simulated core inlet flow conditions. However, the calculated temperature rise of the maximum powered rod based on the one-dimensional core analysis was higher than that of the average powered rod, which contradicts the tendency observed in CCTF tests. (author)

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.

Effect of initial temperature and concentration of catalyst in polyeugenol production

Energy Technology Data Exchange (ETDEWEB)

Widayat, E-mail: yayat-99@yahoo.com [Department of Chemical Engineering, Faculty of Engineering, Diponegoro University (Indonesia); Center of Biomass and Renewable Energy Center of Research and Service Diponegoro University Jln Prof. Soedarto, SH. Semarang 50 239, Tel / Fax: (024) 7460058 (Indonesia); Fatuchrohman, Alviano; Gustiasih, Ellen [Department of Chemical Engineering, Faculty of Engineering, Diponegoro University (Indonesia)

2015-12-29

Objective of this research to study influencing of sulfuric acid concentration and initials temperature on polymerization of eugenol. Eugenol is the largest compound in the clove oil that used as raw material. Eugenol was polymerized laboratory scale. Polymerization processing conducted in reactor at 30 minutes. Polyeugenol was obtained in polymerization was conducted at temperature 40°C and ratio eugenol to sulfuric acid 1:15 mole. This research was pbtained the highest yield 81.49%. However, the weight would be increase in according with increasing of initial temperature. The polymerization in temperature 50°C with 1:1.5 mole ratio has the heaviest molecule weight; 47,530.76 gr/mole.

Effect of initial temperature and concentration of catalyst in polyeugenol production

International Nuclear Information System (INIS)

Widayat; Fatuchrohman, Alviano; Gustiasih, Ellen

2015-01-01

Objective of this research to study influencing of sulfuric acid concentration and initials temperature on polymerization of eugenol. Eugenol is the largest compound in the clove oil that used as raw material. Eugenol was polymerized laboratory scale. Polymerization processing conducted in reactor at 30 minutes. Polyeugenol was obtained in polymerization was conducted at temperature 40°C and ratio eugenol to sulfuric acid 1:15 mole. This research was pbtained the highest yield 81.49%. However, the weight would be increase in according with increasing of initial temperature. The polymerization in temperature 50°C with 1:1.5 mole ratio has the heaviest molecule weight; 47,530.76 gr/mole

Effect of temperature on crack initiation in gas formed structures

Energy Technology Data Exchange (ETDEWEB)

Gohari, S.; Vrcelj, Z.; Sharifi, S.; Sharifishourabi, G.; Abadi, R. [Universiti Teknlogi Malaysia, Skudai (Malaysia)

2013-12-15

In the gas forming process, the work piece is formed by applying gas pressure. However, the gas pressure and the accompanying gas temperature can result in crack initiation and unstable crack growth. Thus, it is vital to determine the critical values of applied gas pressure and temperature to avoid crack and fracture failure. We studied the mechanism of fracture using an experimental approach and finite element simulations of a perfect aluminum sheet containing no inclusions and voids. The definition of crack was based on ductile damage mechanics. For inspection of initiation of crack and rupture in gas-metal forming, the ABAQUS/EXPLICIT simulation was used. In gas forming, the applied load is the pressure applied rather than the punching force. The results obtained from both the experimental approach and finite element simulations were compared. The effects of various parameters, such as temperature and gas pressure value on crack initiation, were taken into account.

Synthesis of Al-5Ti-1B Refiner by Melt Reaction Method

OpenAIRE

LI He; CHAI Li-hua; MA Teng-fei; CHEN Zi-yong

2017-01-01

Al-5Ti-1B refiner was successfully prepared by melt reaction method. Through the thermodynamics calculation, the initial reaction temperature was determined. The influence of reaction temperature on microstructure and absorption rate of the alloy was investigated. The phase and microstructure of the alloy were observed by X-ray diffraction, scanning electron microscope and energy dispersive spectrometer. The Al-5Ti-1B refiner was extruded at high temperature to wire with the diameter of 9.5mm...

Atmospheric Oxidation Mechanism and Kinetic Studies for OH and NO3 Radical-Initiated Reaction of Methyl Methacrylate

Directory of Open Access Journals (Sweden)

Rui Gao

2014-03-01

Full Text Available The mechanism for OH and NO3 radical-initiated oxidation reactions of methyl methacrylate (MMA was investigated by using density functional theory (DFT molecular orbital theory. Geometrical parameters of the reactants, intermediates, transition states, and products were fully optimized at the B3LYP/6-31G(d,p level. Detailed oxidation pathways were presented and discussed. The rate constants were deduced by the canonical variational transition-state (CVT theory with the small-curvature tunneling (SCT correction and the multichannel Rice-Ramspergere-Kassele-Marcus (RRKM theory, based on the potential energy surface profiles over the general atmospheric temperature range of 180–370 K. The calculated results were in reasonable agreement with experimental measurement.

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.

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.

Charging conditions research to increase the initial projected velocity at different initial charge temperatures

Science.gov (United States)

Ishchenko, Aleksandr; Burkin, Viktor; Kasimov, Vladimir; Samorokova, Nina; Zykova, Angelica; Diachkovskii, Alexei

2017-11-01

The problems of the defense industry occupy the most important place in the constantly developing modern world. The daily development of defense technology does not stop, nor do studies on internal ballistics. The scientists of the whole world are faced with the task of managing the main characteristics of a ballistic experiment. The main characteristics of the ballistic experiment are the maximum pressure in the combustion chamber Pmax and the projected velocity at the time of barrel leaving UM. During the work the combustion law of the new high-energy fuel was determined in a ballistic experiment for different initial temperatures. This combustion law was used for a parametric study of depending Pmax and UM from a powder charge mass and a traveling charge was carried out. The optimal conditions for loading were obtained for improving the initial velocity at pressures up to 600 MPa for different initial temperatures. In this paper, one of the most promising schemes of throwing is considered, as well as a method for increasing the muzzle velocity of a projected element to 3317 m/s.

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.

An analysis of hot plate initial temperature effect on rectangular narrow gap quenching process

International Nuclear Information System (INIS)

M-Hadi Kusuma; Mulya Juarsa; Anhar Riza Antariksawan; Nandy Putra

2012-01-01

The understanding about thermal management in the event of a severe accident such as the melting nuclear reactor fuel and reactor core, became a priority to maintain the integrity of reactor pressure vessel. Thus the debris will not out from the reactor pressure vessel and resulting impact of more substantial to the environment. One way to maintain the integrity of the reactor pressure vessel was cooling of the excess heat generated due to the accident. To get understanding of this aspect, there search focused on the effect of the initial temperature of the hot plate in the rectangular narrow gap quenching process. The initial temperature effect on quenching process is related to cooling process (thermal management) when the occurrence of a nuclear accident due to loss of coolant accident or severe accident. In order to address the problem, it is crucial to conduct research to get a better understanding of thermal management regarding to nuclear cooling accident. The research focused on determining the rewetting temperature of hot plate cooling on 220°C, 400°C, and 600°C with 0.2 liters/sec cooling water flowrate. Experiments were carried out by injecting 85°C cooling water temperature into the narrow gap at flowrates of 0.2 liters/sec. Data of transient temperature measurements were recorded using a data acquisition system in order to know the rewetting temperature during the quenching process. This study aims to understand the effect of hot plate initial temperature on rewetting during rectangular narrow gap quenching process. The results obtained show that the rewetting point on cooling the hot plate 220°C, 400°C and 600°occurs at varying rewetting temperatures. At 220°C hot plate initial temperature, the rewetting temperature occurs on 220°C. At 400°C hot plate initial temperature, the rewetting temperature occurs on 379.51°C. At 600°C hot plate initial temperature, the rewetting temperature occurs on 426.63°C. Significant differences of hot plate

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)

Lower limb ice application alters ground reaction force during gait initiation

Directory of Open Access Journals (Sweden)

Thiago B. Muniz

2015-04-01

Full Text Available BACKGROUND: Cryotherapy is a widely used technique in physical therapy clinics and sports. However, the effects of cryotherapy on dynamic neuromuscular control are incompletely explained. OBJECTIVES: To evaluate the effects of cryotherapy applied to the calf, ankle and sole of the foot in healthy young adults on ground reaction forces during gait initiation. METHOD: This study evaluated the gait initiation forces, maximum propulsion, braking forces and impulses of 21 women volunteers through a force platform, which provided maximum and minimum ground reaction force values. To assess the effects of cooling, the task - gait initiation - was performed before ice application, immediately after and 30 minutes after removal of the ice pack. Ice was randomly applied on separate days to the calf, ankle and sole of the foot of the participants. RESULTS: It was demonstrated that ice application for 30 minutes to the sole of the foot and calf resulted in significant changes in the vertical force variables, which returned to their pre-application values 30 minutes after the removal of the ice pack. Ice application to the ankle only reduced propulsion impulse. CONCLUSIONS: These results suggest that although caution is necessary when performing activities that require good gait control, the application of ice to the ankle, sole of the foot or calf in 30-minute intervals may be safe even preceding such activities.

Reaction of LiD with moisture by temperature programmed reaction (TPR)

International Nuclear Information System (INIS)

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

2000-01-01

The temperature programmed reaction technique was performed on LiOH powders and LiD single crystals previously exposed to different moisture levels. Our results show that the LiOH decomposition process has an activation energy barrier of 30 to 33.1 kcal/mol. The LiOH structure is stable at 320 K for 100 years. However, LiOH structures formed on the surface of LiD during moisture exposure at low dosages may have multiple activation energy barriers, some of which may be much lower than 30 kcal/mol. We attribute the lowering of the activation energy barrier for the LiOH decomposition to the existence of dangling bonds, cracks, and other long range disorders in the LiOH structures formed at low levels of moisture exposure. These defective LiOH structures may decompose significantly over the next 100 years of storage even at room temperature. At high moisture exposure levels, LiOH.H 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 13.8 kcal/mol to 16.0 kcal/mol. 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 of LiOH and LiOH.H 2 O significantly

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.

Fast and quantitative differentiation of single-base mismatched DNA by initial reaction rate of catalytic hairpin assembly.

Science.gov (United States)

Li, Chenxi; Li, Yixin; Xu, Xiao; Wang, Xinyi; Chen, Yang; Yang, Xiaoda; Liu, Feng; Li, Na

2014-10-15

The widely used catalytic hairpin assembly (CHA) amplification strategy generally needs several hours to accomplish one measurement based on the prevailingly used maximum intensity detection mode, making it less practical for assays where high throughput or speed is desired. To make the best use of the kinetic specificity of toehold domain for circuit reaction initiation, we developed a mathematical model and proposed an initial reaction rate detection mode to quantitatively differentiate the single-base mismatch. Using the kinetic mode, assay time can be reduced substantially to 10 min for one measurement with the comparable sensitivity and single-base mismatch differentiating ability as were obtained by the maximum intensity detection mode. This initial reaction rate based approach not only provided a fast and quantitative differentiation of single-base mismatch, but also helped in-depth understanding of the CHA system, which will be beneficial to the design of highly sensitive and specific toehold-mediated hybridization reactions. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Method of identification of unbranched chain reaction with cross termination of chain

International Nuclear Information System (INIS)

Poluehktov, V.A.; Begishev, I.R.

1977-01-01

Gas-phase chlorination of unsymmetrical difluoroethane initiated by gamma quanta of Co 60 has been studied. At decreased temperatures the only hydrogen is replaced by a chlorine atom. Over a wide range of ratios of the initial reagents, the reaction occurs with a chain rupture. An analysis of the kinetics of such a reaction provides a method for identification of an unbranched chain reaction with a cross-rupture of the chain

Numerical simulation of shock initiation of Ni/Al multilayered composites

Energy Technology Data Exchange (ETDEWEB)

Sraj, Ihab; Knio, Omar M., E-mail: omar.knio@duke.edu [Department of Mechanical Engineering and Materials Science, Duke University, 144 Hudson Hall, Durham, North Carolina 27708 (United States); Specht, Paul E.; Thadhani, Naresh N. [School of Materials Science and Engineering, Georgia Institute of Technology, 771 Ferst Drive, Atlanta, Georgia 30332 (United States); Weihs, Timothy P. [Department of Materials Science and Engineering, The Johns Hopkins University, 3400 North Charles Street, Baltimore, Maryland 21218 (United States)

2014-01-14

The initiation of chemical reaction in cold-rolled Ni/Al multilayered composites by shock compression is investigated numerically. A simplified approach is adopted that exploits the disparity between the reaction and shock loading timescales. The impact of shock compression is modeled using CTH simulations that yield pressure, strain, and temperature distributions within the composites due to the shock propagation. The resulting temperature distribution is then used as initial condition to simulate the evolution of the subsequent shock-induced mixing and chemical reaction. To this end, a reduced reaction model is used that expresses the local atomic mixing and heat release rates in terms of an evolution equation for a dimensionless time scale reflecting the age of the mixed layer. The computations are used to assess the effect of bilayer thickness on the reaction, as well as the impact of shock velocity and orientation with respect to the layering. Computed results indicate that initiation and evolution of the reaction are substantially affected by both the shock velocity and the bilayer thickness. In particular, at low impact velocity, Ni/Al multilayered composites with thick bilayers react completely in 100 ms while at high impact velocity and thin bilayers, reaction time was less than 100 μs. Quantitative trends for the dependence of the reaction time on the shock velocity are also determined, for different bilayer thickness and shock orientation.

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

Reaction Control Engine for Space Launch Initiative

Science.gov (United States)

2002-01-01

Engineers at the Marshall Space Flight Center (MSFC) have begun a series of engine tests on a new breed of space propulsion: a Reaction Control Engine developed for the Space Launch Initiative (SLI). The engine, developed by TRW Space and Electronics of Redondo Beach, California, is an auxiliary propulsion engine designed to maneuver vehicles in orbit. It is used for docking, reentry, attitude control, and fine-pointing while the vehicle is in orbit. The engine uses nontoxic chemicals as propellants, a feature that creates a safer environment for ground operators, lowers cost, and increases efficiency with less maintenance and quicker turnaround time between missions. Testing includes 30 hot-firings. This photograph shows the first engine test performed at MSFC that includes SLI technology. Another unique feature of the Reaction Control Engine is that it operates at dual thrust modes, combining two engine functions into one engine. The engine operates at both 25 and 1,000 pounds of force, reducing overall propulsion weight and allowing vehicles to easily maneuver in space. The low-level thrust of 25 pounds of force allows the vehicle to fine-point maneuver and dock while the high-level thrust of 1,000 pounds of force is used for reentry, orbit transfer, and coarse positioning. SLI is a NASA-wide research and development program, managed by the MSFC, designed to improve safety, reliability, and cost effectiveness of space travel for second generation reusable launch vehicles.

Performance of an HF chain-reaction laser with high initiation efficiency

International Nuclear Information System (INIS)

Whittier, J.S.; Kerber, R.L.

1974-01-01

Output-pulse observations are presented for a transverse electrically initiated, helium-diluted HF laser pumped by the H 2 + F 2 chain reaction. Performance of this laser is studied over a wide range of the gas composition and for initial pressures between 0.1 and 0.5 atm. The gas mixture was stabilized by premixing O 2 , F 2 , and He and flowing this mixture into a cold trap (84 0 K) before mixing with H 2 . Optimum conversion of electrical-initiation energy into laser energy was found for a 240-torr mixture with a mole ratio 1 F 2 :0.23 H 2 :0.08 O 2 :12 He which, when initiated with a 25-kV, 333-pF discharge, gave a pulse energy of 0.150 J. This corresponds to a ratio of laser output energy to electrical input energy of 144 percent. After unnecessary losses are taken into account, this ratio becomes 160 percent. (U.S.)

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)

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.

Enhanced pycnonuclear reactions in ultrahigh-pressure metals

International Nuclear Information System (INIS)

Ichimaru, Setsuo; Kitamura, Hikaru

1995-01-01

By combining the concepts of pycnonuclear reactions at low temperatures and their enhancement due to strong internuclear Coulomb correlations, we predict the possibilities of a novel scheme for fusion in ultrahigh-pressure liquid-metallic hydrogen near the freezing conditions, for the reactions 2 H(p,γ) 3 He, 3 H(d,n) 4 He, and 7 Li(p,α) 4 He. Time evolution is followed for p-d reaction after a pulsed compression with 1 kJ input and the initial conditions of mass density ≅ 20 g/cm 3 , temperature ≅ 1400 K, pressure ≅ 490 Mbar, and radius ≅ 0.017 cm; an energy yield of 33 kJ in 0.03 fs is thus predicted. (author)

Exchange reaction between hydrogen and deuterium. II - Proposal for an heterogeneous initiation mechanism of gaseous phase reactions

Energy Technology Data Exchange (ETDEWEB)

Marteau, Chantal; Gaillard-Cusin, Francoise; James, Henri [Centre National de la Recherche Scientifique, 45 - Orleans-la-Source (France). Centre de Recherches sur la Chimie de Combustion et des Hautes Temperatures

1978-05-01

Investigation of experimental data related to evolution period exhibited by H/sub 2/-D/sub 2/ exchange process requires to take into account the variation against time of every atomic species -adsorbed or not- implied in the reaction mechanism. The formation of first chain carriers involves: - chemisorption of either gaseous reactant on the surface active centres (..sigma..), e.g.: ..sigma.. + 1/2 H/sub 2/ reversible ..sigma..H; - consecutive generation of atomic species through hetero-homogeneous transfer between chemisorbed species (..sigma..H) and gaseous molecules: ..sigma..H+H/sub 2/..--> sigma..+H/sub 2/+H/sup 0/, ..sigma..H+D/sub 2/..--> sigma..+HD+D/sup 0/. Therefore, it can be shown that the heterogeneous initiation process of a gas phase reaction identifies to a chain linear mechanism. Such an heterogeneous sequence conditions the further proceeding of the homogeneous chain reaction; both evolutions being kinematically connected. Rate constant of hydrogen adsorption on silica glass: ksub(a1) approximately 10/sup 14/ exp(-47/RT)Isup(0,5).molesup(-0,5).S/sup -1/ has been evaluated.

Reactions of aluminum with uranium fluorides and oxyfluorides

Energy Technology Data Exchange (ETDEWEB)

Leitnaker, J.M.; Nichols, R.W.; Lankford, B.S. [Martin Marietta Energy Systems, Inc., Oak Ridge, TN (United States)

1991-12-31

Every 30 to 40 million operating hours a destructive reaction is observed in one of the {approximately}4000 large compressors that move UF{sub 6} through the gaseous diffusion plants. Despite its infrequency, such a reaction can be costly in terms of equipment and time. Laboratory experiments reveal that the presence of moderate pressures of UF{sub 6} actually cools heated aluminum, although thermodynamic calculations indicate the potential for a 3000-4000{degrees}C temperature rise. Within a narrow and rather low (<100 torr; 1 torr = 133.322 Pa) pressure range, however, the aluminum is seen to react with sufficient heat release to soften an alumina boat. Three things must occur in order for aluminum to react vigorously with either UF{sub 6} or UO{sub 2}F{sub 2}. 1. An initiating source of heat must be provided. In the compressors, this source can be friction, permitted by disruption of the balance of the large rotating part or by creep of the aluminum during a high-temperature treatment. In the absence of this heat source, compressors have operated for 40 years in UF{sub 6} without significant reaction. 2. The film protecting the aluminum must be breached. Melting (of UF{sub 5} at 620 K or aluminum at 930 K) can cause such a breach in laboratory experiments. In contrast, holding Al samples in UF{sub 6} at 870 K for several hours produces only moderate reaction. Rubbing in the cascade can undoubtedly breach the protective film. 3. Reaction products must not build up and smother the reaction. While uranium products tend to dissolve or dissipate in molten aluminum, AIF{sub 3} shows a remarkable tendency to surround and hence protect even molten aluminum. Hence the initial temperature rise must be rapid and sufficient to move reactants into a temperature region in which products are removed from the reaction site.

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

Raney copper catalysts for the water-gas shift reaction - II. Initial catalyst optimisation

CSIR Research Space (South Africa)

Mellor, JR

1997-12-23

Full Text Available The initial Raney copper WGS activity based on catalyst volume has been shown to be comparable to industrial and co-precipitated alternatives under varying reaction conditions. The presence of zinc oxide in the Raney copper structure was shown...

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. .

Thermophysical Property Estimation by Transient Experiments: The Effect of a Biased Initial Temperature Distribution

Directory of Open Access Journals (Sweden)

Federico Scarpa

2015-01-01

Full Text Available The identification of thermophysical properties of materials in dynamic experiments can be conveniently performed by the inverse solution of the associated heat conduction problem (IHCP. The inverse technique demands the knowledge of the initial temperature distribution within the material. As only a limited number of temperature sensors (or no sensor at all are arranged inside the test specimen, the knowledge of the initial temperature distribution is affected by some uncertainty. This uncertainty, together with other possible sources of bias in the experimental procedure, will propagate in the estimation process and the accuracy of the reconstructed thermophysical property values could deteriorate. In this work the effect on the estimated thermophysical properties due to errors in the initial temperature distribution is investigated along with a practical method to quantify this effect. Furthermore, a technique for compensating this kind of bias is proposed. The method consists in including the initial temperature distribution among the unknown functions to be estimated. In this way the effect of the initial bias is removed and the accuracy of the identified thermophysical property values is highly improved.

