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Sample records for radical combustion intermediates

  1. Photodissociation dynamics and spectroscopy of free radical combustion intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Osborn, David Lewis [Univ. of California, Berkeley, CA (United States)

    1996-12-01

    The photodissociation spectroscopy and dynamics of free radicals is studied by the technique of fast beam photofragment translational spectroscopy. Photodetachment of internally cold, mass-selected negative ions produces a clean source of radicals, which are subsequently dissociated and detected. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states of the radical. In addition, the photodissociation dynamics, product branching ratios, and bond energies are probed at fixed photon energies by measuring the translational energy, P(ET), and angular distribution of the recoiling fragments using a time- and position-sensitive detector. Ab initio calculations are combined with dynamical and statistical models to interpret the observed data. The photodissociation of three prototypical hydrocarbon combustion intermediates forms the core of this work.

  2. Resonance ionization detection of combustion radicals

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    Cool, T.A. [Cornell Univ., Ithaca, NY (United States)

    1993-12-01

    Fundamental research on the combustion of halogenated organic compounds with emphasis on reaction pathways leading to the formation of chlorinated aromatic compounds and the development of continuous emission monitoring methods will assist in DOE efforts in the management and disposal of hazardous chemical wastes. Selective laser ionization techniques are used in this laboratory for the measurement of concentration profiles of radical intermediates in the combustion of chlorinated hydrocarbon flames. A new ultrasensitive detection technique, made possible with the advent of tunable VUV laser sources, enables the selective near-threshold photoionization of all radical intermediates in premixed hydrocarbon and chlorinated hydrocarbon flames.

  3. Progress on resonance ionization detection of combustion radicals

    International Nuclear Information System (INIS)

    Cool, T.A.

    1994-01-01

    Selective laser ionization techniques are used in our laboratory for the measurement of concentration profiles of radical intermediates in the combustion of chlorinated hydrocarbon flames. A new ultrasensitive detection technique, made possible with the advent of tunable VUV laser sources, enables the selective near-threshold photoionization of all radical intermediates in premixed hydrocarbon and chlorinated hydrocarbon flames. The progress made on the following three separate experiments during the past year is briefly described in this report. Flame Radical Concentration Measurements with VUV Spectroscopy; observation of hyperfine quantum beats in cyanogen; and the spectroscopy of the ClCO radical

  4. Spectroscopy, Kinetics, and Dynamics of Combustion Radicals

    Energy Technology Data Exchange (ETDEWEB)

    Nesbitt, David J. [Research/Professor

    2013-08-06

    Spectroscopy, kinetics and dynamics of jet cooled hydrocarbon transients relevant to the DOE combustion mission have been explored, exploiting i) high resolution IR lasers, ii) slit discharge sources for formation of jet cooled radicals, and iii) high sensitivity detection with direct laser absorption methods and near the quantum shot noise limit. What makes this combination powerful is that such transients can be made under high concentrations and pressures characteristic of actual combustion conditions, and yet with the resulting species rapidly cooled (T ≈10-15K) in the slit supersonic expansion. Combined with the power of IR laser absorption methods, this provides novel access to spectral detection and study of many critical combustion species.

  5. Spectroscopic detection, characterization and dynamics of free radicals relevant to combustion processes

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Terry [The Ohio State Univ., Columbus, OH (United States)

    2015-06-04

    Combustion chemistry is enormously complex. The chemical mechanisms involve a multitude of elementary reaction steps and a comparable number of reactive intermediates, many of which are free radicals. Computer simulations based upon these mechanisms are limited by the validity of the mechanisms and the parameters characterizing the properties of the intermediates and their reactivity. Spectroscopy can provide data for sensitive and selective diagnostics to follow their reactions. Spectroscopic analysis also provides detailed parameters characterizing the properties of these intermediates. These parameters serve as experimental gold standards to benchmark predictions of these properties from large-scale, electronic structure calculations. This work has demonstrated the unique capabilities of near-infrared cavity ringdown spectroscopy (NIR CRDS) to identify, characterize and monitor intermediates of key importance in complex chemical reactions. Our studies have focussed on the large family of organic peroxy radicals which are arguably themost important intermediates in combustion chemistry and many other reactions involving the oxidation of organic compounds. Our spectroscopic studies have shown that the NIR Ã - ˜X electronic spectra of the peroxy radicals allows one to differentiate among chemical species in the organic peroxy family and also determine their isomeric and conformic structure in many cases. We have clearly demonstrated this capability on saturated and unsaturated peroxy radicals and β-hydroxy peroxy radicals. In addition we have developed a unique dual wavelength CRDS apparatus specifically for the purpose of measuring absolute absorption cross section and following the reaction of chemical intermediates. The utility of the apparatus has been demonstrated by measuring the cross-section and self-reaction rate constant for ethyl peroxy.