Interface reactions between Pd thin films and SiC by thermal annealing and SHI irradiation

Energy Technology Data Exchange (ETDEWEB)

Njoroge, E.G., E-mail: eric.njoroge@up.ac.za [Department of Physics, University of Pretoria, Pretoria (South Africa); Theron, C.C. [Department of Physics, University of Pretoria, Pretoria (South Africa); Skuratov, V.A. [Joint Institute for Nuclear Research, Dubna (Russian Federation); Wamwangi, D. [School of Physics, University of Witwatersrand, Johannesburg (South Africa); Hlatshwayo, T.T. [Department of Physics, University of Pretoria, Pretoria (South Africa); Comrie, C.M. [MRD, iThemba LABS, P.O. Box 722, Somerset West 7129 (South Africa); Malherbe, J.B. [Department of Physics, University of Pretoria, Pretoria (South Africa)

2016-03-15

The solid-state reactions between Pd thin films and 6H-SiC substrates induced by thermal annealing, room temperature swift heavy ion (SHI) irradiation and high temperature SHI irradiation have been investigated by in situ and real-time Rutherford backscattering spectrometry (RBS) and Grazing incidence X-ray diffraction (GIXRD). At room temperature, no silicides were detected to have formed in the Pd/SiC samples. Two reaction growth zones were observed in the samples annealed in situ and analysed by real time RBS. The initial reaction growth region led to formation of Pd{sub 3}Si or (Pd{sub 2}Si + Pd{sub 4}Si) as the initial phase(s) to form at a temperature of about 450 °C. Thereafter, the reaction zone did not change until a temperature of 640 °C was attained where Pd{sub 2}Si was observed to form in the reaction zone. Kinetic analysis of the initial reaction indicates very fast reaction rates of about 1.55 × 10{sup 15} at cm{sup −2}/s and the Pd silicide formed grew linear with time. SHI irradiation of the Pd/SiC samples was performed by 167 MeV Xe{sup 26+} ions at room temperature at high fluences of 1.07 × 10{sup 14} and 4 × 10{sup 14} ions/cm{sup 2} and at 400 °C at lower fluences of 5 × 10{sup 13} ions/cm{sup 2}. The Pd/SiC interface was analysed by RBS and no SHI induced diffusion was observed for room temperature irradiations. The sample irradiated at 400 °C, SHI induced diffusion was observed to occur accompanied with the formation of Pd{sub 4}Si, Pd{sub 9}Si{sub 2} and Pd{sub 5}Si phases which were identified by GIXRD analysis.

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

High temperature crack initiation in an austenitic stainless steel

International Nuclear Information System (INIS)

Laiarinandrasana, Lucien

1994-01-01

The study deals with crack initiation at 600 deg. C and 650 deg. C, on an austenitic stainless steel referenced by Z2 CND 17 12. The behaviour laws of the studied plate were updated in comparison with existing data. Forty tests were carried out on CT specimens, with continuous fatigue with load or displacement controlled, pure creep, pure relaxation, creep-fatigue and creep-relaxation loadings. The practical initiation definition corresponds to a small crack growth of about the grain size, monitored by electrical potential drop technique. The time necessary for the crack to initiate is predicted with fracture mechanics global and local approaches, with the help of microstructural observations and finite element results. An identification of a 'Paris' law' for continuous cyclic loading and of a unique correlation between the initiation time and C h * for creep tests was established. For the local approach, crack initiation by creep can be interpreted as the reaching of a critical damage level, by using a damage incremental rule. For creep-fatigue tests, crack growth rates at initiation are greater than those of Paris' law for continuous fatigue. A calculation of a transition time between elastic-plastic and creep domains shows that crack initiation can be interpreted whether by providing Paris' law with an acceleration term when the dwell period is less than the transition time, or by calculating a creep contribution which relies on C h * parameter when the dwell period and/or the initiation times are greater than the transition time. Creep relaxation tests present crack growth rates at initiation which are less than those for 'equivalent' creep-fatigue tests. These crack growth rates decrease when increasing hold time, but also when temperature decreases. Though, for hold times which are important enough and at lower temperature, there is no effect of the dwell period insofar as crack growth rate is equal to continuous fatigue

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

Initial Self-Healing Temperatures of Asphalt Mastics Based on Flow Behavior Index.

Science.gov (United States)

Li, Chao; Wu, Shaopeng; Tao, Guanyu; Xiao, Yue

2018-05-29

Increasing temperature is a simple and convenient method to accelerate the self-healing process of bitumen. However, bitumen may not achieve the healing capability at lower temperature, and may be aged if temperature is too high. In addition, the bitumen is mixed with mineral filler and formed as asphalt mastic in asphalt concrete, so it is more accurate to study the initial self-healing from the perspective of asphalt mastic. The primary purpose of this research was to examine the initial self-healing temperature of asphalt mastic, which was determined by the flow behavior index obtained from the flow characteristics. Firstly, the texture and geometry characteristics of two fillers were analyzed, and then the initial self-healing temperature of nine types of asphalt mastic, pure bitumen (PB) and styrene-butadiene-styrene (SBS) modified bitumen were determined by the flow behavior index. Results demonstrate that the average standard deviation of gray-scale texture value of limestone filler (LF) is 21.24% lower than that of steel slag filler (SSF), showing that the steel slag filler has a better particle distribution and geometry characteristics. Also the initial self-healing temperatures of asphalt mastics with 0.2, 0.4 and 0.6 LF-PB volume ratio are 46.5 °C, 47.2 °C and 49.4 °C, which are 1.4 °C, 0.8 °C and 0.4 °C higher than that of asphalt mastics with SSF-PB, but not suitable for the evaluation of asphalt mastic contained SBS modified bitumen because of unique structure and performance of SBS.

The effect of the initial exciton numbers on 54,56Fe(p, xp) Pre-Equilibrium Reactions

International Nuclear Information System (INIS)

Bölükdemir, M. H.; Tel, E.; Aydın, A.; Okuducu, S.; Kaplan, A.

2011-01-01

In pre-equilibrium nuclear reactions, the geometry-dependent hybrid model is applied with the use of the neutron and proton densities to investigate the effect of initial exciton numbers on the nucleon emission spectra. The initial exciton numbers calculated with the theoretical neutron and proton densities have been obtained within the Skryme-Hartree-Fock method with SKM* and SLy4 forces on target nuclei in the 54,56 Fe(p, xp) reaction at 61.5-MeV incident proton energy by using a new calculationmethod of Tel et al. Also, the differences between the initial exciton numbers for protons and neutrons as a function of nuclear radius, focusing on systematic discrepancies correlated to differences in the proton and neutron densities have been investigated.

Metrology to enable high temperature erosion testing - A new european initiative

DEFF Research Database (Denmark)

Fry, A.T.; Gee, M.G.; Clausen, Sønnik

2014-01-01

is required. However, limitations in current measurement capability within this form of test prevent the advancement. A new European initiative, METROSION, on the development of high temperature solid particle erosion testing has a primary aim to develop this metrological framework. Several key parameters...... have been identified for measurement and control; these include temperature (of the sample, gas and particles), flow rate, size and shape of the erodent, angle of incidence of the particle stream and nozzle design. This paper outlines the aims and objectives of this new initiative. With a particular...

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

Fast chemical reaction in two-dimensional Navier-Stokes flow: initial regime.

Science.gov (United States)

Ait-Chaalal, Farid; Bourqui, Michel S; Bartello, Peter

2012-04-01

This paper studies an infinitely fast bimolecular chemical reaction in a two-dimensional biperiodic Navier-Stokes flow. The reactants in stoichiometric quantities are initially segregated by infinite gradients. The focus is placed on the initial stage of the reaction characterized by a well-defined one-dimensional material contact line between the reactants. Particular attention is given to the effect of the diffusion κ of the reactants. This study is an idealized framework for isentropic mixing in the lower stratosphere and is motivated by the need to better understand the effect of resolution on stratospheric chemistry in climate-chemistry models. Adopting a Lagrangian straining theory approach, we relate theoretically the ensemble mean of the length of the contact line, of the gradients along it, and of the modulus of the time derivative of the space-average reactant concentrations (here called the chemical speed) to the joint probability density function of the finite-time Lyapunov exponent λ with two times τ and τ[over ̃]. The time 1/λ measures the stretching time scale of a Lagrangian parcel on a chaotic orbit up to a finite time t, while τ measures it in the recent past before t, and τ[over ̃] in the early part of the trajectory. We show that the chemical speed scales like κ(1/2) and that its time evolution is determined by rare large events in the finite-time Lyapunov exponent distribution. The case of smooth initial gradients is also discussed. The theoretical results are tested with an ensemble of direct numerical simulations (DNSs) using a pseudospectral model.

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.

Initial kinetics of the direct sulfation of limestone

DEFF Research Database (Denmark)

Hu, Guilin; Shang, Lei; Dam-Johansen, Kim

2008-01-01

The initial kinetics of direct sulfation of Faxe Bryozo, a porous bryozoan limestone was studied in the temperature interval from 873 to 973 K in a pilot entrained flow reactor with very short reaction times (between 0.1 and 0.6 s). The initial conversion rate of the limestone - for conversions...... less than 0.3% - was observed to be significantly promoted by higher SO2 concentrations and lower CO2 concentrations, whereas 02 showed negligible influence. A mathematical model for the sulfation of limestone involving chemical reaction at calcite grain surfaces and solid-state diffusion of carbonate...... ions in calcite grains is established. The validity of the model is limited to the initial sulfation period, in which nucleation of the solid product calcium sulphate is not started. This theoretical reaction-diffusion model gives a good simulation of the initial kinetics of the direct sulfation...

State selective reactions of cosmic dust analogues at cryogenic temperatures

International Nuclear Information System (INIS)

Perry, James Samuel Anthony

2001-01-01

Molecular hydrogen (H 2 ) is the most abundant molecule in interstellar space. It is crucial for initiating all of the chemistry in the Interstellar Medium (ISM) and consequently plays an important role in star formation. However, the amount of H 2 believed to exist in the ISM cannot be accounted for by formation through gas-phase reactions alone. The current, widely accepted theory, is that H 2 forms on the surface of cosmic dust grains. These grains are thought to be composed of amorphous forms of carbon or silicates with temperatures of around 10 K. This thesis describes a new experiment that has been constructed to study H 2 formation on the surface of cosmic dust analogues and presents the initial experimental results. The experiment simulates, through ultra-high vacuum and the use of cryogenics, the conditions of the ISM where cosmic dust grains and H 2 molecules exist. During the experiment, a beam of atomic hydrogen is aimed at a cosmic dust analogue target. H 2 formed on the target's surface is ionised using a laser spectroscopy technique known as Resonance Enhanced Multiphoton lonisation (REMPI) and detected using time-of-flight mass spectrometry. The sensitivity of REMPI is such that H 2 molecules can be ionised in selective internal energy states. This allows the rovibrational populations of the H 2 molecules desorbing from the cosmic dust targets to be determined, providing information on the energy budget of the H 2 formation process in the ISM. Preliminary results from the experiment show that H 2 molecules formed on a diamond-like-carbon surface have a significant non-thermal population of excited vibrational and rotational energy states. (author)

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

The reaction of uranium with moist hydrogen

International Nuclear Information System (INIS)

Pearce, R.J.; Kay, P.

1987-10-01

The reaction of uranium in moist hydrogen at a total pressure of 101 kPa over the temperature range 105 0 -200 0 C and water vapour pressures in the range 5-100 kPa has been examined in a limited thermogravimetric study. It has been shown that initially there is a period during which only linear kinetics are observed with a rate similar to that exhibited in similarly moist argon, i.e. hydrogen has no apparent effect on the reaction. At water vapour pressures of and above 49 kPa, corresponding to hydrogen:water vapour pressure ratios in the range 1:1 to 1:100, over the exposure times studied (not > 20h) only such linear kinetics are observed. Below this water vapour pressure and after an initial period of linear kinetics a continuously increasing reaction rate was observed in some instances resulting from rapid attach on localised areas. The localised reaction rates were approximately 2-3 orders of magnitude faster than the original linear reaction kinetics and the interaction rates in either moist argon or moist air. Comparison with a single experiment carried out at 150 0 C indicated that breakaway rates were approaching that in dry hydrogen. During breakaway attack there was a significant increase in the relative amounts of uranium hydride formed. The duration of the linear kinetics phase was extended by pre-oxidation of the uranium surface, decreasing temperature at a constant water vapour pressure, or increasing water vapour pressure (or water vapour: hydrogen pressure ratio) at a constant temperature. (author)

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.

Pressure-dependent kinetics of initial reactions in iso-octane pyrolysis.

Science.gov (United States)

Ning, HongBo; Gong, ChunMing; Li, ZeRong; Li, XiangYuan

2015-05-07

This study focuses on the studies of the main pressure-dependent reaction types of iso-octane (iso-C8H18) pyrolysis, including initial C-C bond fission of iso-octane, isomerization, and β-scission reactions of the alkyl radicals produced by the C-C bond fission of iso-octane. For the C-C bond fission of iso-octane, the minimum energy potentials are calculated at the CASPT2(2e,2o)/6-31+G(d,p)//CAS(2e,2o)/6-31+G(d,p) level of theory. For the isomerization and the β-scission reactions of the alkyl radicals, the optimization of the geometries and the vibrational frequencies of the reactants, transition states, and products are performed at the B3LYP/CBSB7 level, and their single point energies are calculated by using the composite CBS-QB3 method. Variable reaction coordinate transition state theory (VRC-TST) is used for the high-pressure limit rate constant calculation and Rice-Ramsperger-Kassel-Marcus/master equation (RRKM/ME) is used to calculate the pressure-dependent rate constants of these channels with pressure varying from 0.01-100 atm. The rate constants obtained in this work are in good agreement with those available from literatures. We have updated the rate constants and thermodynamic parameters for species involved in these reactions into a current chemical kinetic mechanism and also have improved the concentration profiles of main products such as C3H6 and C4H6 in the shock tube pyrolysis of iso-octane. The results of this study provide insight into the pyrolysis of iso-octane and will be helpful in the future development of branched paraffin kinetic mechanisms.

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

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

Initial Self-Healing Temperatures of Asphalt Mastics Based on Flow Behavior Index

Directory of Open Access Journals (Sweden)

Chao Li

2018-05-01

Full Text Available Increasing temperature is a simple and convenient method to accelerate the self-healing process of bitumen. However, bitumen may not achieve the healing capability at lower temperature, and may be aged if temperature is too high. In addition, the bitumen is mixed with mineral filler and formed as asphalt mastic in asphalt concrete, so it is more accurate to study the initial self-healing from the perspective of asphalt mastic. The primary purpose of this research was to examine the initial self-healing temperature of asphalt mastic, which was determined by the flow behavior index obtained from the flow characteristics. Firstly, the texture and geometry characteristics of two fillers were analyzed, and then the initial self-healing temperature of nine types of asphalt mastic, pure bitumen (PB and styrene-butadiene-styrene (SBS modified bitumen were determined by the flow behavior index. Results demonstrate that the average standard deviation of gray-scale texture value of limestone filler (LF is 21.24% lower than that of steel slag filler (SSF, showing that the steel slag filler has a better particle distribution and geometry characteristics. Also the initial self-healing temperatures of asphalt mastics with 0.2, 0.4 and 0.6 LF-PB volume ratio are 46.5 °C, 47.2 °C and 49.4 °C, which are 1.4 °C, 0.8 °C and 0.4 °C higher than that of asphalt mastics with SSF-PB, but not suitable for the evaluation of asphalt mastic contained SBS modified bitumen because of unique structure and performance of SBS.

Kinetics of reactions of oxidation of carbon by carbon dioxide and water steam at high temperatures and low pressures

International Nuclear Information System (INIS)

Boulangier, Francois

1956-01-01

The first objective of this research thesis was to obtain new and reliable experimental results about the reaction kinetics of the oxidation of carbon by carbon dioxide and water steam, and to avoid some disturbing phenomena, for example and more particularly the appearance of electric discharges beyond 1900 K initiated by the filament thermoelectric emission. The author tried to identify the mechanism of the accelerating effect. It appears that previous experiments had been performed only in these disturbed conditions. At the lowest temperatures, the author highlighted the existence of a surface contamination by the desorption products from the apparatus [fr

Roles of different initial Maillard intermediates and pathways in meat flavor formation for cysteine-xylose-glycine model reaction systems.

Science.gov (United States)

Hou, Li; Xie, Jianchun; Zhao, Jian; Zhao, Mengyao; Fan, Mengdie; Xiao, Qunfei; Liang, Jingjing; Chen, Feng

2017-10-01

To explore initial Maillard reaction pathways and mechanisms for maximal formation of meaty flavors in heated cysteine-xylose-glycine systems, model reactions with synthesized initial Maillard intermediates, Gly-Amadori, TTCA (2-threityl-thiazolidine-4-carboxylic acids) and Cys-Amadori, were investigated. Relative relativities were characterized by spectrophotometrically monitoring the development of colorless degradation intermediates and browning reaction products. Aroma compounds formed were determined by solid-phase microextraction combined with GC-MS and GC-olfactometry. Gly-Amadori showed the fastest reaction followed by Cys-Amadori then TTCA. Free glycine accelerated reaction of TTCA, whereas cysteine inhibited that of Gly-Amadori due to association forming relatively stable thiazolidines. Cys-Amadori/Gly had the highest reactivity in development of both meaty flavors and brown products. TTCA/Gly favored yielding meaty flavors, whereas Gly-Amadori/Cys favored generation of brown products. Conclusively, initial formation of TTCA and pathway involving TTCA with glycine were more applicable to efficiently produce processed-meat flavorings in a cysteine-xylose-glycine system. Copyright © 2017 Elsevier Ltd. All rights reserved.

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...

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.

Nano-Scale Au Supported on Carbon Materials for the Low Temperature Water Gas Shift (WGS Reaction

Directory of Open Access Journals (Sweden)

Paula Sánchez

2011-12-01

Full Text Available Au-based catalysts supported on carbon materials with different structures such as graphite (G and fishbone type carbon nanofibers (CNF-F were prepared using two different methods (impregnation and gold-sol to be tested in the water gas shift (WGS reaction. Atomic absorption spectrometry, transmission electron microscopy (TEM, temperature-programmed oxidation (TPO, X-ray diffraction (XRD, Raman spectroscopy, elemental analyses (CNH, N2 adsorption-desorption analysis, temperature-programmed reduction (TPR and temperature-programmed decomposition were employed to characterize both the supports and catalysts. Both the crystalline nature of the carbon supports and the method of gold incorporation had a strong influence on the way in which Au particles were deposited on the carbon surface. The higher crystallinity and the smaller and well dispersed Au particle size were, the higher activity of the catalysts in the WGS reaction was noted. Finally, catalytic activity showed an important dependence on the reaction temperature and steam-to-CO molar ratio.

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

Relation of expansion due to alkali silica reaction to the degree of reaction measured by SEM image analysis

International Nuclear Information System (INIS)

Haha, M. Ben; Gallucci, E.; Guidoum, A.; Scrivener, K.L.

2007-01-01

Scanning Electron Microscopy Image Analysis (SEM-IA) was used to quantify the degree of alkali silica reaction in affected microbars, mortar and concrete prisms. It was found that the degree of reaction gave a unique correlation with the macroscopic expansion for three different aggregates, stored at three temperatures and with two levels of alkali. The relationships found for the concretes and the mortars overlap when normalised by the aggregate content. This relationship seems to be linear up to a critical reaction degree which coincides with crack initiation within the reactive aggregates

Incidence and associated factors to adverse reactions of the initial antiretroviral treatment in patients with HIV

OpenAIRE

Astuvilca, Juan; Facultad de Medicina, Universidad Nacional Mayor de San Marcos. Lima, Perú. Sociedad Científica de San Fernando. Lima, Perú. Estudiantes de medicina.; Arce-Villavicencio, Yanet; Facultad de Medicina, Universidad Nacional Mayor de San Marcos. Lima, Perú. Sociedad Científica de San Fernando. Lima, Perú. Estudiantes de medicina.; Sotelo, Raúl; Facultad de Medicina, Universidad Nacional Mayor de San Marcos. Lima, Perú. Sociedad Científica de San Fernando. Lima, Perú. Estudiantes de medicina.; Quispe, José; Facultad de Medicina, Universidad Nacional Mayor de San Marcos. Lima, Perú. Sociedad Científica de San Fernando. Lima, Perú. Estudiantes de medicina.; Guillén, Regina; Facultad de Medicina, Universidad Nacional Mayor de San Marcos. Lima, Perú. Estudiantes de medicina.; Peralta, Lillian; Facultad de Medicina, Universidad Nacional Mayor de San Marcos. Lima, Perú. Estudiantes de medicina.; Huaringa, Jorge; Facultad de Medicina, Universidad Nacional Mayor de San Marcos. Lima, Perú. Estudiantes de medicina.; Gutiérrez, César; Departamento Académico de Medicina Preventiva y Salud Pública, Facultad de Medicina, Universidad Nacional Mayor de San Marcos. Lima-Perú. Médico epidemiólogo.

2007-01-01

The high incidence of adverse reactions to the high activity antiretroviral treatment (HAART) in patients with HIV/AIDS, can affect their quality of life and adherence to the treatment. Objectives: To determinate the incidence of adverse reactions to the initial HAART and to identify the factors associated to the occurrence of adverse reactions when receiving this therapy. Material and methods: Historic cohort study. The population was conformed by all the HIV-infected adult patients (≥18...

Kinetics of gaseous uranium hexafluoride reaction with hydrogen chloride

International Nuclear Information System (INIS)

Ezubchenko, A.N.; Ilyukhin, A.I.; Merzlyakov, A.V.

1993-01-01

Kinetics of decrease of concentration of gaseous uranium hexafluoride in reaction with hydrogen chloride at temperatures close to room ones, was investigated by the method of IR spectroscopy. It was established that the process represented the first order reaction by both UF 6 and HCl. Activation energy of the reaction was determined: 7.6 ± 0.7 kcal/mol. Specific feature of reaction kinetics was noted: inversely proportional dependence of effective constant on UF 6 initial pressure. 5 refs., 3 figs

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.

X-ray Crystal Structures Elucidate the Nucleotidyl Transfer Reaction of Transcript Initiation Using Two Nucleotides

Energy Technology Data Exchange (ETDEWEB)

M Gleghorn; E Davydova; R Basu; L Rothman-Denes; K Murakami

2011-12-31

We have determined the X-ray crystal structures of the pre- and postcatalytic forms of the initiation complex of bacteriophage N4 RNA polymerase that provide the complete set of atomic images depicting the process of transcript initiation by a single-subunit RNA polymerase. As observed during T7 RNA polymerase transcript elongation, substrate loading for the initiation process also drives a conformational change of the O helix, but only the correct base pairing between the +2 substrate and DNA base is able to complete the O-helix conformational transition. Substrate binding also facilitates catalytic metal binding that leads to alignment of the reactive groups of substrates for the nucleotidyl transfer reaction. Although all nucleic acid polymerases use two divalent metals for catalysis, they differ in the requirements and the timing of binding of each metal. In the case of bacteriophage RNA polymerase, we propose that catalytic metal binding is the last step before the nucleotidyl transfer reaction.

Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

Directory of Open Access Journals (Sweden)

Thomas Zeuch

2013-11-01

Full Text Available Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn’s largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br, allyl chloride (C3H5Cl, and 1,5-hexadiene (CH2CH(CH22CHCH2 at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re- combination pathway C3H5+C3H5 → C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re- combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth.

Acceleration of Intended Pozzolanic Reaction under Initial Thermal Treatment for Developing Cementless Fly Ash Based Mortar

Directory of Open Access Journals (Sweden)

Yang-Hee Kwon

2017-02-01

Full Text Available Without using strong alkaline solution or ordinary Portland cement, a new structural binder consisting of fly ash and hydrated lime was hardened through an intensified pozzolanic reaction. The main experimental variables are the addition of silica fume and initial thermal treatment (60 °C for 3 days. A series of experiments consisting of mechanical testing (compressive and flexural strength, modulus of elasticity, X-ray diffraction, and measurements of the heat of hydration, pore structure, and shrinkage were conducted. These tests show that this new fly ash-based mortar has a compressive strength of 15 MPa at 91 days without any silica fume addition or initial thermal treatment. The strength increased to over 50 MPa based on the acceleration of the intensified pozzolanic reaction from the silica fume addition and initial thermal treatment. This is explained by a significant synergistic effect induced by the silica fume. It intensifies the pozzolanic reaction under thermal treatment and provides a space filling effect. This improved material performance can open a new pathway to utilize the industrial by-product of fly ash in cementless construction materials.

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.

Optimization of Maillard Reaction in Model System of Glucosamine and Cysteine Using Response Surface Methodology.

Science.gov (United States)

Arachchi, Shanika Jeewantha Thewarapperuma; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Lee, Yang-Bong

2017-03-01

Sulfur-containing amino acids play important roles in good flavor generation in Maillard reaction of non-enzymatic browning, so aqueous model systems of glucosamine and cysteine were studied to investigate the effects of reaction temperature, initial pH, reaction time, and concentration ratio of glucosamine and cysteine. Response surface methodology was applied to optimize the independent reaction parameters of cysteine and glucosamine in Maillard reaction. Box-Behnken factorial design was used with 30 runs of 16 factorial levels, 8 axial levels and 6 central levels. The degree of Maillard reaction was determined by reading absorption at 425 nm in a spectrophotometer and Hunter's L, a, and b values. ΔE was consequently set as the fifth response factor. In the statistical analyses, determination coefficients (R 2 ) for their absorbance, Hunter's L, a, b values, and ΔE were 0.94, 0.79, 0.73, 0.96, and 0.79, respectively, showing that the absorbance and Hunter's b value were good dependent variables for this model system. The optimum processing parameters were determined to yield glucosamine-cysteine Maillard reaction product with higher absorbance and higher colour change. The optimum estimated absorbance was achieved at the condition of initial pH 8.0, 111°C reaction temperature, 2.47 h reaction time, and 1.30 concentration ratio. The optimum condition for colour change measured by Hunter's b value was 2.41 h reaction time, 114°C reaction temperature, initial pH 8.3, and 1.26 concentration ratio. These results can provide the basic information for Maillard reaction of aqueous model system between glucosamine and cysteine.

Follow-Up Study to Family Members' Reactions to the Initial Special Education Meeting

Science.gov (United States)

Ingalls, Lawrence; Hammond, Helen; Paez, Carlos; Rodriguez, Ivan

2016-01-01

Family involvement is a central component of Individuals with Disabilities Education Act (IDEA). Family members are to be integrated in all aspects of the special education process. At the onset, of family involvement, it is imperative for educators to be aware of possible reactions family members may experience in this initial stage. This…

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.

Non-universal spreading exponents in a catalytic reaction model

International Nuclear Information System (INIS)

De Andrade, Marcelo F; Figueiredo, W

2011-01-01

We investigated the dependence of the spreading critical exponents and the ultimate survival probability exponent on the initial configuration of a nonequilibrium catalytic reaction model. The model considers the competitive reactions between two different monomers, A and B, where we take into account the energy couplings between nearest neighbor monomers, and the adsorption energies, as well as the temperature T of the catalyst. For each value of T the model shows distinct absorbing states, with different concentrations of the two monomers. Employing an epidemic analysis, we established the behavior of the spreading exponents as we started the Monte Carlo simulations with different concentrations of the monomers. The exponents were determined as a function of the initial concentration ρ A, ini of A monomers. We have also considered initial configurations with correlations for a fixed concentration of A monomers. From the determination of three spreading exponents, and the ultimate survival probability exponent, we checked the validity of the generalized hyperscaling relation for a continuous set of initial states, random and correlated, which are dependent on the temperature of the catalyst

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

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.

Crack initiation at high temperature on an austenitic stainless steel

International Nuclear Information System (INIS)

Laiarinandrasana, L.

1994-01-01

The study deals with crack initiation at 600 degrees Celsius and 650 degrees Celsius, on an austenitic stainless steel referenced by Z2 CND 17 12. The behaviour laws of the studied plate were update in comparison with existing data. Forty tests were carried out on CT specimens, with continuous fatigue with load or displacement controlled, pure creep, pure relaxation, creep-fatigue and creep-relaxation loadings. The practical initiation definition corresponds to a small crack growth of about the grain size, monitored by electrical potential drop technique. The time necessary for the crack to initiate is predicted with fracture mechanics global and local approaches, with the helps of microstructural observations and finite elements results. An identification of a 'Paris'law' for continuous cyclic loading and of a unique correlation between the initiation time and C * k for creep tests was established. For the local approach, crack initiation by creep can be interpreted as the reaching of a critical damage level, by using a damage incremental rule. For creep-fatigue tests, crack growth rates at initiation are greater than those of Paris'law for continuous fatigue. A calculation of a transition time between elastic-plastic and creep domains shows that crack initiation can be interpreted whether by providing Paris'law with an acceleration term when the dwell period is less than the transition time, or by calculating a creep contribution which relies on C * k parameter when the dwell period and/or the initiation times are greater than the transition time. Creep relaxation tests present crack growth rates at initiation which are less than those for 'equivalent' creep-fatigue tests. These crack growth rates when increasing hold time, but also when temperature decreases. Though, for hold times which are important enough and at lower temperature, there is no effect of the dwell period insofar as crack growth rate is equal to continuous fatigue Paris law predicted ones

Temperature dependence and hysteresis of the initial permeability of the 50%Ni - 50%Fe alloy

International Nuclear Information System (INIS)

Kekalo, I.B.; Stolyarov, V.L.; Patsionov, V.A.

1979-01-01

Studied has been a temperature dependence of the initial permeability of the 50% Ni - 50% Fe alloy after primary and secondary recrystallization and effect of thermomagnetic treatment upon the dependence. For all the alloys with the structure of primary recrystallization a monotonous increase of initial permeability with temperature and the presence of slight temperature hysteresis are typical. Thermomagnetic treatment, not affecting considerably the temperature dependence of permeability for all the primarily recrystallized alloys, changes to a great extent the character of the dependence in the secondary recrystallized alloys. For 20-200-20 deg C temperature cycle of the alloys with secondary recrystallized structure are characterized after thermomagnetic treatment by the presence of gigantic hysteresis of initial permeability and a maximum on the heating branch of the curve in the vicinity of 130 deg C which are accounted for by peculiarities of temperature hysteresis of domain structure in the given alloy

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

Initial pressure spike and its propagation phenomena in sodium-water reaction tests for MONJU steam generators

International Nuclear Information System (INIS)

Sato, M.; Hiroi, H.; Tanaka, N.; Hori, M.

1977-01-01

With the objective of demonstrating the safe design of steam generators for prototype LMFBR MONJU against the postulated large-leak accident, a number of large-leak sodium-water reaction tests have been conducted using the SWAT-1 and SWAT-3 rigs. Investigation of the potential effects of pressure load on the system is one of the major concerns in these tests. This paper reports the behavior of initial pressure spike in the reaction vessel, its propagation phenomena to the simulated secondary cooling system, and the comparisons with the computer code for one-dimensional pressure wave propagation problems. Both rigs used are the scaled-down models of the helically coiled steam generators of MONJU. The SWAT-1 rig is a simplified model and consists of a reaction vessel (1/8 scale of MONJU evaporator with 0.4 m dia. and 2.5 m height) and a pressure relief system i.e., a pressure relief line and a reaction products tank. On the other hand, the SWAT-3 rig is a 1/2.5 scale of MONJU SG system and consists of an evaporator (reaction vessel with 1.3 m dia. and 6.35 m height), a superheater, an intermediate heat exchanger (IHX), a piping system simulating the secondary cooling circuit and a pressure relief system. The both water injection systems consist of a water injection line with a rupture disk installed in front of injection hole and an electrically heated water tank. Choice of water injection rates in the scaled-down models is made based on the method of iso-velocity modeling. Test results indicated that the characteristics of the initial pressure spike are dominated by those of initial water injection which are controlled by the conditions of water heater and the size of water injection hole, etc

Radiolysis of Aqueous Benzene Solutions at higher temperatures

Energy Technology Data Exchange (ETDEWEB)

Christensen, H

1964-07-15

Aqueous solutions of benzene have been irradiated with Co {gamma}-rays with doses of up to 2.3 Mrad in the temperature region 100 - 200 C. At 100 C a linear relationship between the phenol concentration and the absorbed dose was obtained, but at 150 C and at higher temperatures the rate of the phenol formation increased significantly after an initial constant period. With higher doses the rate decreased again, falling almost to zero at 200 C after a dose of 2.2 Mrad. The G value of phenol in the initial linear period increased from 2.8 at 100 C to 8.0 at 200 C. The reaction mechanism is discussed and reactions constituting a chain reaction are suggested. The result of the addition of iron ions and of a few inorganic oxides to the system is presented and briefly discussed.

Radiolysis of Aqueous Benzene Solutions at higher temperatures

International Nuclear Information System (INIS)

Christensen, H.

1964-07-01

Aqueous solutions of benzene have been irradiated with Co γ-rays with doses of up to 2.3 Mrad in the temperature region 100 - 200 C. At 100 C a linear relationship between the phenol concentration and the absorbed dose was obtained, but at 150 C and at higher temperatures the rate of the phenol formation increased significantly after an initial constant period. With higher doses the rate decreased again, falling almost to zero at 200 C after a dose of 2.2 Mrad. The G value of phenol in the initial linear period increased from 2.8 at 100 C to 8.0 at 200 C. The reaction mechanism is discussed and reactions constituting a chain reaction are suggested. The result of the addition of iron ions and of a few inorganic oxides to the system is presented and briefly discussed

SIMULTANEOUS MEASUREMENT OF FREE RADICAL DECAY IN POLYMERIZATION OF MMA INITIATED BY AIBN USING ESR AND ITS KINETIC MODEL

Institute of Scientific and Technical Information of China (English)

Ping Xia; Qing-song Hu; Xiao-lan Qian; Xul-in Jiang; De-yue Yan

2001-01-01

The kinetics of free radical decay in the polymerization of MMA initiated by AIBN was studied by means of ESR spectroscopy. It was found that the curves of radical decay are strongly associated with the reaction temperature, the initiator concentration and the solvent. In the case of the radical polymerization carried out at high temperature or in solution, the radical concentration first reached a maximum, then declined monotonously with reaction time. It was also found that the greater the amount of initiator or the higher the temperature, the more rapidly the radicals decay. When the bulk polymerization was implemented at a relatively low temperature, the curves of radical decay became more complicated, i.e.,the radical concentration rapidly rose to a maximum, then dropped to a minimum, finally increased again with reaction time.Taking into account the diffusion effect, a semi-empirical equation is suggested to describe the kinetics of propagating radical decay.

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.

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

The influence of initial temperature on flame acceleration and deflagration-to-detonation transition

International Nuclear Information System (INIS)

Ciccarelli, G.; Boccio, J.L.; Ginsberg, T.

1996-01-01

The influence of initial mixture temperature on deflagration-to-detonation transition (DDT) has been investigated experimentally. The experiments were carried out in a 27-cm-inner diameter, 21.3-meter-long heated detonation tube, which was equipped with periodic orifice plates to promote flame acceleration. Hydrogen-air-steam mixtures were tested at a range of temperatures up to 650K and at an initial pressure of 0.1 MPa. In most cases, the limiting hydrogen mole fraction which resulted in transition to detonation corresponded to the mixture whose detonation cell size, λ, was approximately equal to the inner diameter of the orifice plate, d (e.g., d/λ∼1). The only exception was in dry hydrogen-air mixtures at 650K where the DDT limit was observed to be 11 percent hydrogen, corresponding to a value of d/λ equal to 5.5. For a 10.5 percent hydrogen mixture at 650K, the flame accelerated to a maximum velocity of about 120 m/s and then decelerated to below 2 m/s. This observation indicates that the d/λ = 1 DDT limit criterion provides a necessary condition but not a sufficient one for the onset of DDT in obstacle-laden ducts. In this particular case, the mixture initial condition (i.e., temperature) resulted in the inability of the mixture to sustain flame acceleration to the point where DDT could occur. It was also observed that the distance required for the flame to accelerate to the onset of detonation was a function of both the hydrogen mole fraction and the mixture initial temperature. For example, decreasing the hydrogen mole fraction or increasing the initial mixture temperature resulted in longer transition distances

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)

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...

External boundary effects on simultaneous diffusion and reaction processes

International Nuclear Information System (INIS)

Le Roux, M.N.; Wilhelmsson, H.

1989-01-01

External boundaries influence the spatial and temporal structure of evolution of dynamic systems governed by reaction-diffusion equations. Critical limits, i.e. thresholds for explosive growth or onset of diffusion dominated decay, are found to be caused by the presence of the boundary and to depend on: the position of the boundary, where the density is assumed to be zero at any instant of time: the mutual weights (coefficients) and powers of the nonlinear reaction and diffusion processes; and the initial spatial distribution. However, for particular relations between the nonlinear powers of the reaction and diffusion terms the critical limits do not depend on the initial conditions. The results are obtained by simulation experiment for one, two and three dimensions. Trends in the dynamic evolution of the system with an external boundary imposed are compared with the corresponding analytic results obtained for free boundary. Interesting applications are found in various areas, e.g. in the field of high temperature fusion plasma where the evolution of the temperature profile for the so-called H-mode (constant plasma density) is described

Effects of roasting temperature and duration on fatty acid composition, phenolic composition, Maillard reaction degree and antioxidant attribute of almond (Prunus dulcis) kernel.

Science.gov (United States)

Lin, Jau-Tien; Liu, Shih-Chun; Hu, Chao-Chin; Shyu, Yung-Shin; Hsu, Chia-Ying; Yang, Deng-Jye

2016-01-01

Roasting treatment increased levels of unsaturated fatty acids (linoleic, oleic and elaidic acids) as well as saturated fatty acids (palmitic and stearic acids) in almond (Prunus dulcis) kernel oils with temperature (150 or 180 °C) and duration (5, 10 or 20 min). Nonetheless, higher temperature (200 °C) and longer duration (10 or 20 min) roasting might result in breakdown of fatty acids especially for unsaturated fatty acids. Phenolic components (total phenols, flavonoids, condensed tannins and phenolic acids) of almond kernels substantially lost in the initial phase; afterward these components gradually increased with roasting temperature and duration. Similar results also observed for their antioxidant activities (scavenging DPPH and ABTS(+) radicals and ferric reducing power). The changes of phenolic acid and flavonoid compositions were also determined by HPLC. Maillard reaction products (estimated with non-enzymatic browning index) also increased with roasting temperature and duration; they might also contribute to enhancing the antioxidant attributes. Copyright © 2015 Elsevier Ltd. All rights reserved.

The initial stages of the reaction between ZrCo and hydrogen studied by hot-stage microscopy

International Nuclear Information System (INIS)

Bloch, J.; Brill, M.; Ben-Eliahu, Y.; Gavra, Z.

1998-01-01

The development of hydride phase on the surface of ZrCo under 1 bar of hydrogen was investigated at temperatures between 75 and 300 C. Both surface modifications of the parent alloy and the nucleation and growth of hydride phase were observed. Surface modifications included: grain boundary outgrowth, intra-granular precipitation in the form of fine lamellar hydride phase and micro cracks. It is suggested that the surface modifications result from a combination of hydrogen solubility and the parent metal ductility. These modifications were enhanced near areas which had been previously transformed. The nucleation was self catalyzed, with new nuclei preferentially formed at the vicinity of growing former nuclei. All this suggested that the transport of hydrogen through the hydride phase is faster than its transfer through the surface passivation layer. The growth rate of the nuclei was similar to that of uranium. The activation energy for the growth was E a =24±3 kJ/mol. The results were compared with several other metal-hydrogen systems. It is suggested that the important physical factors controlling the mechanism of the initial hydriding reaction are hydrogen solubility and the brittleness of the parent metal/alloy. These parameters are responsible to the different changes observed during the initial hydriding stages which include: surface modifications, cracking, nucleation and growth. (orig.)

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.

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.

Temperature escalation in PWR fuel rod simulators due to the zircaloy/steam reaction ESSI-4 ESSI-11

International Nuclear Information System (INIS)

Hagen, S.; Kapulla, H.; Malauscheck, H.; Wallenfels, K.P.; Buescher, B.J.

1985-03-01

The tests had the initial heatup rate as main parameter. The experimental arrangement consisted of a fuel rod simulator (central tungsten heater, UO 2 ring pellets and zircaloy cladding), a zircaloy shroud and the fiber ceramic insulation. A steam flow of ca. 20 g/min was introduced at the lower end of the bundle. A temperature escalation was observed in every test. The maximum cladding surface temperature in the single rod tests never exceeded 2200 0 C. The escalation began in the upper region of the rods and moved down the rods, opposite to the direction of steam flow. For fast initial heatup rates, the runoff of molten zircaloy was a limiting process for the escalation. For slow heatup rates, the formation of a protective oxide layer reduced the reaction rate. The test with less insulation thickness showed a reduction of the escalation. A stronger influence was found for the gap between shroud and insulation. This is caused by convection heat losses to the steam circulating in this gap by natural convection. Removal of the gap between shroud and insulation in essentially the same experimental arrangement produced a faster escalation. The posttest appearance of the fuel rod simulators showed that, at slow heatup rates oxidation of the cladding was complete, and the fuel rod was relatively intact. Conversely, at fast heatup rates, relatively little cladding oxidation with extensive dissolution of the UO 2 pellets and runoff of molten cladding was observed. (orig./HP) [de

Unique base-initiated depolymerization of limonene-derived polycarbonates

NARCIS (Netherlands)

Li, C.; Sablong, R.J.; van Benthem, R.A.T.M.; Koning, C.E.