  6. Identification of combustion intermediates in low-pressure premixed pyridine/oxygen/argon flames.

    Science.gov (United States)

    Tian, Zhenyu; Li, Yuyang; Zhang, Taichang; Zhu, Aiguo; Qi, Fei

    2008-12-25

    Combustion intermediates of two low-pressure premixed pyridine/oxygen flames with respective equivalence ratios of 0.56 (C/O/N = 1:4.83:0.20) and 2.10 (C/O/N = 1:1.29:0.20) have been identified with tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry techniques. About 80 intermediates in the rich flame and 60 intermediates in the lean flame, including nitrogenous, oxygenated, and hydrocarbon intermediates, have been identified by measurements of photoionization mass spectra and photoionization efficiency spectra. Some radicals and new nitrogenous intermediates are identified in the present work. The experimental results are useful for studying the conversion of volatile nitrogen compounds and understanding the formation mechanism of NO(x) in flames of nitrogenous fuels.

  7. Long-lived gas-phase radicals from combustion

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    Kaneko, Takashi; Furusawa, Koji; Amano, Toshiji; Okubo, Yoichi; Tsuchiya, Jun' ichi; Yoshizawa, Fujiroku; Akutsu, Yoshiaki; Tamura, Masamitsu; Yoshida, Tadao (Univ. of Tokyo (Japan))

    1989-04-20

    On indoor air pollution or fire, it is feared that the gas-phase radicals from the combustion of inflammables or fuel seriously exert an influence on the organisms as harmful matter. The gas-phase radicals were studied using the electron spin resonance (ESR) spin-trapping technique. For the spin trap solution, 0.1 mol solution of {alpha}-phenyl-N-t-butylnitron in benzene was used. As a result, apparently long-lived and highly reactive oxygen-centered radicals were detected in the smoke from polyethylene, polypropylene, polystyrene, polymethylmethacrylate, cellulose, kerosene, benzene, acetone, methanol and butylalcohol. It is suggested that the production mechanism for the radicals should be different from olefin-NOx-air system reaction, which is considered for the radicals from cigarette smoke. 11 refs., 6 figs., 2 tabs.

  8. Final Technical Report: Vibrational Spectroscopy of Transient Combustion Intermediates Trapped in Helium Nanodroplets

    Energy Technology Data Exchange (ETDEWEB)

    Douberly, Gary Elliott [Univ. of Georgia, Athens, GA (United States)

    2017-11-16

    The objective of our experimental research program is to isolate and stabilize transient intermediates and products of prototype combustion reactions. This will be accomplished by Helium Nanodroplet Isolation, a novel technique where liquid helium droplets freeze out high energy metastable configurations of a reacting system, permitting infrared spectroscopic characterizations of products and intermediates that result from hydrocarbon radical reactions with molecular oxygen and other small molecules relevant to combustion environments. The low temperature (0.4 K) and rapid cooling associated with He droplets provides a perfectly suited medium to isolate and probe a broad range of molecular radical and carbene systems important to combustion chemistry. The sequential addition of molecular species to He droplets often leads to the stabilization of high-energy, metastable cluster configurations that represent regions of the potential energy surface far from the global minimum. Single and double resonance IR laser spectroscopy techniques, along with Stark and Zeeman capabilities, are being used to probe the structural and dynamical properties of these systems.

  9. Study of the Radical Chain Mechanism of Hydrocarbon Oxidation for In Situ Combustion Process

    Directory of Open Access Journals (Sweden)

    Alexandra Ushakova

    2017-01-01

    Full Text Available Despite the abundance of in situ combustion models of oil oxidation, many of the effects are still beyond consideration. For example, until now, initial stages of oxidation were not considered from a position of radical chain process. This is a serious difficulty for the simulation of oil recovery process that involves air injection. To investigate the initial stages of oxidation, the paper considers the sequence of chemical reactions, including intermediate short-living compounds and radicals. We have attempted to correlate the main stages of the reaction with areas of heat release observed in the experiments. The system of differential equations based on the equations of oxidation reactions was solved. Time dependence of peroxides formation and start of heat release is analytically derived for the initial stages. We have considered the inhibition of initial oxidation stages by aromatic oil compounds and have studied the induction time in dependence on temperature. Chain ignition criteria for paraffins and crude oil in presence of core samples were obtained. The calculation results are compared with the stages of oxidation that arise by high-pressure differential scanning calorimetry. According to experimental observations we have determined which reactions are important for the process and which can be omitted or combined into one as insignificant.