2017-01-01

The depolymerization of poly(limonene carbonate) (PLC) initiated by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was investigated. The strong organic base TBD was capable of deprotonating the OH-terminated PLC, leading to fast degradation via backbiting reactions at high temperature. An interesting

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.

Use of nanostructure initiator mass spectrometry (NIMS to deduce selectivity of reaction in glycoside hydrolases

Directory of Open Access Journals (Sweden)

Kai eDeng

2015-10-01

Full Text Available Chemically synthesized nanostructure-initiator mass spectrometry (NIMS probes derivatized with tetrasaccharides were used to study the reactivity of representative Clostridium thermocellum β-glucosidase, endoglucanases and cellobiohydrolase. Diagnostic patterns for reactions of these different classes of enzymes were observed. Results show sequential removal of glucose by the β-glucosidase and a progressive increase in specificity of reaction from endoglucanases to cellobiohydrolase. Time-dependent reactions of these polysaccharide-selective enzymes were modeled by numerical integration, which provides a quantitative basis to make functional distinctions among a continuum of naturally evolved catalytic properties. Consequently, our method, which combines automated protein translation with high-sensitivity and time-dependent detection of multiple products, provides a new approach to annotate glycoside hydrolase phylogenetic trees with functional measurements.

Determination of the number of radicals in the initial chain reactions by mathematical methods

Directory of Open Access Journals (Sweden)

Pejović Branko B.

2009-01-01

Full Text Available Starting from the fact that the real mechanism in a chemical equation takes places through a certain number of radicals which participate in simultaneous reactions and initiate chain reactions according to a particular pattern, the aim of this study is to determine their number in the first couple of steps of the reaction. Based on this, the numbers of radicals were determined in the general case, in the form of linear difference equations, which, by certain mathematical transformations, were reduced to one equation that satisfies a particular numeric series, entirely defined if its first members are known. The equation obtained was solved by a common method developed in the theory of numeric series, in which its solutions represent the number of radicals in an arbitrary step of the reaction observed, in the analytical form. In the final part of the study, the method was tested and verified using two characteristic examples from general chemistry. The study also gives a suggestion of a more efficient procedure by reducing the difference equation to a lower order.

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.

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

New mechanism of spiral wave initiation in a reaction-diffusion-mechanics system.

Science.gov (United States)

Weise, Louis D; Panfilov, Alexander V

2011-01-01

Spiral wave initiation in the heart muscle is a mechanism for the onset of dangerous cardiac arrhythmias. A standard protocol for spiral wave initiation is the application of a stimulus in the refractory tail of a propagating excitation wave, a region that we call the "classical vulnerable zone." Previous studies of vulnerability to spiral wave initiation did not take the influence of deformation into account, which has been shown to have a substantial effect on the excitation process of cardiomyocytes via the mechano-electrical feedback phenomenon. In this work we study the effect of deformation on the vulnerability of excitable media in a discrete reaction-diffusion-mechanics (dRDM) model. The dRDM model combines FitzHugh-Nagumo type equations for cardiac excitation with a discrete mechanical description of a finite-elastic isotropic material (Seth material) to model cardiac excitation-contraction coupling and stretch activated depolarizing current. We show that deformation alters the "classical," and forms a new vulnerable zone at longer coupling intervals. This mechanically caused vulnerable zone results in a new mechanism of spiral wave initiation, where unidirectional conduction block and rotation directions of the consequently initiated spiral waves are opposite compared to the mechanism of spiral wave initiation due to the "classical vulnerable zone." We show that this new mechanism of spiral wave initiation can naturally occur in situations that involve wave fronts with curvature, and discuss its relation to supernormal excitability of cardiac tissue. The concept of mechanically induced vulnerability may lead to a better understanding about the onset of dangerous heart arrhythmias via mechano-electrical feedback.

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)

HIgh Temperature Photocatalysis over Semiconductors

Science.gov (United States)

Westrich, Thomas A.

Due in large part to in prevalence of solar energy, increasing demand of energy production (from all sources), and the uncertain future of petroleum energy feedstocks, solar energy harvesting and other photochemical systems will play a major role in the developing energy market. This dissertation focuses on a novel photochemical reaction process: high temperature photocatalysis (i.e., photocatalysis conducted above ambient temperatures, T ≥ 100°C). The overarching hypothesis of this process is that photo-generated charge carriers are able to constructively participate in thermo-catalytic chemical reactions, thereby increasing catalytic rates at one temperature, or maintaining catalytic rates at lower temperatures. The photocatalytic oxidation of carbon deposits in an operational hydrocarbon reformer is one envisioned application of high temperature photocatalysis. Carbon build-up during hydrocarbon reforming results in catalyst deactivation, in the worst cases, this was shown to happen in a period of minutes with a liquid hydrocarbon. In the presence of steam, oxygen, and above-ambient temperatures, carbonaceous deposits were photocatalytically oxidized over very long periods (t ≥ 24 hours). This initial experiment exemplified the necessity of a fundamental assessment of high temperature photocatalytic activity. Fundamental understanding of the mechanisms that affect photocatalytic activity as a function of temperatures was achieved using an ethylene photocatalytic oxidation probe reaction. Maximum ethylene photocatalytic oxidation rates were observed between 100 °C and 200 °C; the maximum photocatalytic rates were approximately a factor of 2 larger than photocatalytic rates at ambient temperatures. The loss of photocatalytic activity at temperatures above 200 °C is due to a non-radiative multi-phonon recombination mechanism. Further, it was shown that the fundamental rate of recombination (as a function of temperature) can be effectively modeled as a

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)

On the initial corrosion mechanism of zirconium alloy: Interaction of oxygen and water with Zircaloy at room temperature and 450 C evaluated by x-ray absorption spectroscopy and photoelectron spectroscopy

International Nuclear Information System (INIS)

Doebler, U.; Knop, A.

1994-01-01

The initial stages of zirconium oxide formation on Zircaloy after water (H 2 O) and oxygen (O 2 ) exposures have been investigated in situ using photoelectron spectroscopy and X-ray-absorption spectroscopy. The reactivity of the zirconium alloy with O 2 at room temperature is about 1,000 times higher than for H 2 O. Up to 100 L (1 L = 1 Langmuir unit = 1 · 10 -6 mbar · s) H 2 O exposure, the reactivity of the zirconium alloy at 450 C is comparable to the room temperature reaction. At higher H 2 O exposure, a sharp increase in the reaction rate for the high-temperature oxidation is observed. From the energy position of the Zr 3d photo emission line and their oxygen-induced chemical shifts, one can really follow the formation of the oxide films. Two different substoichiometric oxides were found during reaction with water. Suboxide (1) is located at the zirconium/zirconium-oxide interface. Subsequently, a Suboxide (2) is concluded from the chemical shift of the zirconium photoelectrons. After an oxide thickness of 2 nm, the stoichiometric ZrO 2 phase is not yet developed

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.

Characterization and reaction behavior of ferrocyanide simulants and Hanford Site high-level ferrocyanide waste

International Nuclear Information System (INIS)

Jeppson, D.W.; Simpson, B.C.

1994-02-01

Nonradioactive waste simulants and initial ferrocyanide tank waste samples were characterized to assess potential safety concerns associated with ferrocyanide high-level radioactive waste stored at the Hanford Site in underground single-shell tanks (SSTs). Chemical, physical, thermodynamic, and reaction properties of the waste simulants were determined and compared to properties of initial samples of actual ferrocyanide wastes presently in the tanks. The simulants were shown to not support propagating reactions when subjected to a strong ignition source. The simulant with the greatest ferrocyanide concentration was shown to not support a propagating reaction that would involve surrounding waste because of its high water content. Evaluation of dried simulants indicated a concentration limit of about 14 wt% disodium mononickel ferrocyanide, below which propagating reactions could not occur in the ambient temperature bulk tank waste. For postulated localized hot spots where dried waste is postulated to be at an initial temperature of 130 C, a concentration limit of about 13 wt% disodium mononickel ferrocyanide was determined, below which propagating reactions could not occur. Analyses of initial samples of the presently stored ferrocyanide waste indicate that the waste tank ferrocyanide concentrations are considerably lower than the limit for propagation for dry waste and that the water content is near that of the as-prepared simulants. If the initial trend continues, it will be possible to show that runaway ferrocyanide reactions are not possible under present tank conditions. The lower ferrocyanide concentrations in actual tank waste may be due to tank waste mixing and/or degradation from radiolysis and/or hydrolysis, which may have occurred over approximately 35 years of storage

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

Temperature-dependent elimination efficiency on Phaeocystis globosa by different initial population sizes of rotifer Brachionus plicatilis.

Science.gov (United States)

Sun, Yunfei; Wang, Yuanyuan; Lei, Jin; Qian, Chenchen; Zhu, Xuexia; Akbar, Siddiq; Huang, Yuan; Yang, Zhou

2018-07-01

Due to sea water eutrophication and global warming, the harmful Phaeocystis blooms outbreak frequently in coastal waters, which cause a serious threat to marine ecosystem. The application of rotifer to control the harmful alga is a promising way. To investigate the influence of initial rotifer density and temperature on the ability of rotifer Brachionus plicatilis to eliminate Phaeocystis globosa population, we cultured P. globosa with different initial rotifer densities (1, 3, 5 inds mL -1 ) at 19, 22, 25, 28, and 31 °C for 9-16 d. Results showed that the population of rotifer feeding on Phaeocystis increased rapidly and higher temperatures favored the growth of P. globosa and B. plicatilis. With increased initial rotifer density and temperature, both the clearance rate of rotifer and the reduction rate of P. globosa increased, and thus P. globosa were eliminated earlier. Both temperature and initial rotifer density had significant effects on clearance rate of rotifer and the time to Phaeocystis extinction, and there was a significant interaction between the two factors on the two parameters, i.e., the effect of initial rotifer density on eliminating Phaeocystis decreased with increasing temperature. The rotifer in 5 inds mL -1 at 28 °C eliminated P. globosa in 4 d, whereas the rotifer in 1 ind mL -1 at 19 °C spent about 16 d on eliminating P. globosa. In conclusion, higher temperature and bigger initial rotifer density promote rotifer to eliminate the harmful P. globosa, and the optimal temperature for rotifer to clear P. globosa is 28 °C. Copyright © 2018 Elsevier Ltd. All rights reserved.

[Evaluation of the influence of humidity and temperature on the drug stability by initial average rate experiment].

Science.gov (United States)

He, Ning; Sun, Hechun; Dai, Miaomiao

2014-05-01

To evaluate the influence of temperature and humidity on the drug stability by initial average rate experiment, and to obtained the kinetic parameters. The effect of concentration error, drug degradation extent, humidity and temperature numbers, humidity and temperature range, and average humidity and temperature on the accuracy and precision of kinetic parameters in the initial average rate experiment was explored. The stability of vitamin C, as a solid state model, was investigated by an initial average rate experiment. Under the same experimental conditions, the kinetic parameters obtained from this proposed method were comparable to those from classical isothermal experiment at constant humidity. The estimates were more accurate and precise by controlling the extent of drug degradation, changing humidity and temperature range, or by setting the average temperature closer to room temperature. Compared with isothermal experiments at constant humidity, our proposed method saves time, labor, and materials.

New mechanism of spiral wave initiation in a reaction-diffusion-mechanics system.

Directory of Open Access Journals (Sweden)

Louis D Weise

Full Text Available Spiral wave initiation in the heart muscle is a mechanism for the onset of dangerous cardiac arrhythmias. A standard protocol for spiral wave initiation is the application of a stimulus in the refractory tail of a propagating excitation wave, a region that we call the "classical vulnerable zone." Previous studies of vulnerability to spiral wave initiation did not take the influence of deformation into account, which has been shown to have a substantial effect on the excitation process of cardiomyocytes via the mechano-electrical feedback phenomenon. In this work we study the effect of deformation on the vulnerability of excitable media in a discrete reaction-diffusion-mechanics (dRDM model. The dRDM model combines FitzHugh-Nagumo type equations for cardiac excitation with a discrete mechanical description of a finite-elastic isotropic material (Seth material to model cardiac excitation-contraction coupling and stretch activated depolarizing current. We show that deformation alters the "classical," and forms a new vulnerable zone at longer coupling intervals. This mechanically caused vulnerable zone results in a new mechanism of spiral wave initiation, where unidirectional conduction block and rotation directions of the consequently initiated spiral waves are opposite compared to the mechanism of spiral wave initiation due to the "classical vulnerable zone." We show that this new mechanism of spiral wave initiation can naturally occur in situations that involve wave fronts with curvature, and discuss its relation to supernormal excitability of cardiac tissue. The concept of mechanically induced vulnerability may lead to a better understanding about the onset of dangerous heart arrhythmias via mechano-electrical feedback.

REACTION KINETICS SELF-PROPOGATION REGIME DURING PRE-IGNITION PERIOD

Directory of Open Access Journals (Sweden)

D. D. Polishchuk

2015-11-01

Full Text Available Self-propagation high temperature synthesis (SHS technological regulations application is mainly limited by transformation processes taking place in the pre-ignition period. Zn-S, Zn-Se, Ti-C and 3Ni-Al small sample systems ignition experimental study was carried out under heating conditions in inert atmosphere with temperature values T = 1200K.It was shown that at this temperature level a chemical reaction can be initiated, turning into a self-sustaining mode. Wherein the reaction limiting factors can be mass transfer processes. Ignition temperatures were determined and plotted via the samples size. A physical ignition model was developed assuming the pre-ignition period limiting reaction Arrhenius law.The inverse combustion problem solution made it possible to calculate the low-temperature (T = 800 ÷ 1200K reaction kinetic constant values. Comparison thus obtained values  with the known data of other researchers showed their good agreement.Activation energy values for the Zn-S system were used to calculate the heat wave propagation speed. This value appeared to coincide with experimental values.Obtained results analysis leads to the conclusion about the availability and justification for the proposed method of express-analysis of presupposed, but previously not studied SHS systems. The results thus obtained allow us to estimate conditions for the SHS technology implementation, the reactor characteristic sizes and the thermal wave’s propagation speed.

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

for the inference of Furan combustion reaction rate

KAUST Repository

Long, Quan

2016-01-06

We carry out the design of experiments for the identification of the reaction parameters in Furan combustion. The lacks of information on the true value of the control parameters, specifically, the initial temperature and the initial TBHP concentration, are considered in the design procedure by errors-invariables models. We use two types of observables. The first is a scaler observable, i.e., half decay time of the [TBHP]. The second is the time history of the concentration.

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...

Large eddy simulation of the low temperature ignition and combustion processes on spray flame with the linear eddy model

Science.gov (United States)

Wei, Haiqiao; Zhao, Wanhui; Zhou, Lei; Chen, Ceyuan; Shu, Gequn

2018-03-01

Large eddy simulation coupled with the linear eddy model (LEM) is employed for the simulation of n-heptane spray flames to investigate the low temperature ignition and combustion process in a constant-volume combustion vessel under diesel-engine relevant conditions. Parametric studies are performed to give a comprehensive understanding of the ignition processes. The non-reacting case is firstly carried out to validate the present model by comparing the predicted results with the experimental data from the Engine Combustion Network (ECN). Good agreements are observed in terms of liquid and vapour penetration length, as well as the mixture fraction distributions at different times and different axial locations. For the reacting cases, the flame index was introduced to distinguish between the premixed and non-premixed combustion. A reaction region (RR) parameter is used to investigate the ignition and combustion characteristics, and to distinguish the different combustion stages. Results show that the two-stage combustion process can be identified in spray flames, and different ignition positions in the mixture fraction versus RR space are well described at low and high initial ambient temperatures. At an initial condition of 850 K, the first-stage ignition is initiated at the fuel-lean region, followed by the reactions in fuel-rich regions. Then high-temperature reaction occurs mainly at the places with mixture concentration around stoichiometric mixture fraction. While at an initial temperature of 1000 K, the first-stage ignition occurs at the fuel-rich region first, then it moves towards fuel-richer region. Afterwards, the high-temperature reactions move back to the stoichiometric mixture fraction region. For all of the initial temperatures considered, high-temperature ignition kernels are initiated at the regions richer than stoichiometric mixture fraction. By increasing the initial ambient temperature, the high-temperature ignition kernels move towards richer

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

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

Detonation cell size measurements in high-temperature hydrogen-air-steam mixtures at the BNL high-temperature combustion facility

International Nuclear Information System (INIS)

Ciccarelli, G.; Ginsberg, T.; Boccio, J.L.

1997-11-01

The High-Temperature Combustion Facility (HTCF) was designed and constructed with the objective of studying detonation phenomena in mixtures of hydrogen-air-steam at initially high temperatures. The central element of the HTCF is a 27-cm inner-diameter, 21.3-m long cylindrical test vessel capable of being heating to 700K ± 14K. A unique feature of the HTCF is the 'diaphragmless' acetylene-oxygen gas driver which is used to initiate the detonation in the test gas. Cell size measurements have shown that for any hydrogen-air-steam mixture, increasing the initial mixture temperature, in the range of 300K to 650K, while maintaining the initial pressure of 0.1 MPa, decreases the cell size and thus makes the mixture more detonable. The effect of steam dilution on cell size was tested in stoichiometric and off-stoichiometric (e.g., equivalence ratio of 0.5) hydrogen-air mixtures. Increasing the steam dilution in hydrogen-air mixtures at 0.1 MPa initial pressure increases the cell size, irrespective of initial temperature. It is also observed that the desensitizing effect of steam diminished with increased initial temperature. A 1-dimensional, steady-state Zel'dovich, von Neumann, Doring (ZND) model, with full chemical kinetics, has been used to predict cell size for hydrogen-air-steam mixtures at different initial conditions. Qualitatively the model predicts the overall trends observed in the measured cell size versus mixture composition and initial temperature and pressure. It was found that the proportionality constant used to predict detonation cell size from the calculated ZND model reaction zone varies between 10 and 100 depending on the mixture composition and initial temperature. 32 refs., 35 figs

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.)

Mathematical modeling of the ethanol fermentation of cashew apple juice by a flocculent yeast: the effect of initial substrate concentration and temperature.

Science.gov (United States)

Pinheiro, Álvaro Daniel Teles; da Silva Pereira, Andréa; Barros, Emanuel Meneses; Antonini, Sandra Regina Ceccato; Cartaxo, Samuel Jorge Marques; Rocha, Maria Valderez Ponte; Gonçalves, Luciana Rocha B

2017-08-01

In this work, the effect of initial sugar concentration and temperature on the production of ethanol by Saccharomyces cerevisiae CCA008, a flocculent yeast, using cashew apple juice in a 1L-bioreactor was studied. The experimental results were used to develop a kinetic model relating biomass, ethanol production and total reducing sugar consumption. Monod, Andrews, Levenspiel and Ghose and Tyagi models were investigated to represent the specific growth rate without inhibition, with inhibition by substrate and with inhibition by product, respectively. Model validation was performed using a new set of experimental data obtained at 34 °C and using 100 g L -1 of initial substrate concentration. The model proposed by Ghose and Tyagi was able to accurately describe the dynamics of ethanol production by S. cerevisiae CCA008 growing on cashew apple juice, containing an initial reducing sugar concentration ranging from 70 to 170 g L -1 and temperature, from 26 to 42 °C. The model optimization was also accomplished based on the following parameters: percentage volume of ethanol per volume of solution (%V ethanol /V solution ), efficiency and reaction productivity. The optimal operational conditions were determined using response surface graphs constructed with simulated data, reaching an efficiency and a productivity of 93.5% and 5.45 g L -1  h -1 , respectively.

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.

Temperatures during flower bud development affect pollen germination, self-incompatibility reaction and early fruit development of clementine (Citrus clementina Hort. ex Tan.).

Science.gov (United States)

Distefano, G; Gentile, A; Hedhly, A; La Malfa, S

2018-03-01

One of the key environmental factors affecting plant reproductive systems is temperature. Characterising such effects is especially relevant for some commercially important genera such as Citrus. In this genus, failure of fertilisation results in parthenocarpic fruit development and seedlessness, which is a much-prized character. Here, we characterise the effects of temperature on flower and ovary development, and on pollen-pistil interactions in 'Comune' clementine (Citrus clementina Hort. ex Tan.). We examine flower bud development, in vitro pollen germination and pollen-pistil interaction at different temperatures (15, 20, 25 or 30 °C). These temperatures span the range from 'cold' to 'hot' weather during the flowering season in many citrus-growing regions. Temperature had a strong effect on flower and ovary development, pollen germination, and pollen tube growth kinetics. In particular, parthenocarpic fruit development (indicated by juice vesicle growth) was initiated early if flowers were exposed to warmer temperatures during anthesis. Exposure to different temperatures during flower bud development also alters expression of the self-incompatibility reaction. This affects the point in the pistil at which pollen tube growth is arrested and confirms the role of sub- and supra-optimal temperatures in determining the numbers of pollen tubes reaching the ovary. © 2017 German Society for Plant Sciences and The Royal Botanical Society of the Netherlands.

Kinetics of the hydrogen production reaction in a copper-chlorine water splitting plant

International Nuclear Information System (INIS)

Zamfirescu, C.; Naterer, G.F.; Dincer, I.