  10. Biochemical failure after radical prostatectomy in intermediate-risk group men increases with the number of risk factors

    Directory of Open Access Journals (Sweden)

    Nobuki Furubayashi

    2017-01-01

    Conclusion: The number of intermediate risk factors is significantly associated with the PSA failure-free survival rate after radical prostatectomy in the intermediate-risk group. Patients classified into the intermediate-risk group based on all three intermediate risk factors are less likely to achieve a complete cure through surgery alone.

  11. Identification of the substrate radical intermediate derived from ethanolamine during catalysis by ethanolamine ammonia-lyase.

    Science.gov (United States)

    Bender, Güneş; Poyner, Russell R; Reed, George H

    2008-10-28

    Rapid-mix freeze-quench (RMFQ) methods and electron paramagnetic resonance (EPR) spectroscopy have been used to characterize the steady-state radical in the deamination of ethanolamine catalyzed by adenosylcobalamin (AdoCbl)-dependent ethanolamine ammonia-lyase (EAL). EPR spectra of the radical intermediates formed with the substrates, [1-13C]ethanolamine, [2-13C]ethanolamine, and unlabeled ethanolamine were acquired using RMFQ trapping methods from 10 ms to completion of the reaction. Resolved 13C hyperfine splitting in EPR spectra of samples prepared with [1-13C]ethanolamine and the absence of such splitting in spectra of samples prepared with [2-13C]ethanolamine show that the unpaired electron is localized on C1 (the carbinol carbon) of the substrate. The 13C splitting from C1 persists from 10 ms throughout the time course of substrate turnover, and there was no evidence of a detectable amount of a product like radical having unpaired spin on C2. These results correct an earlier assignment for this radical intermediate [Warncke, K., et al. (1999) J. Am. Chem. Soc. 121, 10522-10528]. The EPR signals of the substrate radical intermediate are altered by electron spin coupling to the other paramagnetic species, cob(II)alamin, in the active site. The dipole-dipole and exchange interactions as well as the 1-13C hyperfine splitting tensor were analyzed via spectral simulations. The sign of the isotropic exchange interaction indicates a weak ferromagnetic coupling of the two unpaired electrons. A Co2+-radical distance of 8.7 A was obtained from the magnitude of the dipole-dipole interaction. The orientation of the principal axes of the 13C hyperfine splitting tensor shows that the long axis of the spin-bearing p orbital on C1 of the substrate radical makes an angle of approximately 98 degrees with the unique axis of the d(z2) orbital of Co2+.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-12-01

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

  13. A paradigm shift for radical SAM reactions: The organometallic intermediate Ω is central to catalysis.

    Science.gov (United States)

    Byer, Amanda S; Yang, Hao; McDaniel, Elizabeth C; Kathiresan, Venkatesan; Impano, Stella; Pagnier, Adrien; Watts, Hope; Denler, Carly; Vagstad, Anna; Piel, Jörn; Duschene, Kaitlin S; Shepard, Eric M; Shields, Thomas P; Scott, Lincoln G; Lilla, Edward A; Yokoyama, Kenichi; Broderick, William E; Hoffman, Brian M; Broderick, Joan B

    2018-06-28

    Radical S-adenosyl-L-methionine (SAM) en-zymes comprise a vast superfamily catalyzing diverse reactions essential to all life through ho-molytic SAM cleavage to liberate the highly-reactive 5-deoxyadenosyl radical (5-dAdo•). Our recent observation of a catalytically compe-tent organometallic intermediate Ω that forms dur-ing reaction of the radical SAM (RS) enzyme py-ruvate formate-lyase activating-enzyme (PFL-AE) was therefore quite surprising, and led to the question of its broad relevance in the superfamily. We now show that Ω in PFL-AE forms as an in-termediate under a variety of mixing order condi-tions, suggesting it is central to catalysis in this enzyme. We further demonstrate that Ω forms in a suite of RS enzymes chosen to span the totality of superfamily reaction types, implicating Ω as essential in catalysis across the RS superfamily. Finally, EPR and electron nuclear double reso-nance spectroscopy establish that Ω involves an Fe-C5 bond between 5-dAdo• and the [4Fe-4S] cluster. An analogous organometallic bond is found in the well-known adenosylcobalamin (co-enzyme B12) cofactor used to initiate radical reac-tions via a 5'-dAdo• intermediate. Generation of a 5'-dAdo• intermediate via homolytic metal-carbon bond cleavage thus appears to be similar for Ω and coenzyme B12. However coenzyme B12 is involved in enzymes catalyzing of only a small number (~12) of distinct reactions, while the RS superfamily has more than 100,000 distinct se-quences and over 80 reaction types character-ized to date. The appearance of Ω across the RS superfamily therefore dramatically enlarges the sphere of bio-organometallic chemistry in Nature.

  14. Palladium-Catalyzed Atom-Transfer Radical Cyclization at Remote Unactivated C(sp3 )-H Sites: Hydrogen-Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates.

    Science.gov (United States)

    Ratushnyy, Maxim; Parasram, Marvin; Wang, Yang; Gevorgyan, Vladimir

    2018-03-01

    A novel mild, visible-light-induced palladium-catalyzed hydrogen atom translocation/atom-transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5-HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo- and heterocyclic structures. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Analysis of combustion in an ATAC engine with measurement of radical luminescence; Radical hakko keisoku ni yoru ATAC engine no nensho kaiseki

    Energy Technology Data Exchange (ETDEWEB)

    Park, Y; Oguma, H; Ueda, H; Iida, N [Keio University, Tokyo (Japan)

    1997-10-01

    In order to make clear of the combustion mechanism and the frame structure in two stake, so called, active thermo-atmosphere combustion (ATAC) engine fueled by gasoline and methanol, we measured the 2-demensional images of OH, CH and C2 radical band spectra in both ATAC and SI combustion mode. From the results of pressure data in the cylinder, the heat release rate was calculated. We evaluated the correlation of radical luminescence intensity and the rate of heat release. 3 refs., 4 figs., 2 tabs.

  16. Experimental investigation of H2 combustion in the Sandia VGES Intermediate-scale burn tank

    International Nuclear Information System (INIS)

    Benedick, W.B.; Berman, M.; Cummings, J.C.; Prassinos, P.G.

    1983-01-01

    Sandia National Laboratories is presently involved in several NRC-sponsored experimental projects to provide data that will help quantify the threat of hydrogen combustion during LWR accidents. One project, which employs several experimental facilities is the Variable Geometry Experimental System (VGES). The purpose of this paper is to present the experimental results from one of these facilities; the intermediate-scale burn tank ( about5m 3 ). The data provided by this facility can be used in the development and assessment of analytical models used to predict hydrogen combustion behavior

  17. Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH +allene reaction

    Science.gov (United States)

    Raman, Arjun S.; Justine Bell, M.; Lau, Kai-Chung; Butler, Laurie J.

    2007-10-01

    These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH2CCH2OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl +CH2CCH2OH photofragments, a spin-orbit branching ratio for Cl(P1/22):Cl(P3/22) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH2CCH2OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH2CCH2OH radical intermediate to the three most important product channels for the OH +allene reaction expected from this radical intermediate: formaldehyde+C2H3, H +acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH3 product channel. We compare our results to a previous theoretical study of the O +allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates.

  18. Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH+allene reaction

    International Nuclear Information System (INIS)

    Raman, Arjun S.; Justine Bell, M.; Lau, K.-C.; Butler, Laurie J.