2009-01-01

The exothermic reaction of HCl with particulate Cu occurs during hydrogen production step in the thermochemical copper-chlorine (Cu-Cl) water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the reaction kinetics. It is determined that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55 and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches about 3,000 W/m 2 when the particle shrinks to 0.1% from its initial size. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction. It predicts the shrinking of copper particles based on the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for estimation of the temperature of the copper particle, assumed spherical, in the radial direction. The maximum temperature at the interface is higher than the melting point of CuCl by 10-50 o C, depending on the assumed operating conditions. (author)

Study of the Synchrotron Photoionization Oxidation of 2-Methylfuran Initiated by O(3P) under Low-Temperature Conditions at 550 and 650 K.

Science.gov (United States)

Fathi, Yasmin; Meloni, Giovanni

2017-09-21

The O-( 3 P)-initiated oxidation of 2-methylfuran (2-MF) was investigated using vacuum-ultraviolet synchrotron radiation from the Advanced Light Source at Lawrence Berkeley National Laboratory. Reaction species were studied by multiplexed photoionization mass spectrometry at 550 and 650 K. The oxygen addition pathway is favored in this reaction, forming four triplet diradicals that undergo intersystem crossing into singlet epoxide species that lead to the formation of products at m/z 30 (formaldehyde), 42 (propene), 54 (1-butyne, 1,3-butadiene, and 2-butyne), and 70 (2-butenal, methyl vinyl ketone, and 3-butenal). Mass-to-charge ratios, photoionization spectra, and adiabatic ionization energies for each primary reaction species were obtained and used to characterize their identities. In addition, by means of electronic structure calculations, potential energy surface scans of the different species produced throughout the oxidation were examined to further validate the primary chemistry occurring. Branching fractions for the formation of the primary products were calculated at the two temperatures and contribute 81.0 ± 21.4% at 550 K and 92.1 ± 25.5% at 650 K.

Stabilization of silver nanoparticles in nonanoic acid: A temperature activated conformation reaction observed with surface enhanced Raman spectroscopy

International Nuclear Information System (INIS)

Henneke, Dale E.; Malyavanatham, Gokul; Kovar, Desiderio; O'Brien, D.T.; Becker, M.F.; Nichols, William T.; Keto, J.W.

2003-01-01

Silver nanoparticles were synthesized by ultraviolet (λ=248 nm) laser ablation of an aerosol of micron-sized source particles entrained in nitrogen. As a result of thermionic electron emission and photoionization, nanoparticles produced in this manner were highly charged. The resulting aerosol was primarily composed of nanometer sized particles. The charged nanoparticles were deflected by an electric field that was perpendicular to the aerosol flow. Deflected nanoparticles were deposited directly into n-nonanoic acid flowing along the negative collection electrode. Suspensions of nanoparticles collected in this manner were dark gray in color and were found to be flocculated. When the suspensions were heated to temperatures above 75 deg. C, a color change from gray to clear was observed. Ultraviolet/visible extinction spectroscopy was performed on each suspension following annealing at different temperatures and times. By modeling the absorption decrease as a first order reaction, a good fit for the data was found. Analysis by dynamic light scattering (DLS) showed that the initial mean flocculent size of the gray suspensions was 602 nm. DLS analysis of the suspensions taken at different annealing intervals showed that the flocculent size decreased, but maintained a narrow size distribution until the size shrank below the instrument resolution limit. The reduction in flocculent size coincided with the observed color change, and an irreversible transition to a deflocculated primary nanoparticle suspension is observed. Surface enhanced Raman scattering is used to confirm that the reaction results from a change in the orientation of the nonanoic molecule on the surface of the nanoparticle

A study of the tyramine/glucose Maillard reaction: Variables, characterization, cytotoxicity and preliminary application.

Science.gov (United States)

Jiang, Wei; Chen, Yaxin; He, Xiaoxia; Hu, Shiwei; Li, Shijie; Liu, Yu

2018-01-15

The tyramine/glucose Maillard reaction was proposed as an emerging tool for tyramine reduction in a model system and two commercial soy sauce samples. The model system was composed of tyramine and glucose in buffer solutions with or without NaCl. The results showed that tyramine was reduced in the model system, and the reduction rate was affected by temperature, heating time, initial pH value, NaCl concentration, initial glucose concentration and initial tyramine concentration. Changes in fluorescence intensity and ultraviolet-visible (UV-vis) absorption spectra showed three stages of the Maillard reaction between tyramine and glucose. Cytotoxicity assay demonstrated that tyramine/glucose Maillard reaction products (MRPs) were significantly less toxic than that of tyramine (pMaillard reaction is a promising method for tyramine reduction in foods. Copyright © 2017 Elsevier Ltd. All rights reserved.

A unique approach to demonstrating that apical bud temperature specifically determines leaf initiation rate in the dicot Cucumis sativus

NARCIS (Netherlands)

Savvides, Andreas; Dieleman, Anja; Ieperen, van Wim; Marcelis, Leo F.M.

2016-01-01

Main conclusion: Leaf initiation rate is largely determined by the apical bud temperature even when apical bud temperature largely deviates from the temperature of other plant organs.We have long known that the rate of leaf initiation (LIR) is highly sensitive to temperature, but previous studies

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

Electromigration-induced cracks in Cu/Sn3.5Ag/Cu solder reaction couple at room temperature

International Nuclear Information System (INIS)

He Hongwen; Xu Guangchen; Guo Fu

2009-01-01

Electromigration (EM) behavior of Cu/Sn 3.5 Ag/Cu solder reaction couple was investigated with a high current density of 5 x 10 3 A/cm 2 at room temperature. One dimensional structure, copper wire/solder ball/copper wire SRC was designed and fabricated to dissipate the Joule heating induced by the current flow. In addition, thermomigration effect was excluded due to the symmetrical structure of the SRC. The experimental results indicated that micro-cracks initially appeared near the cathode interface between solder matrix and copper substrate after 474 h current stressing. With current stressing time increased, the cracks propagated and extended along the cathode interface. It should be noted that the continuous Cu 6 Sn 5 intermetallic compounds (IMCs) layer both at the anode and at the cathode remained their sizes. Interestingly, tiny cracks appeared at the root of some long column-type Cu 6 Sn 5 at the cathode interface due to the thermal stress.

Investigating Initial Disclosures and Reactions to Unexpected, Positive HPV Diagnosis.

Science.gov (United States)

Smith, Rachel A; Hernandez, Rachael; Catona, Danielle

2014-07-01

Initial disclosures of health conditions are critical communication moments. Existing research focuses on disclosers; integrating confidants into studies of initial disclosures is needed. Guided by the disclosure decision-making model (DD-MM; Greene, 2009), this study examined what diagnosed persons and confidants may say when faced with unexpected test results and unexpected disclosures, respectively. Participants ( N = 151) recorded an audio-visual message for another person, after imagining that they or the other person had just received unexpected, positive HPV test results. The qualitative analysis revealed four themes: (1) impression management and social distance, (2) invisible symptoms and advice regarding future disclosures, (3) expressing and acknowledging emotional reactions, and (4) misunderstandings and lacking knowledge about HPV. These findings suggested that DD-MM may be a relevant framework for understanding not only when disclosers share, but what disclosers and confidants say in early conversations about new diagnoses. While disclosers' and confidants' messages showed marked similarities, important differences appeared. For example, confidants focused on assuaging disclosers' fear about the consequences, whereas disclosers expressed distress related to their uncertainty about the prognosis of an HPV infection and how to prepare for next steps. The discussion highlighted implications for the DD-MM, HPV disclosures, and future interventions.

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-02-05

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

Ab initio chemical kinetics for the ClOO + NO reaction: Effects of temperature and pressure on product branching formation

Science.gov (United States)

Raghunath, P.; Lin, M. C.

2012-07-01

The kinetics and mechanism for the reaction of ClOO with NO have been investigated by ab initio molecular orbital theory calculations based on the CCSD(T)/6-311+G(3df)//PW91PW91/6-311+G(3df) method, employed to evaluate the energetics for the construction of potential energy surfaces and prediction of reaction rate constants. The results show that the reaction can produce two key low energy products ClNO + 3O2 via the direct triplet abstraction path and ClO + NO2 via the association and decomposition mechanism through long-lived singlet pc-ClOONO and ClONO2 intermediates. The yield of ClNO + O2 (1△) from any of the singlet intermediates was found to be negligible because of their high barriers and tight transition states. As both key reactions initially occur barrierlessly, their rate constants were evaluated with a canonical variational approach in our transition state theory and Rice-Ramspergen-Kassel-Marcus/master equation calculations. The rate constants for ClNO + 3O2 and ClO + NO2 production from ClOO + NO can be given by 2.66 × 10-16 T1.91 exp(341/T) (200-700 K) and 1.48 × 10-24 T3.99 exp(1711/T) (200-600 K), respectively, independent of pressure below atmospheric pressure. The predicted total rate constant and the yields of ClNO and NO2 in the temperature range of 200-700 K at 10-760 Torr pressure are in close agreement with available experimental results.

Novel Synthesis of Ultra-Small Dextran Coated Maghemite Nanoparticles for MRI and CT Contrast Agents via a Low Temperature Co-Precipitation Reaction.

Science.gov (United States)

Rabias, Ioannis; Fardis, Michael; Kehagias, Thomas; Kletsas, Dimitris; Pratsinis, Harris; Tsitrouli, Danai; Maris, Thomas G; Papavassiliou, George

2015-01-01

Ultra-small dextran coated maghemite nanoparticles are synthesized via a low temperature modified co-precipitation method. A monoethylene glycol/water solution of 1:1 molar ratios and a fixed apparatus is used at a constant temperature of 5-10 degrees C. The growth of nanoparticles is prohibited due to low temperature synthesis and differs from usual thermal decomposition methods via Ostwald ripening. Strict temperature control and reaction timing of less than 20 minutes are essential to maintain narrow distribution in particle size. These nanoparticles are water-dispersible and biocompatible by capping with polyethylene glycol ligands. The aqueous suspensions are tested for cytotoxic activity on normal human skin fibroblasts. There is no reduction of the cells' viability at any concentration tested, the highest being 1% v/v of the suspension in culture medium, corresponding to the highest concentrations to be administered in vivo. Initial comparison with a T1 MRI contrast agent in sale shows that maghemite nanoparticles exhibit high r1 and r2 relaxivities in MRI tomography and strong contrast in computed tomography, demonstrating that these nanoparticles can be efficient T1, T2 and CT contrast agents.

Limonene and its ozone-initiated reaction products attenuate allergic lung inflammation in mice.

Science.gov (United States)

Hansen, Jitka S; Nørgaard, Asger W; Koponen, Ismo K; Sørli, Jorid B; Paidi, Maya D; Hansen, Søren W K; Clausen, Per Axel; Nielsen, Gunnar D; Wolkoff, Peder; Larsen, Søren Thor

2016-11-01

Inhalation of indoor air pollutants may cause airway irritation and inflammation and is suspected to worsen allergic reactions. Inflammation may be due to mucosal damage, upper (sensory) and lower (pulmonary) airway irritation due to activation of the trigeminal and vagal nerves, respectively, and to neurogenic inflammation. The terpene, d-limonene, is used as a fragrance in numerous consumer products. When limonene reacts with the pulmonary irritant ozone, a complex mixture of gas and particle phase products is formed, which causes sensory irritation. This study investigated whether limonene, ozone or the reaction mixture can exacerbate allergic lung inflammation and whether airway irritation is enhanced in allergic BALB/cJ mice. Naïve and allergic (ovalbumin sensitized) mice were exposed via inhalation for three consecutive days to clean air, ozone, limonene or an ozone-limonene reaction mixture. Sensory and pulmonary irritation was investigated in addition to ovalbumin-specific antibodies, inflammatory cells, total protein and surfactant protein D in bronchoalveolar lavage fluid and hemeoxygenase-1 and cytokines in lung tissue. Overall, airway allergy was not exacerbated by any of the exposures. In contrast, it was found that limonene and the ozone-limonene reaction mixture reduced allergic inflammation possibly due to antioxidant properties. Ozone induced sensory irritation in both naïve and allergic mice. However, allergic but not naïve mice were protected from pulmonary irritation induced by ozone. This study showed that irritation responses might be modulated by airway allergy. However, aggravation of allergic symptoms was observed by neither exposure to ozone nor exposure to ozone-initiated limonene reaction products. In contrast, anti-inflammatory properties of the tested limonene-containing pollutants might attenuate airway allergy.

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.

High temperature initiation and propagation of cracks in 12%Cr-steel turbine disks

Directory of Open Access Journals (Sweden)

S. Foletti

2013-10-01

Full Text Available This work aims to study the crack propagation in 12%Cr steel for turbine disks. Creep Crack Growth (CCG tests on CT specimens have been performed to define the proper fracture mechanics which describes the initiation of the crack propagation and the crack growth behaviour for the material at high temperature. Results have been used to study the occurrence of crack initiation on a turbine disk at the extreme working temperature and stress level experienced during service, and validate the use of C* integral in correlating creep growth rate on the disk component, in case C* is numerically calculated through FEM analysis or calculated by the use of reference stress concept.

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.

A study on the boron injection initiation temperature curve of BWR

International Nuclear Information System (INIS)

Wang, S.-J.; Chien, C.-S.; Fann, S.-Y.; Chiang, S.-C.

2007-01-01

Boron injection initiation temperature (BIIT) provides important information for the safe shutdown of the reactor using boron injection system during anticipated transient without scram (ATWS). The purpose of this paper is to study BIIT curve of boiling water reactor owners' group (BWROG). The unreasonable and non-conservative parts of BIIT are pointed out and suggested modifications are made. The starting reactor power of BIIT is increased in order to meet the actual application. The lower limit of suppression pool temperature of BIIT is revised for conservative operation during ATWS conditions. Analysis of the effects of maximum temperature capacity of the suppression chamber and concentration of boron in standby liquid control tank shows that BIIT is decreased by adopting a more conservative value of maximum temperature capacity of the suppression chamber. Consequently, early boron injection is anticipated. For system with automatic boron injection system, BIIT is not required

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

Photon Energy Threshold in Direct Photocatalysis with Metal Nanoparticles: Key Evidence from the Action Spectrum of the Reaction.

Science.gov (United States)

Sarina, Sarina; Jaatinen, Esa; Xiao, Qi; Huang, Yi Ming; Christopher, Philip; Zhao, Jin Cai; Zhu, Huai Yong

2017-06-01

By investigating the action spectra (the relationship between the irradiation wavelength and apparent quantum efficiency of reactions under constant irradiance) of a number of reactions catalyzed by nanoparticles including plasmonic metals, nonplasmonic metals, and their alloys at near-ambient temperatures, we found that a photon energy threshold exists in each photocatalytic reaction; only photons with sufficient energy (e.g., higher than the energy level of the lowest unoccupied molecular orbitals) can initiate the reactions. This energy alignment (and the photon energy threshold) is determined by various factors, including the wavelength and intensity of irradiation, molecule structure, reaction temperature, and so forth. Hence, distinct action spectra were observed in the same type of reaction catalyzed by the same catalyst due to a different substituent group, a slightly changed reaction temperature. These results indicate that photon-electron excitations, instead of the photothermal effect, play a dominant role in direct photocatalysis of metal nanoparticles for many reactions.

Influence of the initial grain size of silicon on microstructure and mechanical properties of reaction-sintered silicon nitride

International Nuclear Information System (INIS)

Heinrich, J.

1977-01-01

The influence of the initial grain size of the silicon powder on the microstructure and the resulting mechanical properties are studied. The smaller the grain size of the silicon powders used, the higher will be the degree of reaction at the beginning of the nitridation reaction and the higher the amount of α-modification in the fully nitridated samples. Moreover, the nitrification time can be considerably shortened when fine-grained silicon powders ( [de

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)

Use of a temperature-initiated passive cooling system (TIPACS) for the modular high-temperature gas-cooled reactor cavity cooling system (RCCS)

International Nuclear Information System (INIS)

Forsberg, C.W.; Conklin, J.; Reich, W.J.

1994-04-01

A new type of passive cooling system has been invented (Forsberg 1993): the Temperature-Initiated Passive Cooling System (TIPACS). The characteristics of the TIPACS potentially match requirements for an improved reactor-cavity-cooling system (RCCS) for the modular high-temperature gas-cooled reactor (MHTGR). This report is an initial evaluation of the TIPACS for the MHTGR with a Rankines (steam) power conversion cycle. Limited evaluations were made of applying the TIPACS to MHTGRs with reactor pressure vessel temperatures up to 450 C. These temperatures may occur in designs of Brayton cycle (gas turbine) and process heat MHTGRs. The report is structured as follows. Section 2 describes the containment cooling issues associated with the MHTGR and the requirements for such a cooling system. Section 3 describes TIPACS in nonmathematical terms. Section 4 describes TIPACS's heat-removal capabilities. Section 5 analyzes the operation of the temperature-control mechanism that determines under what conditions the TIPACS rejects heat to the environment. Section 6 addresses other design and operational issues. Section 7 identifies uncertainties, and Section 8 provides conclusions. The appendixes provide the detailed data and models used in the analysis

Use of a temperature-initiated passive cooling system (TIPACS) for the modular high-temperature gas-cooled reactor cavity cooling system (RCCS)

Energy Technology Data Exchange (ETDEWEB)

Forsberg, C.W.; Conklin, J.; Reich, W.J.

1994-04-01

A new type of passive cooling system has been invented (Forsberg 1993): the Temperature-Initiated Passive Cooling System (TIPACS). The characteristics of the TIPACS potentially match requirements for an improved reactor-cavity-cooling system (RCCS) for the modular high-temperature gas-cooled reactor (MHTGR). This report is an initial evaluation of the TIPACS for the MHTGR with a Rankines (steam) power conversion cycle. Limited evaluations were made of applying the TIPACS to MHTGRs with reactor pressure vessel temperatures up to 450 C. These temperatures may occur in designs of Brayton cycle (gas turbine) and process heat MHTGRs. The report is structured as follows. Section 2 describes the containment cooling issues associated with the MHTGR and the requirements for such a cooling system. Section 3 describes TIPACS in nonmathematical terms. Section 4 describes TIPACS`s heat-removal capabilities. Section 5 analyzes the operation of the temperature-control mechanism that determines under what conditions the TIPACS rejects heat to the environment. Section 6 addresses other design and operational issues. Section 7 identifies uncertainties, and Section 8 provides conclusions. The appendixes provide the detailed data and models used in the analysis.

Reaction Equilibrium of the ω-Transamination of (S)-Phenylethylamine

DEFF Research Database (Denmark)

Voges, Matthias; Abu, Rohana; Deslauriers, Maria Gundersen

2017-01-01

This work focuses on the thermodynamic equilibrium of the ω-transaminase-catalyzed reaction of (S)-phenylethylamine with cyclohexanone to acetophenone and cyclohexylamine in aqueous solution. For this purpose, the equilibrium concentrations of the reaction were experimentally investigated under...... varying reaction conditions. It was observed that the temperature (30 and 37 °C), the pH (between pH 7 and pH 9), as well as the initial reactant concentrations (between 5 and 50 mmol·kg-1) influenced the equilibrium position of the reaction. The position of the reaction equilibrium was moderately shifted...... position to the reactant side. In order to explain these effects, the activity coefficients of the reacting agents were calculated and the activity-based thermodynamic equilibrium constant Kth of the reaction was determined. For this purpose, the activity coefficients of the reacting agents were modeled...

Connecting the dots: Semi-analytical and random walk numerical solutions of the diffusion–reaction equation with stochastic initial conditions

Energy Technology Data Exchange (ETDEWEB)

Paster, Amir, E-mail: paster@tau.ac.il [Environmental Fluid Mechanics Laboratories, Dept. of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN (United States); School of Mechanical Engineering, Tel Aviv University, Tel Aviv, 69978 (Israel); Bolster, Diogo [Environmental Fluid Mechanics Laboratories, Dept. of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN (United States); Benson, David A. [Hydrologic Science and Engineering, Colorado School of Mines, Golden, CO, 80401 (United States)

2014-04-15

We study a system with bimolecular irreversible kinetic reaction A+B→∅ where the underlying transport of reactants is governed by diffusion, and the local reaction term is given by the law of mass action. We consider the case where the initial concentrations are given in terms of an average and a white noise perturbation. Our goal is to solve the diffusion–reaction equation which governs the system, and we tackle it with both analytical and numerical approaches. To obtain an analytical solution, we develop the equations of moments and solve them approximately. To obtain a numerical solution, we develop a grid-less Monte Carlo particle tracking approach, where diffusion is modeled by a random walk of the particles, and reaction is modeled by annihilation of particles. The probability of annihilation is derived analytically from the particles' co-location probability. We rigorously derive the relationship between the initial number of particles in the system and the amplitude of white noise represented by that number. This enables us to compare the particle simulations and the approximate analytical solution and offer an explanation of the late time discrepancies. - Graphical abstract:.