    2007-01-01

    These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH 2 CCH 2 OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193 nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl+CH 2 CCH 2 OH photofragments, a spin-orbit branching ratio for Cl( 2 P 1/2 ):Cl( 2 P 3/2 ) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH 2 CCH 2 OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH 2 CCH 2 OH radical intermediate to the three most important product channels for the OH+allene reaction expected from this radical intermediate: formaldehyde+C 2 H 3 , H+acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH 3 product channel. We compare our results to a previous theoretical study of the O+allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates

  19. Theoretical Investigation of Kinetic Processes in Small Radicals of Importance in Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, Millard [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Dagdigian, Paul J. [Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry

    2017-12-12

    Our group studies inelastic and reactive collisions of small molecules, focusing on radicals important in combustion environments. The goal is the better understanding of kinetic processes that may be difficult to access experimentally. An essential component is the accurate determination and fitting of potential energy surfaces (PESs). After fitting the ab initio points to obtain global PESs, we treat the dynamics using time-independent (close-coupling) methods. Cross sections and rate constants for collisions of are determined with our Hibridon program suite . We have studied energy transfer (rotationally, vibrationally, and/or electronically inelastic) in small hydrocarbon radicals (CH2 and CH3) and the CN radical. We have made a comparison with experimental measurements of relevant rate constants for collisions of these radicals. Also, we have calculated accurate transport properties using state-of-the-art PESs and to investigate the sensitivity to these parameters in 1-dimensional flame simulations. Of particular interest are collision pairs involving the light H atom.

  20. Radical intermediates involved in the bleaching of the carotenoid crocin. Hydroxyl radicals, superoxide anions and hydrated electrons

    International Nuclear Information System (INIS)

    Bors, W.; Saran, M.; Michel, C.

    1982-01-01

    The participation of the primary radicals in the bleaching of aqueous solutions of the carotenoid crocin by ionizing radiation was investigated, employing both X-radiolysis and pulse radiolysis. The pulse-radiolytic data demonstrated a very rapid diffusion-controlled attack by both hydroxyl radicals (radicalsOH) and hydrated electrons (e - sub(aq)), while superoxide anions (O 2 - ) did not react at all. The site of the initial reaction of these radicals was not limited to the polyene chromophore. Slower secondary reactions involving crocin alkyl or peroxy radicals contribute mainly to the overall bleaching, in particular during steady-state irradiation. (author)

  1. Intermediate Radical Termination Theory in Elucidation of RAFT Kinetics and Comparison to Experimental Data

    Directory of Open Access Journals (Sweden)

    M. Baqeri-Jagharq

    2008-12-01

    Full Text Available In current work a comprehensive mechanism based on intermediate radical termination theory is assumed for RAFT polymerization of styrene over cumyl dithiobenzoate as RAFT agent. Rate constants for addition (ka and fragmentation reactions (kf are set to 6×106 and 5×104 respectively, which lead to an equilibrium constant value of K = ka/kf = 1.2 x 102. Moment equations method was used to model this mechanism and the results were compared to experimental data to verify modeling. The effects of changing RAFT agent concentration on conversion, molecular weight and polydispersity index of the final product were investigated through the modeling. According to the results, the likelihood of living polymerization increases with raising RAFT agent concentration which leads to linearity of conversion and molecular weight curves and therefore lowering the polydispersity index and narrowing the molecular weight distribution.

  2. Probing the structure of ribosome assembly intermediates in vivo using DMS and hydroxyl radical footprinting.

    Science.gov (United States)

    Hulscher, Ryan M; Bohon, Jen; Rappé, Mollie C; Gupta, Sayan; D'Mello, Rhijuta; Sullivan, Michael; Ralston, Corie Y; Chance, Mark R; Woodson, Sarah A

    2016-07-01

    The assembly of the Escherichia coli ribosome has been widely studied and characterized in vitro. Despite this, ribosome biogenesis in living cells is only partly understood because assembly is coupled with transcription, modification and processing of the pre-ribosomal RNA. We present a method for footprinting and isolating pre-rRNA as it is synthesized in E. coli cells. Pre-rRNA synthesis is synchronized by starvation, followed by nutrient upshift. RNA synthesized during outgrowth is metabolically labeled to facilitate isolation of recent transcripts. Combining this technique with two in vivo RNA probing methods, hydroxyl radical and DMS footprinting, allows the structure of nascent RNA to be probed over time. Together, these can be used to determine changes in the structures of ribosome assembly intermediates as they fold in vivo. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. High-Resolution Photoionization, Photoelectron and Photodissociation Studies. Determination of Accurate Energetic and Spectroscopic Database for Combustion Radicals and Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Cheuk-Yiu [Univ. of California, Davis, CA (United States)

    2016-04-25

    The main goal of this research program was to obtain accurate thermochemical and spectroscopic data, such as ionization energies (IEs), 0 K bond dissociation energies, 0 K heats of formation, and spectroscopic constants for radicals and molecules and their ions of relevance to combustion chemistry. Two unique, generally applicable vacuum ultraviolet (VUV) laser photoion-photoelectron apparatuses have been developed in our group, which have used for high-resolution photoionization, photoelectron, and photodissociation studies for many small molecules of combustion relevance.

  4. Experimental evidence for cobalt(III)-carbene radicals: key intermediates in cobalt(II)-based metalloradical cyclopropanation

    NARCIS (Netherlands)

    Lu, H.; Dzik, W.I.; Xu, X.; Wojtas, L.; de Bruin, B.; Zhang, X.P.

    2011-01-01

    New and conclusive evidence has been obtained for the existence of cobalt(III)-carbene radicals that have been previously proposed as the key intermediates in the underlying mechanism of metalloradical cyclopropanation by cobalt(II) complexes of porphyrins. In the absence of olefin substrates,

  5. Investigation of the O+allyl addition/elimination reaction pathways from the OCH2CHCH2 radical intermediate

    International Nuclear Information System (INIS)

    FitzPatrick, Benjamin L.; Lau, K.-C.; Butler, Laurie J.; Lee, S.-H.; Lin, Jim Jr-Min

    2008-01-01

    These experiments study the preparation of and product channels resulting from OCH 2 CHCH 2 , a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH 2 CHCH 2 radicals; these undergo a facile ring opening to the OCH 2 CHCH 2 radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcal/mol. To elucidate the product channels resulting from the OCH 2 CHCH 2 radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C 3 H 4 O (acrolein)+H, C 2 H 4 +HCO (formyl radical), and H 2 CO (formaldehyde)+C 2 H 3 . A small signal from C 2 H 2 O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at m/e=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C 2 H 5 +CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to

  6. Investigation of the O+allyl addition/elimination reaction pathways from the OCH2CHCH2 radical intermediate

    Science.gov (United States)

    Fitzpatrick, Benjamin L.; Lau, Kai-Chung; Butler, Laurie J.; Lee, Shih-Huang; Lin, Jim-Min, Jr.

    2008-08-01

    These experiments study the preparation of and product channels resulting from OCH2CHCH2, a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH2CHCH2 radicals; these undergo a facile ring opening to the OCH2CHCH2 radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcal/mol. To elucidate the product channels resulting from the OCH2CHCH2 radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C3H4O (acrolein)+H, C2H4+HCO (formyl radical), and H2CO (formaldehyde)+C2H3. A small signal from C2H2O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at m/e=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C2H5+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to each of these product channels

  7. Comparison of thermal and radical effects of EGR gases on combustion process in dual fuel engines at part loads

    International Nuclear Information System (INIS)

    Pirouzpanah, V.; Khoshbakhti Saray, R.; Sohrabi, A.; Niaei, A.

    2007-01-01

    Dual fuel engines at part load inevitably suffer from lower thermal efficiency and higher emission of carbon monoxide and unburned fuel. This work is conducted to investigate the combustion characteristics of a dual fuel (Diesel-gas) engine at part loads using a single zone combustion model with detailed chemical kinetics for combustion of natural gas fuel. In this home made software, the presence of the pilot fuel is considered as a heat source that is deriving form two superposed Wiebe's combustion functions to account for its contribution to ignition of the gaseous fuel and the rest of the total released energy. The chemical kinetics mechanism consists of 112 reactions with 34 species. This combustion model is able to establish the development of the combustion process with time and the associated important operating parameters, such as pressure, temperature, heat release rate (HRR) and species concentration. Therefore, this work is an attempt to investigate the combustion phenomenon at part load and using exhaust gas recirculation (EGR) to improve the above mentioned problems. Also, the results of this work show that each of the different cases of EGR (thermal, chemical and radical cases) has an important role on the combustion process in dual fuel engines at part loads. It is found that all the different cases of EGR have positive effects on the performance and emission parameters of dual fuel engines at part loads despite the negative effect of some diluent gases in the chemical case, which moderates too much the positive effects of the thermal and radical cases of EGR. Predicted values show good agreement with corresponding experimental values over the whole range of engine operating conditions. Implications will be discussed in detail

  8. Radical intermediates of low temperature radiolysis of di-tert-butylcyclohexano-18-crown-6/1-octanol extractant

    International Nuclear Information System (INIS)

    Zakurdaeva, O.A.; Nesterov, S.V.; Moscow State Univ.; Feldman, V.I.