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

Temperature-programmed desorption study of NO reactions on rutile TiO2(110)-1×1

Energy Technology Data Exchange (ETDEWEB)

Kim, Boseong; Dohnalek, Zdenek; Szanyi, Janos; Kay, Bruce D.; Kim, Yu Kwon

2016-10-01

Systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO2(110)-1×1 surface reveal several distinct reaction channels in a temperature range of 50 – 500 K. NO readily reacts on TiO2(110) to form N2O which desorbs between 50 and 200 K (LT N2O channels), which leaves the TiO2 surface populated with adsorbed oxygen atoms (Oa) as a byproduct of N2O formation. In addition, we observe simultaneous desorption peaks of NO and N2O at 270 K (HT1 N2O) and 400 K (HT2 N2O), respectively, both of which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO2(110) surface above 500 K or higher, while the surface may be populated with Oa’s and oxidized products such as NO2 and NO3. The adsorbate-free TiO2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.

Kinetics of Waterborne Alkyd/Acrylic Hybrid Resin Free Radical Polymerization by Two Systems of Redox and Thermal Initiators

OpenAIRE

shirin Madadi; ali akbar Yousefi; elham Keshmirizadeh

2012-01-01

Kinetics of radical polymerizations of waterborne alkyd/acrylic hybrid resin via batch mini-emulsion technique was studied using redox initiators (TBHP/Fe2+/EDTA/AsAc  and  TBHP/Fe2+/EDTA/SFS) at relatively low temperatures and thermal initiators (BPO, KPS and AIBN) at higher temperatures to seek the most suitable initiator system. At the end of all reactions the unreacted monomer content was reduced using post-polymerization technique; consequently, leading to increased monomer conversion an...

Exciplexes versus Loose Ion Pairs: How Does the Driving Force Impact the Initial Product Ratio of Photoinduced Charge Separation Reactions?

Science.gov (United States)

2014-01-01

Many donor–acceptor systems can undergo a photoinduced charge separation reaction, yielding loose ion pairs (LIPs). LIPs can be formed either directly via (distant) electron transfer (ET) or indirectly via the dissociation of an initially formed exciplex or tight ion pair. Establishing the prevalence of one of the reaction pathways is challenging because differentiating initially formed exciplexes from LIPs is difficult due to similar spectroscopic footprints. Hence, no comprehensive reaction model has been established for moderately polar solvents. Here, we employ an approach based on the time-resolved magnetic field effect (MFE) of the delayed exciplex luminescence to distinguish the two reaction channels. We focus on the effects of the driving force of ET and the solvent permittivity. We show that, surprisingly, the exciplex channel is significant even for an exergonic ET system with a free energy of ET of −0.58 eV and for the most polar solutions studied (butyronitrile). Our findings demonstrate that exciplexes play a crucial role even in polar solvents and at moderate driving forces, contrary to what is usually assumed. PMID:25243054

Kinetics of the reaction of iron blast furnace slag/hydrated lime sorbents with SO{sub 2} at low temperatures: effects of the presence of CO{sub 2}, O{sub 2}, and NOx

Energy Technology Data Exchange (ETDEWEB)

Liu, C.F.; Shih, S.M. [Industrial Technological Research Institute, Hsinchu (Taiwan)

2009-09-15

The effects of the presence of CO{sub 2}, O{sub 2}, and NOx in the flue gas on the kinetics of the sulfation of blast furnace slag/hydrated lime sorbents at low temperatures were studied using a differential fixed-bed reactor. When O{sub 2} and NOx were not present simultaneously, the reaction kinetics was about the same as that under the gas mixtures containing SO{sub 2}, H{sub 2}O, and N{sub 2} only, being affected mainly by the relative humidity. The sulfation of sorbents can be described by the surface coverage model and the model equations derived for the latter case. When both O{sub 2} and NOx, were present, the sulfation of sorbents was greatly enhanced, forming a great amount of sulfate in addition to sulfite. The surface coverage model is still valid in this case, but the model equations obtained show a more marked effect of relative humidity and negligible effects of SO{sub 2} concentration and temperature on the reaction. The effect of sorbent composition on the reaction kinetics was entirely represented by the effects of the initial specific surface area (S{sub g0}) and the Ca molar content (M{sup -1}) of sorbent. The initial conversion rate of sorbent increased linearly with increasing S{sub g0}, and the ultimate conversion increased linearly with increasing S{sub g0}M{sup -1}. The model equations obtained in this work are applicable to describe the kinetics of the sulfation of the sorbents in the low-temperature dry and semidry fine gas desulfurization processes either with an upstream NOx, removal unit or without.111

Multiple cracks initiation and propagation behavior of stainless steel in high temperature water environment

International Nuclear Information System (INIS)

Kamaya, Masayuki; Chiba, Goro; Nakajima, Nobuo; Totsuka, Nobuo

2001-01-01

Environmentally assisted crack initiation behavior is greatly affected by applied stress and environmental factors, such as water temperature, contained impurities and so on. On the other hand, crack initiation behavior also influences crack propagation. A typical example of this influence can be observed as the interference effects of multiple cracks, such as the coalescence of approaching crack tips or the arrest phenomena in the relaxation zone of an adjacent crack. To understand these effects of crack initiation on crack propagation behavior is very important to predict the lifetime of components, in which quite a few cracks tend to occur. This study aimed at revealing the crack initiation behavior and the influence of this behavior on propagation. At first, to evaluate the effect of applied stress on crack initiation behavior, sensitized stainless steel was subjected to a four-point bending test in a high temperature water environment at the constant potentials of ECP +50 mV and ECP +150 mV. Secondly, a crack initiation and growth simulation model was developed, in which the interference effect of multiple cracks is evaluated by the finite element method, based on the experimental results. Using this model, the relationship between crack initiation and propagation was studied. From the model, it was revealed that the increasing number of the cracks accelerates crack propagation and reduces life. (author)

Initiation and propagation of multiple cracks of stainless steel in high temperature water environment

Energy Technology Data Exchange (ETDEWEB)

Kamaya, Masayuki; Chiba, Goro; Nakajima, Nobuo; Totsuka, Nobuo [Institute of Nuclear Safety System Inc., Mihama, Fukui (Japan)

2001-09-01

Environmentally assisted crack initiation behavior is greatly affected by applied stress and environmental factors, such as water temperature, contained impurities and so on. Crack initiation behavior also influences crack propagation. A typical example of this influence can be observed as the interference effects of multiple cracks, such as the coalescence of approaching crack tips or the arrest phenomena in the relaxation zone of an adjacent crack. To understand these effects of crack initiation on crack propagation behavior is very important to predict the lifetime of components, in which relatively large number of cracks tend to occur. This study aimed at revealing the crack initiation behavior and the influence of this behavior on propagation. At first, to evaluate the effect of applied stress on crack initiation behavior, sensitized stainless steel was subjected to a four-point bending test in high temperature water environment at the constant potentials of +50 mV SHE and +150 mV SHE Secondly, a crack initiation and growth simulation model was developed, in which the interference effect of multiple cracks is evaluated by the finite element method, based on the experimental results. Using this model, the relationship between crack initiation and propagation was investigated, and it was revealed that the increasing number of the cracks accelerates crack propagation and reduces life. (author)

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].

Simultaneous effect of initial weight, initial crowding, temperature and O2 concentration on the nutritional use of food by rainbow trout (Oncorhynchus mykiss).

Science.gov (United States)

Martinez, F J; Garcia, M P; Canteras, M; De Costa, J; Zamora, S

1992-01-01

The simultaneous effects of initial weight, initial crowding, temperature and O2 concentration on the following ratios: relative growth rate percent (RGRP), feed efficiency (FE), protein efficiency ratio (PER) and protein productive value (PPV) were studied in the rainbow trout. Multivariant equations were obtained for each of the mentioned indices. The joint effects of these factors were evidenced by means of a multiple correlation analysis. The influence of temperature and, to a lesser extent, of crowding, and O2 concentration on the nutritional use of food by the trout was demonstrated, their fundamental dependence on factors extrinsic to the animal being underlined. The non proportional changes in PER and PPV as temperature rises revealed that an increasing part of the ingested aminoacids were used for synthesis of fat, non for proteins edification.

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.

Predicting Comfort Temperature in Indonesia, an Initial Step to Reduce Cooling Energy Consumption

Directory of Open Access Journals (Sweden)

Tri Harso Karyono

2015-07-01

Full Text Available Indonesia has no reliable thermal comfort standard that is based on research works. The current national standard (SNI 6390:2011 states only a single range of comfort temperature that is 25.5 °C Ta, with a range of +1.5 °C Ta. Previous thermal studies in a number of different buildings in Indonesia showed that the neutral (comfort temperatures of subjects were about 27 to 28 °C, which is higher than the values stated in the standard. As a big country with various ambient temperatures, Indonesian needs a better and more reliable thermal comfort predictor which can be applied properly across the country. This study is an attempt to propose an initial Indonesian thermal predictor, in the form of a simple equation, which could predict comfort temperatures properly across the country. Reanalysing the previous comfort studies in Indonesia, a simple regression equation is constructed as to be used as the initial Indonesian comfort predictor. Using this predictor, the comfort temperatures in a lowland or coastal cities like Jakarta is found to be higher than the current comfort standard. It is expected that this predictor would help to provide a better indoor thermal environment and at the same reduce the cooling energy in air conditioning (AC building, thus reducing a building’s carbon emissions.

Carbamoyl anion-initiated cascade reaction for stereoselective synthesis of substituted α-hydroxy-β-amino amides.

Science.gov (United States)

Lin, Chao-Yang; Ma, Peng-Ju; Sun, Zhao; Lu, Chong-Dao; Xu, Yan-Jun

2016-01-18

A carbamoyl anion-initiated cascade reaction with acylsilanes and imines has been used to rapidly construct substituted α-hydroxy-β-amino amides. The Brook rearrangement-mediated cascade allows the formation of two C-C bonds and one O-Si bond in a single pot. Using this approach, a range of α-aryl α-hydroxy-β-amino amides has been synthesized in high yields with excellent diastereoselectivities.

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

Formation of simple nitrogen hydrides NH and NH2 at cryogenic temperatures through N + NH3→ NH + NH2 reaction: dark cloud chemistry of nitrogen.

Science.gov (United States)

Nourry, Sendres; Krim, Lahouari

2016-07-21

Although NH3 molecules interacting with ground state nitrogen atoms N((4)S) seem not to be a very reactive system without providing additional energy to initiate the chemical process, we show through this study that, in the solid phase, at very low temperature, NH3 + N((4)S) reaction leads to the formation of the amidogen radical NH2. Such a dissociation reaction previously thought to occur exclusively through UV photon or energetic particle irradiation is in this work readily occurring just by stimulating the mobility of N((4)S)-atoms in the 3-10 K temperature range in the solid sample. The N((4)S)-N((4)S) recombination may be the source of metastable molecular nitrogen N2(A), a reactive species which might trigger the NH3 dissociation or react with ground state nitrogen atoms N((4)S) to form excited nitrogen atoms N((4)P/(2)D) through energy transfer processes. Based on our obtained results, it is possible to propose reaction pathways to explain the NH2 radical formation which is the first step in the activation of stable species such as NH3, a chemical induction process that, in addition to playing an important role in the origin of molecular complexity in interstellar space, is known to require external energy supplies to occur in the gas phase.

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.

The OH-initiated atmospheric oxidation of divinyl sulfoxide: A theoretical investigation on the reaction mechanism

Science.gov (United States)

Zhang, Weichao; Zhang, Dongju

2012-08-01

The potential energy surfaces for the OH + divinyl sulfoxide reaction in the presence of O2/NO are theoretically characterized at the CCSD(T)/6-311+G(d,p)//BH&HLYP/6-311++G(d,p)+ZPE level of theory. Various possible pathways including the direct hydrogen abstraction channels and the addition-elimination channels are considered. The calculations show that the exclusive feasible entrance channel is the formation of adduct CH2(OH)CHS(O)CHdbnd CH2 (IM1) in the initial reaction pathways. In the atmosphere, the newly formed adduct IM1 can further react with O2/NO to form the dominant products HCHO + C(O)HS(O)CHdbnd CH2 (P9). The calculated results confirm the experimental studies.

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.

Low-Temperature Synchrotron Photoionization Study of 2-Methyl-3-buten-2-ol (MBO) Oxidation Initiated by O(3P) Atoms in the 298-650 K Range.

Science.gov (United States)

Fathi, Yasmin; Price, Chelsea; Meloni, Giovanni

2017-04-20

This work studies the oxidation of 2-methyl-3-buten-2-ol initiated by O( 3 P) atoms. The oxidation was investigated at room temperature, 550, and 650 K. Using the synchrotron radiation from the Advanced Light Source (ALS) of the Lawrence Berkley National Laboratory, reaction intermediates and products were studied by multiplexed photoionization mass spectrometry. Mass-to-charge ratios, kinetic time traces, photoionization spectra, and adiabatic ionization energies for each primary reaction species were obtained and used to characterize their identity. Using electronic structure calculations, potential energy surface scans of the different species produced throughout the oxidation were examined and presented in this paper to further validate the primary chemistry occurring. Branching fractions of primary products at all three temperatures were also provided. At room temperature only three primary products formed: ethenol (26.6%), acetaldehyde (4.2%), and acetone (53.4%). At 550 and 650 K the same primary products were observed in addition to propene (5.1%, 11.2%), ethenol (18.1%, 2.8%), acetaldehyde (8.9%, 5.7%), cyclobutene (1.6%, 10.8%), 1-butene (2.0%, 10.9%), trans-2-butene (3.2%, 23.1%), acetone (50.4%, 16.8%), 3-penten-2-one (1.0%, 11.5%), and 3-methyl-2-butenal (0.9%, 2.5%), where the first branching fraction value in parentheses corresponds to the 550 K data. At the highest temperature, a small amount of propyne (1.0%) was also observed.

The OH-initiated atmospheric chemical reactions of polyfluorinated dibenzofurans and polychlorinated dibenzofurans: A comparative theoretical study.

Science.gov (United States)

Zeng, Xiaolan; Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

2017-02-01

The atmospheric chemical reactions of some polyfluorinated dibenzofurans (PFDFs) and polychlorinated dibenzofurans (PCDFs), initiated by OH radical, were investigated by performing theoretical calculations using density functional theory (DFT) and B3LYP/6-311++G(2df,p) method. The obtained results indicate that OH addition reactions of PFDFs and PCDFs occurring at C 1∼4 and C A sites are thermodynamic spontaneous changes and the branching ratio of the PF(C)DF-OH adducts is decided primarily by kinetic factor. The OH addition reactions of PFDFs taking place at fluorinated C 1∼4 positions are kinetically comparable with those occurring at nonfluorinated C 1∼4 positions, while OH addition reactions of PCDFs occurring at chlorinated C 1∼4 sites are negligible. The total rate constants of the addition reactions of PFDFs or PCDFs become smaller with consecutive fluorination or chlorination, and substituting at C 1 position has more adverse effects than substitution at other sites. The succedent O 2 addition reactions of PF(C)DF-OH adducts are thermodynamic nonspontaneous processes under the atmospheric conditions, and have high Gibbs free energies of activation (Δ r G ≠ ). The substituted dibenzofuranols are the primary oxidation products for PCDFs under the atmospheric conditions. However, other oxidative products may also be available for PFDFs besides substituted dibenzofuranols. Copyright © 2016 Elsevier Ltd. All rights reserved.

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).

Hydrogen addition reactions of aliphatic hydrocarbons in comets

Science.gov (United States)

Kobayashi, Hitomi; Watanabe, N.; Watanabe, Y.; Fukushima, T.; Kawakita, H.

2013-10-01

Comets are thought as remnants of early solar nebula. Their chemical compositions are precious clue to chemical and physical evolution of the proto-planetary disk. Some hydrocarbons such as C2H6, C2H2 and CH4 in comets have been observed by using near-infrared spectroscopy. Although the compositions of C2H6 were about 1% relative to the water in normal comets, there are few reports on the detection of C2H6 in ISM. Some formation mechanisms of C2H6 in ISM have been proposed, and there are two leading hypotheses; one is the dimerizations of CH3 and another is the hydrogen addition reactions of C2H2 on cold icy grains. To evaluate these formation mechanisms for cometary C2H6 quantitatively, it is important to search the C2H4 in comets, which is the intermediate product of the hydrogen addition reactions toward C2H6. However, it is very difficult to detect the C2H4 in comets in NIR (3 microns) regions because of observing circumstances. The hydrogen addition reactions of C2H2 at low temperature conditions are not well characterized both theoretically and experimentally. For example, there are no reports on the reaction rate coefficients of those reaction system. To determine the production rates of those hydrogen addition reactions, we performed the laboratory experiments of the hydrogenation of C2H2 and C2H4. We used four types of the initial composition of the ices: pure C2H4, pure C2H2, C2H2 on amorphous solid water (ASW) and C2H4 on ASW at three different temperatures of 10, 20, and 30K. We found 1) reactions are more efficient when there are ASW in the initial compositions of the ice; 2) hydrogenation of C2H4 occur more rapid than that of C2H2.

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.

Shock-induced hotspot formation and chemical reaction initiation in PETN containing a spherical void

International Nuclear Information System (INIS)

Shan, Tzu-Ray; Thompson, Aidan P

2014-01-01

We present results of reactive molecular dynamics simulations of hotspot formation and chemical reaction initiation in shock-induced compression of pentaerythritol tetranitrate (PETN) with the ReaxFF reactive force field. A supported shockwave is driven through a PETN crystal containing a 20 nm spherical void at a sub-threshold impact velocity of 2 km/s. Formation of a hotspot due to shock-induced void collapse is observed. During void collapse, NO 2 is the dominant species ejected from the upstream void surface. Once the ejecta collide with the downstream void surface and the hotspot develops, formation of final products such as N 2 and H 2 O is observed. The simulation provides a detailed picture of how void collapse and hotspot formation leads to initiation at sub-threshold impact velocities.

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.

Gas phase polymerization of propylene. Reaction kinetics and molecular weight distribution

NARCIS (Netherlands)

Meier, G.B.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

2001-01-01

Gas-phase polymerizations have been executed at different temperatures, pressures, and hydrogen concentrations using Me2Si[Ind]2ZrCl2 / methylaluminoxane / SiO2(Pennsylvania Quarts) as a catalyst. The reaction rate curves have been described by a kinetic model, which takes into account the initially

Protein synthesis during the initial phase of the temperature-induced bleaching response in Euglena gracilis

International Nuclear Information System (INIS)

Ortiz, W.

1990-01-01

Growing cultures of photoheterotrophic Euglena gracilis experience an increase in chlorophyll accumulation during the initial phase of the temperature-induced bleaching response suggesting an increase in the synthesis of plastid components at the bleaching temperature of 33 degree C. A primary goal of this work was to establish whether an increase in the synthesis of plastid proteins accompanies the observed increase in chlorophyll accumulation. In vivo pulse-labeling experiments with [ 35 S]sodium sulfate were carried out with cells grown at room temperature or at 33 degree C. The synthesis of a number of plastid polypeptides of nucleocytoplasmic origin, including some presumably novel polypeptides, increased in cultures treated for 15 hours at 33 degree C. In contrast, while synthesis of thylakoid proteins by the plastid protein synthesis machinery decreased modestly, synthesis of the large subunit of the enzyme ribulosebisphosphate carboxylase was strongly affected at the elevated temperature. Synthesis of novel plastid-encoded polypeptides was not induced at the bleaching temperature. It is concluded that protein synthesis in plastids declines during the initial phase of the temperature response in Euglena despite an overall increase in cellular protein synthesis and an increase in chlorophyll accumulation per cell

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.

Chlorine Dioxide-Iodide-Methyl Acetoacetate Oscillation Reaction Investigated by UV-Vis and Online FTIR Spectrophotometric Method

Directory of Open Access Journals (Sweden)

Laishun Shi

2012-01-01

Full Text Available In order to study the chemical oscillatory behavior and mechanism of a new chlorine dioxide-iodide ion-methyl acetoacetate reaction system, a series of experiments were done by using UV-Vis and online FTIR spectrophotometric method. The initial concentrations of methyl acetoacetate, chlorine dioxide, potassium iodide, and sulfuric acid and the pH value have great influence on the oscillation observed at wavelength of 289 nm. There is a preoscillatory or induction period, and the amplitude and the number of oscillations are associated with the initial concentration of reactants. The equations for the triiodide ion reaction rate changing with reaction time and the initial concentrations in the oscillation stage were obtained. Oscillation reaction can be accelerated by increasing temperature. The apparent activation energies in terms of the induction period and the oscillation period were 26.02 KJ/mol and 17.65 KJ/mol, respectively. The intermediates were detected by the online FTIR analysis. Based upon the experimental data in this work and in the literature, a plausible reaction mechanism was proposed for the oscillation reaction.

Reductive and oxidative reactions with inorganic colloids in aqueous solution initiated by ultrasound

International Nuclear Information System (INIS)

Mulvaney, P.C.; Sostaric, J.Z.; Ashokkumar, M.; Grieser, F.