    2013-01-01

    Intermediates of low temperature (77 K) X-rays radiolysis of 1-octanol and di-tert-butylcyclohexano-18-crown-6 solutions in 1-octanol were studied by ESR spectroscopy. Hydroxyalkyl CH 3 (CH 2 ) 6 C circle HOH and interior-type alkyl R 1 C circle HR 2 OH radicals were found to be main paramagnetic products stabilized in 1-octanol irradiated at 77 K. In addition to abovementioned radicals, macrocyclic -O-CH 2 -C circle H- and acyclic -C circle H-C(H)=O radicals produced from crown ether were identified in irradiated 1.0 M DtBuCH18C6 solution in octanol. No deviation in radiation-chemical yield of the stabilized acyclic radicals from the value expected in accord with 'additive' rule was observed in the latter case. It was supposed that macrocycle cleavage in DtBuCH18C6 occurred at early stages of radiolysis rather than in secondary radical reactions between products of 1-octanol radiolysis and crown ether. Meanwhile, alkyl radicals formed from 1-octanol can react with crown ether, resulting in formation of macrocyclic products of radiolysis. (orig.)

  9. Radical intermediates of low temperature radiolysis of di-tert-butylcyclohexano-18-crown-6/1-octanol extractant

    Energy Technology Data Exchange (ETDEWEB)

    Zakurdaeva, O.A.; Nesterov, S.V. [Russian Academy of Sciences, Moscow (Russian Federation). Enikolopov Institute of Synthetic Polymer Materials; Moscow State Univ. (Russian Federation). Dept. of Chemistry; Feldman, V.I. [Moscow State Univ. (Russian Federation). Dept. of Chemistry

    2013-03-01

    Intermediates of low temperature (77 K) X-rays radiolysis of 1-octanol and di-tert-butylcyclohexano-18-crown-6 solutions in 1-octanol were studied by ESR spectroscopy. Hydroxyalkyl CH{sub 3}(CH{sub 2}){sub 6}C {sup circle} HOH and interior-type alkyl R{sub 1}C {sup circle} HR{sub 2}OH radicals were found to be main paramagnetic products stabilized in 1-octanol irradiated at 77 K. In addition to abovementioned radicals, macrocyclic -O-CH{sub 2}-C {sup circle} H- and acyclic -C {sup circle} H-C(H)=O radicals produced from crown ether were identified in irradiated 1.0 M DtBuCH18C6 solution in octanol. No deviation in radiation-chemical yield of the stabilized acyclic radicals from the value expected in accord with 'additive' rule was observed in the latter case. It was supposed that macrocycle cleavage in DtBuCH18C6 occurred at early stages of radiolysis rather than in secondary radical reactions between products of 1-octanol radiolysis and crown ether. Meanwhile, alkyl radicals formed from 1-octanol can react with crown ether, resulting in formation of macrocyclic products of radiolysis. (orig.)

  10. Selective deuteration illuminates the importance of tunneling in the unimolecular decay of Criegee intermediates to hydroxyl radical products.

    Science.gov (United States)

    Green, Amy M; Barber, Victoria P; Fang, Yi; Klippenstein, Stephen J; Lester, Marsha I

    2017-11-21

    Ozonolysis of alkenes, an important nonphotolytic source of hydroxyl (OH) radicals in the atmosphere, proceeds through unimolecular decay of Criegee intermediates. Here, we report a large kinetic isotope effect associated with the rate-limiting hydrogen-transfer step that releases OH radicals for a prototypical Criegee intermediate, CH 3 CHOO. IR excitation of selectively deuterated syn -CD 3 CHOO is shown to result in deuterium atom transfer and release OD radical products. Vibrational activation of syn -CD 3 CHOO is coupled with direct time-resolved detection of OD products to measure a 10-fold slower rate of unimolecular decay upon deuteration in the vicinity of the transition state barrier, which is confirmed by microcanonical statistical theory that incorporates quantum mechanical tunneling. The corresponding kinetic isotope effect of ∼10 is attributed primarily to the decreased probability of D-atom vs. H-atom transfer arising from tunneling. Master equation modeling is utilized to compute the thermal unimolecular decay rates for selectively and fully deuterated syn methyl-substituted Criegee intermediates under atmospheric conditions. At 298 K (1 atm), tunneling is predicted to enhance the thermal decay rate of syn -CH 3 CHOO compared with the deuterated species, giving rise to a significant kinetic isotope effect of ∼50.