1998-01-01

Full text: The absorption of ultrasound in an aqueous solution can lead to the formation of H and OH radicals which can act as redox species or react with solutes to produce secondary radicals which themselves may participate in electron transfer reactions. The radical formation occurs through the growth then rapid collapse of microbubbles a process that produces localised hot spots with an internal temperature of the order of 5000 K. We have examined two colloidal systems one involving the reductive dissolution of MnO 2 colloids and the other the oxidative dissolution of CdS colloids. In the case of MnO 2 dissolution we found that the reduction of the colloidal metal oxide was considerably enhanced in the presence of aliphatic alcohols in solution and the longer the alkyl chain length on the alcohol the greater its effect. The dissolution of CdS colloids which we ascribe to the reaction of H 2 O 2 and O 2 - with the metal sulfide lo yield Cd 2+ and S could be significantly retarded by the presence of excess S 2- in solution. The mechanisms involved in these two dissolution processes will he presented. Our results clearly show that sonochemical reactions are quite efficient in colloidal solutions and this fact needs to be considered when using sonication to disperse colloidal material in solution, a common practice among colloid chemists

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)

Study of aniline polymerization reactions through the particle size formation in acidic and neutral medium

Science.gov (United States)

Aribowo, Slamet; Hafizah, Mas Ayu Elita; Manaf, Azwar; Andreas

2018-04-01

In the present paper, we reported particle size kinetic studies on the conducting polyaniline (PANI) which synthesized through a chemical oxidative polymerization technique from aniline monomer. PANI was prepared using ammonium persulfate (APS) as oxidizing agent which carried out in acidic and neutral medium at various batch temperatures of respectively 20, 30 and 50 °C. From the studies, it was noticed that the complete polymerization reaction progressed within 480 minutes duration time. The pH of the solution during reaction kinetic reached values 0.8 - to 1.2 in acidic media, while in the neutral media the pH value reached values 3.8 - 4.9. The batch temperature controlled the polymerization reaction in which the reaction progressing, which followed by the temperature rise of solution above the batch temperature before settled down to the initial temperature. An increment in the batch temperature gave highest rise in the solution temperature for the two media which cannot be more than 50 °C. The final product of polymerization reaction was PANI confirmed by Fourier Transform Infra-Red (FTIR) spectrophotometer for molecule structure identification. The averages particle size of PANI which carried out in the two different media is evidently similar in the range 30 - 40 μm and insensitive to the batch temperature. However, the particle size of PANI which obtained from the polymerization reaction at a batch temperature of 50 °C under acidic condition reached ˜53.1 μm at the tip of the propagation stage which started in the first 5 minutes. The size is obviously being the largest among the batch temperatures. Whereas, under neutral condition the particle size is much larger which reached the size 135 μm at the batch temperature of 20 °C. It is concluded that the particle size formation during the polymerization reaction being one of the important parameter to determine particle growing of polymer which indicated the reaction kinetics mechanism of synthesize

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

Defects level evaluation of LiTiZn ferrite ceramics using temperature dependence of initial permeability

Science.gov (United States)

Malyshev, A. V.; Petrova, A. B.; Sokolovskiy, A. N.; Surzhikov, A. P.

2018-06-01

The method for evaluating the integral defects level and chemical homogeneity of ferrite ceramics based on temperature dependence analysis of initial permeability is suggested. A phenomenological expression for the description of such dependence was suggested and an interpretation of its main parameters was given. It was shown, that the main criterion of the integral defects level of ferrite ceramics is relation of two parameters correlating with elastic stress value in a material. An indicator of structural perfection can be a maximum value of initial permeability close to Curie point as well. The temperature dependences of initial permeability have analyzed for samples sintered in laboratory conditions and for the ferrite industrial product. The proposed method allows controlling integral defects level of the soft ferrite products and has high sensitivity compare to typical X-ray methods.

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.

A Surface Temperature Initiated Closure (STIC) for surface energy balance fluxes

DEFF Research Database (Denmark)

Mallick, Kaniska; Jarvis, Andrew J.; Boegh, Eva

2014-01-01

The use of Penman–Monteith (PM) equation in thermal remote sensing based surface energy balance modeling is not prevalent due to the unavailability of any direct method to integrate thermal data into the PM equation and due to the lack of physical models expressing the surface (or stomatal......) and boundary layer conductances (gS and gB) as a function of surface temperature. Here we demonstrate a new method that physically integrates the radiometric surface temperature (TS) into the PM equation for estimating the terrestrial surface energy balance fluxes (sensible heat, H and latent heat, λ......E). The method combines satellite TS data with standard energy balance closure models in order to derive a hybrid closure that does not require the specification of surface to atmosphere conductance terms. We call this the Surface Temperature Initiated Closure (STIC), which is formed by the simultaneous solution...

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.

Dynamic Fracture Initiation Toughness at Elevated Temperatures With Application to the New Generation of Titanium Aluminide Alloys. Chapter 8

Science.gov (United States)

Shazly, Mostafa; Prakash, Vikas; Draper, Susan; Shukla, Arun (Editor)

2006-01-01

Recently, a new generation of titanium aluminide alloy, named Gamma-Met PX, has been developed with better rolling and post-rolling characteristics. I'revious work on this alloy has shown the material to have higher strengths at room and elevated temperatures when compared with other gamma titanium aluminides. In particular, this new alloy has shown increased ductility at elevated temperatures under both quasi-static and high strain rate uniaxial compressive loading. However, its high strain rate tensile ductility at room and elevated temperatures is limited to approx. 1%. In the present chapter, results of a study to investigate the effects of loading rate and test temperature on the dynamic fracture initiation toughness in Gamma-Met PX are presented. Modified split Hopkinson pressure bar was used along with high-speed photography to determine the crack initiation time. Three-point bend dynamic fracture experiments were conducted at impact speeds of approx. 1 m/s and tests temperatures of up-to 1200 C. The results show that thc dynamic fracture initiation toughness decreases with increasing test temperatures beyond 600 C. Furthermore, thc effect of long time high temperature air exposure on the fracture toughness was investigated. The dynamic fracture initiation toughness was found to decrease with increasing exposure time. The reasons behind this drop are analyzed and discussed.

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

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

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.

Reaction analysis of initial oxidation of silicon by UV-light-excited ozone and the application to rapid and uniform SiO2 film growth

International Nuclear Information System (INIS)

Tosaka, Aki; Nonaka, Hidehiko; Ichimura, Shingo; Nishiguchi, Tetsuya

2007-01-01

UV-light-excited O 3 prepared by irradiation of nearly 100% pure O 3 with a KrF excimer laser (λ=248 nm, irradiated area=30x10 mm 2 ) was utilized for low-temperature Si oxidation. The initial oxidation rate was determined, and the activation energy was shown to be almost zero (0.049 eV). To clarify the optimum oxidation conditions, the dependence of the SiO 2 film growth rate on the total photon number and the photon density was investigated. The evolution of O 3 density after UV-light irradiation was experimentally measured, and the O( 1 D) density change is discussed. O( 1 D) density changes are successfully explained by using a second-order reaction model, indicating that a pulse supply of oxygen atoms is essential in the initial oxidation process. The uniform oxidation of 8 in. Si wafer has been carried out using a wafer-transfer type chamber by irradiating the wafer with KrF excimer laser light expanded linearly to the wafer width by a concave lens

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.

Lin's theory of flux and nuclear reactions

International Nuclear Information System (INIS)

Ping-Wha Lin

2002-01-01

Mathematical development of Lin's theory of flux is presented. Based on the Theory, when a chemical reaction system is subjected to a high time rate of temperature change, it changes from equilibrium to non-equilibrium conditions. It is proved mathematically that, when a gas system is subjected to a high time rate of temperature increase, the activities of particles (molecules, atoms or nuclei, and electrons) are increased: the particles are accelerated; frequencies and amplitudes of electron and atomic vibrations in a molecule increased; average kinetic energy of the particles increased; atomic bonds are ruptured; electrons are caused to leave their orbits. If most or all of the electrons leave their orbits, the gas fluid becomes plasma, which is very active chemically. The acceleration of nuclei in the dynamic condition can lead to nuclear reactions. In the pilot plant studies conducted at Research Triangle, NC, USA, for SO 2 conversion to SO 3 by rapid heating, a 10-ft high vertically fired combustor (VFC) was used. Air containing 0.5% SO 2 is forced continuously through the VFC, where it is heated by burners for conversion of SO 2 to SO 3 . During the idle period of operation, no external heat is added to the system by turning off the burners. It is observed that, as the air passing through the VFC during the idle period of sixteen hours, the temperature of the flowing air consistently rises up rapidly from ambient temperature (90 deg F) at inlet of the VFC to an average temperature as high as 582 deg F (in the range of 840 deg F to 455 deg F) at one section of the VFC, an increase of about 500 deg F. The air flow temperature increase of such large magnitude and long duration clearly indicates that nuclear reactions are present in VFC. It is also found that the water vapour in the air stream has completely disappeared in the VFC, for no sulphuric acid formation resulting from the reaction of water and SO 3 is detected there. Presumably, the water vapour in the

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.

Production of nanocrystalline metal powders via combustion reaction synthesis

Science.gov (United States)

Frye, John G.; Weil, Kenneth Scott; Lavender, Curt A.; Kim, Jin Yong

2017-10-31

Nanocrystalline metal powders comprising tungsten, molybdenum, rhenium and/or niobium can be synthesized using a combustion reaction. Methods for synthesizing the nanocrystalline metal powders are characterized by forming a combustion synthesis solution by dissolving in water an oxidizer, a fuel, and a base-soluble, ammonium precursor of tungsten, molybdenum, rhenium, or niobium in amounts that yield a stoichiometric burn when combusted. The combustion synthesis solution is then heated to a temperature sufficient to substantially remove water and to initiate a self-sustaining combustion reaction. The resulting powder can be subsequently reduced to metal form by heating in a reducing gas environment.

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.

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.

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

International Nuclear Information System (INIS)

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

1998-01-01

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

Kinetics of Waterborne Alkyd/Acrylic Hybrid Resin Free Radical Polymerization by Two Systems of Redox and Thermal Initiators

Directory of Open Access Journals (Sweden)

shirin Madadi

2012-12-01

Full Text Available Kinetics of radical polymerizations of waterborne alkyd/acrylic hybrid resin via batch mini-emulsion technique was studied using redox initiators (TBHP/Fe2+/EDTA/AsAc  and  TBHP/Fe2+/EDTA/SFS at relatively low temperatures and thermal initiators (BPO, KPS and AIBN at higher temperatures to seek the most suitable initiator system. At the end of all reactions the unreacted monomer content was reduced using post-polymerization technique; consequently, leading to increased monomer conversion and flm formation with improved properties. The kinetics of mini-emulsion polymerization showed that in all redox initiator systems (Fe2+ catalyst + EDTA chelating agent, the radials are produced at relatively low temperature with more effcient control of the reactor temperature. It was found that at 45°C TBHP/Fe2+/EDTA/SFS redox initiator system leads to 98% monomer conversion, a much higher rate than that of systems involved thermal initiators.

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)

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.

Thermal decomposition pathways of hydroxylamine: theoretical investigation on the initial steps.

Science.gov (United States)

Wang, Qingsheng; Wei, Chunyang; Pérez, Lisa M; Rogers, William J; Hall, Michael B; Mannan, M Sam

2010-09-02

Hydroxylamine (NH(2)OH) is an unstable compound at room temperature, and it has been involved in two tragic industrial incidents. Although experimental studies have been carried out to study the thermal stability of hydroxylamine, the detailed decomposition mechanism is still in debate. In this work, several density functional and ab initio methods were used in conjunction with several basis sets to investigate the initial thermal decomposition steps of hydroxylamine, including both unimolecular and bimolecular reaction pathways. The theoretical investigation shows that simple bond dissociations and unimolecular reactions are unlikely to occur. The energetically favorable initial step of decomposition pathways was determined as a bimolecular isomerization of hydroxylamine into ammonia oxide with an activation barrier of approximately 25 kcal/mol at the MPW1K level of theory. Because hydroxylamine is available only in aqueous solutions, solvent effects on the initial decomposition pathways were also studied using water cluster methods and the polarizable continuum model (PCM). In water, the activation barrier of the bimolecular isomerization reaction decreases to approximately 16 kcal/mol. The results indicate that the bimolecular isomerization pathway of hydroxylamine is more favorable in aqueous solutions. However, the bimolecular nature of this reaction means that more dilute aqueous solution will be more stable.

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

Topics in the numerical simulation of high temperature flows

International Nuclear Information System (INIS)

Cheret, R.; Dautray, R.; Desgraz, J.C.; Mercier, B.; Meurant, G.; Ovadia, J.; Sitt, B.

1984-06-01

In the fields of inertial confinement fusion, astrophysics, detonation, or other high energy phenomena, one has to deal with multifluid flows involving high temperatures, high speeds and strong shocks initiated e.g. by chemical reactions or even by thermonuclear reactions. The simulation of multifluid flows is reviewed: first are Lagrangian methods which have been successfully applied in the past. Then we describe our experience with newer adaptive mesh methods, originally designed to increase the accuracy of Lagrangian methods. Finally, some facts about Eulerian methods are recalled, with emphasis on the EAD scheme which has been recently extended to the elasto-plastic case. High temperature flows is then considered, described by the equations of radiation hydrodynamics. We show how conservation of energy can be preserved while solving the radiative transfer equation via the Monte Carlo method. For detonation, some models, introduced to describe the initiation of detonation in heterogeneous explosives. Finally we say a few words about instability of these flows

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

Energy Technology Data Exchange (ETDEWEB)

Gerber, T.; Radi, P.; Knopp, G.; Tulej, M.

2007-07-01

This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Paul Scherrer Institute PSI in Switzerland on the quantitative description of ignition. processes and the influence of peroxy radicals that determine ignition and speciation of the intermediates initially present and, thereby, the progress of subsequent reactions. The authors note that for the preparation of peroxy radicals, a dedicated molecular beam apparatus has been built by the PSI's 'Molecular Dynamics' group. A novel radical source is operational. In many cases, specific radicals can be prepared with high selectivity. A description of flame chemistry is being worked on that can reliably predict the speciation of intermediate products during ignition. Laser-based measurement techniques are being applied at PSI to measure the static and dynamic properties of alkyl peroxy radicals in order to accurately describe their reaction behaviour in combustion processes. A dedicated synchrotron beam line is installed at the Swiss Light Source (SLS) that extends the available range of spectroscopic measurements into the VUV (vacuum-ultraviolet) wavelength domain. The results obtained are presented and discussed.

The effect of initial temperature on flame acceleration and deflagration-to-detonation transition phenomenon

International Nuclear Information System (INIS)

Ciccarelli, G.; Boccio, J.L.; Ginsberg, T.; Finfrock, C.; Gerlach, L.; Tagawa, H.; Malliakos, A.

1998-05-01

The High-Temperature Combustion Facility at BNL was used to conduct deflagration-to-detonation transition (DDT) experiments. Periodic orifice plates were installed inside the entire length of the detonation tube in order to promote flame acceleration. The orifice plates are 27.3-cm-outer diameter, which is equivalent to the inner diameter of the tube, and 20.6-cm-inner diameter. The detonation tube length is 21.3-meters long, and the spacing of the orifice plates is one tube diameter. A standard automobile diesel engine glow plug was used to ignite the test mixture at one end of the tube. Hydrogen-air-steam mixtures were tested at a range of temperatures up to 650K and at an initial pressure of 0.1 MPa. In most cases, the limiting hydrogen mole fraction which resulted in DDT corresponded to the mixture whose detonation cell size, λ, was equal to the inner diameter of the orifice plate, d (e.g., d/λ=1). The only exception was in the dry hydrogen-air mixtures at 650K where the DDT limit was observed to be 11 percent hydrogen, corresponding to a value of d/λ equal to 5.5. For a 10.5 percent hydrogen mixture at 650K, the flame accelerated to a maximum velocity of about 120 mIs and then decelerated to below 2 mIs. By maintaining the first 6.1 meters of the vessel at the ignition end at 400K, and the rest of the vessel at 650K, the DDT limit was reduced to 9.5 percent hydrogen (d/λ=4.2). This observation indicates that the d/λ=1 DDT limit criteria provides a necessary condition but not a sufficient one for the onset of DDT in obstacle laden ducts. In this particular case, the mixture initial condition (i.e., temperature) resulted in the inability of the mixture to sustain flame acceleration to the point where DDT could occur. It was also observed that the distance required for the flame to accelerate to the point of detonation initiation, referred to as the run-up distance, was found to be a function of both the hydrogen mole fraction and the mixture initial

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...

On the Reaction of 1,3-Diphenylisobenzofuran and (2-Iodoethynyl(phenyliodonium Triflate. A Unique Case of Oxygen Transfer from the Diels-Alder Adduct to the Diene

Directory of Open Access Journals (Sweden)

Mercè Font-Bardia

2012-07-01

Full Text Available Reaction of 1,3-diphenylisobenzofuran (DPIBF with 2-(iodoethynyl(phenyl-iodonium triflate at room temperature gave the expected Diels-Alder adduct, but using an excess of DFIBF (2 equiv. and performing the reaction at 55 °C or heating at this temperature during the concentration stage, the initial orange solution or product mixture became dark brown and the products 1,2-phenylene-1,2-bis(phenylmethanone and 2-(3-iodo-1,4-diphenylnaphthyl(phenyliodonium triflate were obtained, which suggests an oxygen transfer between DPIBF and the initial adduct.

Crack initiation at high temperature on an austenitic stainless steel; Amorcage de fissure a haute temperature dans un acier inoxydable austenitique

Energy Technology Data Exchange (ETDEWEB)

Laiarinandrasana, L

1994-11-25

The study deals with crack initiation at 600 and 650 degrees Celsius, on an austenitic stainless steel referenced by Z2 CND 17 12. The behaviour laws of the studied plate were update in comparison with existing data. Forty tests were carried out on CT specimens, with continuous fatigue with load or displacement controlled, pure creep, pure relaxation, creep-fatigue and creep-relaxation loadings. The practical initiation definition corresponds to a small crack growth of about the grain size. The time necessary for the crack to initiate is predicted with fracture mechanics global and local approaches, with the helps of microstructural observations and finite elements results. An identification of a `Paris`law` for continuous cyclic loading and of a unique correlation between the initiation time and C{sup *}{sub k} for creep tests was established. For the local approach, crack initiation by creep can be interpreted as the reaching of a critical damage level, by using a damage incremental rule. For creep-fatigue tests, crack growth rates at initiation are greater than those of Paris`law for continuous fatigue. A calculation of a transition time between elastic-plastic and creep domains shows that crack initiation can be interpreted whether by providing Paris`law with an acceleration term when the dwell period is less than the transition time, or by calculating a creep contribution which relies on C{sup *}{sub k} parameter when the dwell period and/or the initiation times are greater than the transition time. Creep relaxation tests present crack growth rates at initiation which are less than those for `equivalent` creep-fatigue tests. These crack growth rates when increasing hold time, but also when temperature decreases. Though, for hold times which are important enough and at lower temperature, there is no effect of the dwell period insofar as crack growth rate is equal to continuous fatigue Paris law predicted ones. (Abstract Truncated)

Synthesis of Al-5Ti-1B Refiner by Melt Reaction Method

Directory of Open Access Journals (Sweden)

LI He

2017-02-01

Full Text Available Al-5Ti-1B refiner was successfully prepared by melt reaction method. Through the thermodynamics calculation, the initial reaction temperature was determined. The influence of reaction temperature on microstructure and absorption rate of the alloy was investigated. The phase and microstructure of the alloy were observed by X-ray diffraction, scanning electron microscope and energy dispersive spectrometer. The Al-5Ti-1B refiner was extruded at high temperature to wire with the diameter of 9.5mm, and then the refinement experiment was carried out on pure aluminium. The results indicate that the refiner consists of TiB2, TiAl3 and α-Al, and the microstructure prepared at 850℃ is the optimum and the absorption rate of Ti and B matches the best. The TiAl3 and TiB2 phases distribute homogeneously in the matrix after extrusion. When adding 0.2%(mass fraction of Al-5Ti-1B refiner, the grain size of pure aluminium reduces from 3.99mm to 0.45mm.

Influence of temperature on spring flight initiation for southwestern ponderosa pine bark beetles (Coleoptera: Curculionidae, Scolytinae)

Science.gov (United States)

M. L. Gaylord; K. K. Williams; R. W. Hofstetter; J. D. McMillin; T. E. Degomez; M. R. Wagner

2008-01-01

Determination of temperature requirements for many economically important insects is a cornerstone of pest management. For bark beetles (Coleoptera: Curculionidae, Scolytinae), this information can facilitate timing of management strategies. Our goals were to determine temperature predictors for flight initiation of three species of Ips bark beetles...

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

A kinetic study on non-catalytic reactions in hydroprocessing Boscan crude oil

Energy Technology Data Exchange (ETDEWEB)

A. Marafi; E. Kam; A. Stanislaus [Kuwait Institute for Scientific Research, Safat (Kuwait). Petroleum Refining Department, Petroleum Research and Studies Center

2008-08-15

Non-catalytic hydrothermal cracking reactions are known to associate with catalytic hydrocracking reactions. In a recent study on hydroprocessing of Boscan crude over a specific catalyst system containing three distinct catalysts, it was found that hydrodesulfurization (HDS) and hydrodemetallation (HDM) reactions continued even when the catalyst is severely deactivated. Since the reactor was packed with considerable amount of inert material besides the three catalysts, it will be advantage to determine if the inert materials can also facilitate hydroprocessing reactions. A series of kinetic experiments for the inert particles was undertaken under different space velocity and temperature conditions. The extent of catalytic and non-catalytic hydroprocessing reactions was assessed. Through statistical analysis, the initial reaction rate constant, reaction order and activation energy for various hydroprocessing reactions were then determined. The absolute average deviations (AAD) of the kinetics values obtained for inert materials are less than 10%. 25 refs., 7 figs., 4 tabs.

The vapour phase deposition of boron on titanium by the reaction between gaseous boron trichloride and titanium metal. Final report

International Nuclear Information System (INIS)

Cameron, D.J.; Shelton, R.A.J.

1965-03-01

The reaction, between boron trichloride vapour and titanium has been investigated in the temperature range 200 - 1350 deg. C. It has been found that an initial reaction leads to the formation of titanium tetrachloride and the deposition of boron on titanium, but that except for reactions between 900 and 1000 deg. C, the system is complicated by the formation of lower titanium chlorides due to secondary reactions between the titanium and titanium tetrachloride

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....

HBr Formation from the Reaction between Gas-phase Bromine Atom and Vibrationally Excited Chemisorbed Hydrogen Atoms on a Si(001)-(2 x 1) Surface

International Nuclear Information System (INIS)

Ree, J.; Yoon, S. H.; Park, K. G.; Kim, Y. H.

2004-01-01

We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 x 1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond (vHSi = 0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond

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.

Studies on the catalysts for coal liquefaction. ; Kinetic discussion in initial stage of coal liquefaction. Sekitan ekikayo shokubai ni kansuru kenkyu. ; Sekitan ekika shoki dankai no sokudoronteki kosatsu

Energy Technology Data Exchange (ETDEWEB)

Muraoka, T; Ikenaga, N; Oda, H; Yokokawa, C [Kansai University, Osaka (Japan). Faculty of Engineering

1990-11-29

Discussions were given on features of various kinds of coal liquefaction catalysts exhibited by them in hydrocracking of coal (Taiheiyo coal), and particularly on selectivity of the reaction in its initial stage. Four kinds of catalysts were tested: Adkins catalyst which is an oxide of copper and chromium, Fe2O3+S, Mo-TiO2 and MoS3-Al2O3. Three grams of coal and 0.3 gram each of the catalysts were charged into an autoclave reactor and experiment was conducted under an initial hydrogen pressure of 10 MPa, temperatures from 653 K to 693 K and for durations of 0 to 120 minutes to derive apparent reaction rate constants. The MoS3-Al2O3 catalyst has promoting the reaction apparently in the primary reaction at any temperature, while the other catalysts had the rate constants varied in the initial and the later stages. It was recognized that the temperature dependence of rate constants varies considerably according to the types of catalyst. Particularly the MoO3-TiO3 catalyst has small temperature dependence in the rate constants, and high molecular weight reducing power. 3 refs., 4 figs., 3 tabs.

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.

The stereodynamics of photon-initiated bimolecular reactions

International Nuclear Information System (INIS)

Hughes, D.W.

1999-01-01

This thesis concerns the stereodynamics of the product state resolved reaction: H( 2 S) + CO 2 → (HOCO) → OH(X 2 Π Ω ; v, N, f) + CO( 1 Σ + ). Translationally excited hydrogen atoms were generated from HBr and HCl precursor molecules, via polarised laser photolysis, and the Doppler lineshapes of nascent OH products were monitored using polarised laser radiation. Four different OH product channels were investigated at a collision energy of 2.5 eV, and two OH product channels were studied at a collision energy of 1.8 eV. Three main sources of product state specific information were recovered from the Doppler profiles: Differential cross-sections (DCS); Product translational energy distributions (P(f)); Product rotational angular momentum distributions. Product state specific differential cross-sections (generated through collisions at 2.5 eV) suggest that OH( 2 Π 1/2 ) products may be produced through a more 'direct' route than OH( 2 Π 3/2 ) products. Differential cross-sections recorded for OH products generated through collisions at 1.8 eV, however, imply that neither OH spin-orbit state is populated through a 'direct' mechanism. The P(f t ) distributions for all OH product channels exhibit more product translational excitation than would be expected on the basis of phase space theory. This may imply either that the lifetimes of the collision complexes are short with respect to the timescale for intramolecular internal energy randomisation, or that there are significant exit channel interactions. The polarisation of the OH rotational angular momentum distribution is seen to be highly sensitive to the rotational and spin-orbit state of the OH products, but less sensitive to the collision energy and lambda-doublet state of the OH product. This thesis outlines the scope of present day experimental stereodynamical studies of gas-phase reactions (chapter 1), the theory of vector correlations in photoninitiated bimolecular reactions (chapter 2) and the

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.

Volatile emission in dry seeds as a way to probe chemical reactions during initial asymptomatic deterioration.

Science.gov (United States)

Mira, Sara; Hill, Lisa M; González-Benito, M Elena; Ibáñez, Miguel Angel; Walters, Christina

2016-03-01

The nature and kinetics of reactions in dry seeds determines how long the seeds survive. We used gas chromatography to assay volatile organic compounds (VOCs) emitted from seeds of three unrelated species as a means to non-invasively probe chemical changes during very dry, dry, and humid storage (seeds were dried to 5.5, 33, and 75% relative humidity at room temperature). VOCs emitted from seeds stored in humid conditions reflected fermentation-type reactions, with methanol and ethanol being predominant in Lactuca sativa and Carum carvi, and acetaldehyde and acetone being predominant in Eruca vesicaria. Dried C. carvi seeds continued to emit fermentation-type products, although at slower rates than the seeds stored in humid conditions. In contrast, drying caused a switch in VOC emission in L. sativa and E. vesicaria seeds towards higher emission of pentane and hexanal, molecules considered to be byproducts from the peroxidation of polyunsaturated fatty acids. Longevity correlated best with the rate of fermentation-type reactions and appeared unrelated to the rate of lipid peroxidation. Emission of VOCs decreased when seed species were mixed together, indicating that seeds adsorbed VOCs. Adsorption of VOCs did not appear to damage seeds, as longevity was not affected in seed mixtures. Collectively, the study shows similarity among species in the types of reactions that occur in dry seeds, but high diversity in the substrates, and hence the byproducts, of the reactions. Moreover, the study suggests that the most abundant VOCs arise from degradation of storage reserves within seed cells, and that these reactions and their byproducts are not, in themselves, damaging. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology.

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

An Investigation of Porous Structure of TiNi-Based SHS-Materials Produced at Different Initial Synthesis Temperatures

Science.gov (United States)

Khodorenko, V. N.; Anikeev, S. G.; Kokorev, O. V.; Yasenchuk, Yu. F.; Gunther, V. É.

2018-02-01

An investigation of structural characteristics and behavior of TiNi-based pore-permeable materials manufactured by the methods of selfpropagating high-temperature synthesis (SHS) at the initial synthesis temperatures T = 400 and 600°C is performed. It is shown that depending on the temperature regime, the resulting structure and properties of the material can differ. It is found out that the SHS-material produced at the initial synthesis temperature T = 400°C possesses the largest number of micropores in the pore wall surface structure due to a high phase inhomogeneity of the alloy. The regime of structure optimization of the resulting materials is described and the main stages of formation of the pore wall microporous surfaces are revealed. It is demonstrated that after optimization of the surface structure of a TiNi-based fine-pore alloy by its chemical etching, the fraction of micropores measuring in size less than 50 nm increased from 59 to 68%, while the number of pores larger than 1 μm increased twofold from 11 to 22%. In addition, peculiar features of interaction between certain cell cultures with the surface of the SHS-material manufactured at different initial synthesis temperatures are revealed. It is found out that the dynamics of the cell material integration depends on the pore wall surface morphology and dimensions of macropores.

The Effect of Temperature and Ionic Strength on the Oxidation of Iodide by Iron(III): A Clock Reaction Kinetic Study

Science.gov (United States)

Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

2012-01-01

A laboratory exercise has recently been reported in which the students use the initial rates method based on the clock reaction approach to deduce the rate law and propose a reaction mechanism for the oxidation of iodide by iron(III) ions. The same approach is used in the exercise proposed herein; the students determine the dependence of the…

Radical Initiated Hydrosilylation on Silicon Nanocrystal Surfaces: An Evaluation of Functional Group Tolerance and Mechanistic Study.

Science.gov (United States)

Yang, Zhenyu; Gonzalez, Christina M; Purkait, Tapas K; Iqbal, Muhammad; Meldrum, Al; Veinot, Jonathan G C

2015-09-29

Hydrosilylation is among the most common methods used for modifying silicon surface chemistry. It provides a wide range of surface functionalities and effective passivation of surface sites. Herein, we report a systematic study of radical initiated hydrosilylation of silicon nanocrystal (SiNC) surfaces using two common radical initiators (i.e., 2,2'-azobis(2-methylpropionitrile) and benzoyl peroxide). Compared to other widely applied hydrosilylation methods (e.g., thermal, photochemical, and catalytic), the radical initiator based approach is particle size independent, requires comparatively low reaction temperatures, and yields monolayer surface passivation after short reaction times. The effects of differing functional groups (i.e., alkene, alkyne, carboxylic acid, and ester) on the radical initiated hydrosilylation are also explored. The results indicate functionalization occurs and results in the formation of monolayer passivated surfaces.

Method for solving the problem of nonlinear heating a cylindrical body with unknown initial temperature

Science.gov (United States)

Yaparova, N.

2017-10-01

We consider the problem of heating a cylindrical body with an internal thermal source when the main characteristics of the material such as specific heat, thermal conductivity and material density depend on the temperature at each point of the body. We can control the surface temperature and the heat flow from the surface inside the cylinder, but it is impossible to measure the temperature on axis and the initial temperature in the entire body. This problem is associated with the temperature measurement challenge and appears in non-destructive testing, in thermal monitoring of heat treatment and technical diagnostics of operating equipment. The mathematical model of heating is represented as nonlinear parabolic PDE with the unknown initial condition. In this problem, both the Dirichlet and Neumann boundary conditions are given and it is required to calculate the temperature values at the internal points of the body. To solve this problem, we propose the numerical method based on using of finite-difference equations and a regularization technique. The computational scheme involves solving the problem at each spatial step. As a result, we obtain the temperature function at each internal point of the cylinder beginning from the surface down to the axis. The application of the regularization technique ensures the stability of the scheme and allows us to significantly simplify the computational procedure. We investigate the stability of the computational scheme and prove the dependence of the stability on the discretization steps and error level of the measurement results. To obtain the experimental temperature error estimates, computational experiments were carried out. The computational results are consistent with the theoretical error estimates and confirm the efficiency and reliability of the proposed computational scheme.

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

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

Science.gov (United States)

Bulut, Niyazi; Kłos, Jacek; Roncero, Octavio

2015-06-07

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

The DARPA manufacturing initiative in high temperature superconductivity

International Nuclear Information System (INIS)

Adams, K.R.

1989-01-01

The Defense Advanced Research Projects Agency (DARPA) has a very aggressive Technology Base program in high temperature superconductivity. This program is expected to provide the basis for a specialized set of military products - passive microwave and millimeter wave devices - within the next three years. In order to get these high leverage products into military systems, a manufacturing base must be developed for HTSC components. A plan for DARPA in HTSC manufacturing is directly coupled with the ongoing DARPA materials and device oriented R and D program. In essence, this plan recommends a three phased effort: 1. Phase I (two years); Fund companies through R and D contracts for specialized HTSC components; prepare a detailed plan and develop an HTSC consortium. 2. Phase II (six years): Establish an HTSC Sematech initiative for electronic applications, including active devices. 3. Phase III (optional): Continue the HTSC Sematech with emphasis on high power applications

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

Report on thermic effects in the study of the control and propagation of nuclear reactions

International Nuclear Information System (INIS)

Naudet, R.

It is very likely that nuclear reactions in natural reactors are governed by temperature, chiefly as a result of the moderation rate when the water density is altered. Since reactors operate under high pressure, with supercritical water, high temperatures (at least 350 to 400 0 C in some instances) are required in order to stabilize the reactors. Some typical calculations are shown in order to illustrate the changes in the control temperature during irradiation. The speed and, therefore, the duration of reactions is determined by the need to maintain the necessary temperature required for criticality, with heat dissipation conditions taken into account. Apparent measured durations are compatible with heat dissipation by simple conduction. However, it is likely that convection currents exist, and that their effects are superimposed on those of simple conduction. Reaction propagation must also be taken into consideration since criticality cannot be realized simultaneously at every point. The presence of impurities such as gadolinium or samarium in the mineral ore allows reactions to propagate in initially subcritical increments, through progressive breakdown of the impurities by means of neutronic diffusion. However, it has been shown that this phenomenon is seriously affected by thermic effects. Typical calculations are presented. Results clearly depend on temperature distribution hypotheses; sufficient thermic coupling can totally inhibit reaction propagation. It is concluded that, if convection currents are present, propagation is favored inversely with respect to the currents, and therefore a priori downstream of the reactors. 6 figures

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

Radiation-Initiated Chlorination of 1, 2-Dichloroethane

Energy Technology Data Exchange (ETDEWEB)

Danno, A.; Abe, T.; Washino, M.; Souda, T.; Shimada, K. [Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy Research Institute, Watanuki-machi, Takasaki-shi, Gunma-ken (Japan)

1969-12-15

Radiation-initiated chlorination of 1,2-dichloroethane was carried out with a batch system to study the chlorination reaction in the laboratory and also with a flow system to obtain information on its scale-up. It was found that the direct chlorination of 1,2-dichloroethane in the presence of gamma radiation takes place by a free-radical chain reaction with a high G-value of the order of 10{sup 5}. Successive chlorination of 1,2-dichloroethane gives 1,1, 2-trichloroethane, 1,1,1, 2- and 1,1, 2, 2-tetrachloroethane, pentachloroethane and hexachloroethane. No products other than these polychloro ethanes were detected. The composition of the reaction products depends on the degree of chlorination; it is independent of the dose rate and the chlorine feed rate. A promising application of this process is to produce trichloroethylene and perchloroethylene by thermal dehydrochlorination of a mixture of tetrachloroethane and pentachloroethane. The optimum conditions of producing these compounds with high yields depend on the feed rate of 1, 2-dichloroethane and chlorine gas, the dose rate and the reaction temperature. A pilot experimental facility with a 2-litre reaction vessel has been completed and is now in operation. (author)

Study of initial stage in coal liquefaction. Increase in oil yield with suppression of retrogressive reaction during initial stage; Ekika hanno no shoki katei ni kansuru kenkyu. 1.

Energy Technology Data Exchange (ETDEWEB)

Uesugi, K.; Kanaji, M.; Kaneko, T.; Shimasaki, K. [Nippon Brown Coal Liquefaction Co. Ltd., Tokyo (Japan)

1996-10-28

For the coal liquefaction, improvement of liquefaction conditions and increase of liquefied oil yield are expected by suppressing the recombination through rapid stabilization of pyrolytic radicals which are formed at the initial stage of liquefaction. Two-stage liquefaction combining prethermal treatment and liquefaction was performed under various conditions, to investigate the effects of reaction conditions on the yields and properties of products as well as to increase liquefied oil yield. Consequently, it was found that the catalyst contributes greatly to the hydrogen transfer to coal at the prethermal treatment. High yield of n-hexane soluble fraction with products having low condensation degree could be obtained by combining the prethermal treatment in the presence of hydrogen and catalyst with the concentration of slurry after the treatment. This was considered to be caused by the synergetic effect between the improvement of liquefaction by suppressing polymerization/condensation at the initial stage of reaction through the prethermal treatment and the effective hydrogen transfer accompanied with the improvement of contact efficiency of coal/catalyst by the concentration of slurry at the stage of liquefaction. 4 refs., 8 figs.

Low energy electron-initiated ion-molecule reactions of ribose analogues

International Nuclear Information System (INIS)

Mozejko, P.

2003-01-01

Recent experiments in which plasmid DNA samples were bombarded with low energy ( 2 O, DNA bases, and sugar-phosphate backbone analogues. To this end, the cyclic molecule tetrahydrofuran, and its derivatives, provide useful models for the sugar-like molecules contained in the backbone of DNA. In addition to LEE induced dissociation by processes such as dissociative electron attachment (DEA), molecules may be damaged by ions and neutral species of non-thermal energies created by LEE in the surrounding environment. In this contribution, we investigate with electron stimulated desorption techniques, LEE damage to films of desoxy-ribose analogues in the presence of various molecular coadsorbates, that simulate changes in local molecular environment. In one type of experiments tetrahydrofuran is deposited onto multilayer O2. A desorbed signal of OH - indicates ion-molecule reactions of the type O - + C 4 H 8 O -> OH - + C 4 H 7 O, where the O - was formed initially by DEA to O 2 . Further electron stimulated desorption measurements for tetrahydrofuran and derivatives adsorbed on H 2 O, Kr, N 2 O and CH 3 OH will be presented and discussed

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

Thermal theory of autowave processes in low-temperature solid-phase radiochemical reactions

International Nuclear Information System (INIS)

Barelko, V.V.; Barkalov, I.M.; Vaganov, D.A.; Zanin, A.M.; Kiryukhin, D.P.

1982-01-01

A new phenomenon in radiation cryochemistry concerning the class of autowave processes was previously discovered. It was observed in halogenation and hydrohalogenation of hydrocarbons and consisted of spontaneous, laminar propagation of a chemical transformation wave based on a frozen mixture of reagents previously irradiated with 60 Co γ-rays. The effect of the positive inverse correlation between the chemical conversion and brittle fracture of a solid sample of reagents is the phenomenological basis of the phenomenon; formation of fractures triggers a reactive process which takes place on their active surface (or in the layer adjacent to it), and the chemical reaction, in turn, stimulates the subsequent development of the process of decomposition. As a result, a single brittle fracture and chemical conversion wave which moves along the solid sample arises. Different mechanisms of generation of fracture surfaces under the effect of the reaction are possible. A difference in the densities of the initial reagents and the products of the reaction could be one of the causes of brittle fracture, and the thermal stresses induced by the exothermicity of the chemical processes could be another cause. The present work concerns the analysis of the features of the wave process which occurs based on the second, thermal mechanism. The analysis was conducted within the framework of a phenomenological approach which does not require specific definition of the nature of the chemical activation of the system during its brittle fracture

Thermal runaway reaction hazards and mechanisms of hydroxylamine with acid/base contaminants

International Nuclear Information System (INIS)

Wei Chunyang; Saraf, Sanjeev R.; Rogers, William J.; Sam Mannan, M.

2004-01-01

Hydroxylamine (HA) has been involved in two incidents since 1999 because of its thermal instability and incompatibility. In this study, thermal runaway reactions of hydroxylamine with various concentrations of KOH and HCl were studied using the reactive system screening tool (RSST) and automatic pressure tracking adiabatic calorimeter (APTAC). The thermokinetic data, such as onset temperature, heat of reaction, maximum self-heat rate, maximum pressure rate, and non-condensable gas pressure, were compared with those of hydroxylamine solution without added impurity. Our study shows that the thermal decomposition behavior of hydroxylamine is affected by the presence of acid/base, and mixing of hydroxylamine with acid/base may cause thermal decomposition at lower temperatures. Different decomposition pathways can be initiated by hydrogen ion and hydroxide ion. The decomposition mechanisms of hydroxylamine in alkaline and acidic solutions are proposed based on the products, information from the literature, and quantum mechanical calculations. The experimental results are discussed in terms of the proposed reaction mechanisms

Initial substrate moisture content and storage temperature affects chemical properties of bagged substrates containing controlled release fertilizer at two different temperatures

Science.gov (United States)

Bagged potting mixes can be stored for weeks or months before being used by consumers. Some bagged potting mixes are amended with controlled release fertilizers (CRF). The objective of this research was to observe how initial substrate moisture content and storage temperature affect the chemical p...

Effect of Initial Backfill Temperature on the Deformation Behavior of Early Age Cemented Paste Backfill That Contains Sodium Silicate

Directory of Open Access Journals (Sweden)

Aixiang Wu

2016-01-01

Full Text Available Enhancing the knowledge on the deformation behavior of cemented paste backfill (CPB in terms of stress-strain relations and modulus of elasticity is significant for economic and safety reasons. In this paper, the effect of the initial backfill temperature on the CPB’s stress-strain behavior and modulus of elasticity is investigated. Results show that the stress-strain relationship and the modulus of elasticity behavior of CPB are significantly affected by the curing time and initial temperature of CPB. Additionally, the relationship between the modulus of elasticity and unconfined compressive strength (UCS and the degree of hydration was evaluated and discussed. The increase of UCS and hydration degree leads to an increase in the modulus of elasticity, which is not significantly affected by the initial temperature.

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