  11. Shock tube study of the reactions of the hydroxyl radical with combustion species and pollutants. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, N.; Koffend, J.B.

    1998-02-01

    Shock heating t-butyl hydroperoxide behind a reflected shock wave has proved to be as a convenient source of hydroxyl radicals at temperatures near 1000 K. We applied this technique to the measurement of reaction rate coefficients of OH with several species of interest in combustion chemistry, and developed a thermochemical kinetics/transition state theory (TK-TST) model for predicting the temperature dependence of OH rate coefficients.

  12. Radical Intermediates in the Catalytic Oxidation of Hydrocarbons by Bacterial and Human Cytochrome P450 Enzymes†

    OpenAIRE

    Jiang, Yongying; He, Xiang; Ortiz de Montellano, Paul R.

    2006-01-01

    Cytochromes P450cam and P450BM3 oxidize α- and β-thujone into multiple products, including 7-hydroxy-α-(or β-)thujone, 7,8-dehydro-α-(or β-)thujone, 4-hydroxy-α-(or β-)thujone, 2-hydroxy α-(or β-)thujone, 5-hydroxy-5-isopropyl-2-methyl-2-cyclohexen-1-one, 4,10-dehydrothujone, and carvacrol. Quantitative analysis of the 4-hydroxylated isomers and the ring opened product indicates that the hydroxylation proceeds via a radical mechanism with a radical recombination rate ranging from 0.7 ± 0.3 × ...

  13. Combustion

    CERN Document Server

    Glassman, Irvin

    1987-01-01

    Combustion, Second Edition focuses on the underlying principles of combustion and covers topics ranging from chemical thermodynamics and flame temperatures to chemical kinetics, detonation, ignition, and oxidation characteristics of fuels. Diffusion flames, flame phenomena in premixed combustible gases, and combustion of nonvolatile fuels are also discussed. This book consists of nine chapters and begins by introducing the reader to heats of reaction and formation, free energy and the equilibrium constants, and flame temperature calculations. The next chapter explores the rates of reactio

  14. Combustion

    CERN Document Server

    Glassman, Irvin

    2008-01-01

    Combustion Engineering, a topic generally taught at the upper undergraduate and graduate level in most mechanical engineering programs, and many chemical engineering programs, is the study of rapid energy and mass transfer usually through the common physical phenomena of flame oxidation. It covers the physics and chemistry of this process and the engineering applications-from the generation of power such as the internal combustion automobile engine to the gas turbine engine. Renewed concerns about energy efficiency and fuel costs, along with continued concerns over toxic and particulate emissions have kept the interest in this vital area of engineering high and brought about new developments in both fundamental knowledge of flame and combustion physics as well as new technologies for flame and fuel control. *New chapter on new combustion concepts and technologies, including discussion on nanotechnology as related to combustion, as well as microgravity combustion, microcombustion, and catalytic combustion-all ...

  15. Formation and determination of perinaphthenyl radical and PCAH in combustion processes

    Energy Technology Data Exchange (ETDEWEB)

    Franceschi, A [Univ., Pisa, Italy; Gerbaz, G P; Mangolini, S

    1976-09-01

    The concentration profiles of polycyclic aromatic hydrocarbons (PCAH) and perinaphthenyl radical along a vertical flow reactor have been determined for fuel rich premixed flames of n-heptane with small fractions of other hydrocarbons, methanol, and nitrogen oxide. It has been found that there is a strict relation between the concentrations of the higher molecular weight PCAH, which are the main components of soluble fraction of soot, and the perinaphthenyl radical. The aromatic ring of the fuel supplying the reactor plays the most significant role in the formation of PCAH and perinaphthenyl radical. Furthermore their concentrations increase passing from benzene toluene and, lastly, to mesitylene, because the energy of the C(arom)--C(alif) bond is lower than that of the C(arom)--C(arom) bond. The promoting action of methanol, when added to benzene, in the formation of PCAH and perinaphthenyl radical could be explained by the increased presence of CH/sub 3/ . radicals, which, can overcome the inhibiting action of OH. radicals. The contrary happens when methanol is added to toluene, because CH/sub 3/. coming from alcohol represents only a small fraction of the overall concentration, while the oxidant activity of OH. is prevailing. Finally the strong action of NO in reducing the free radical concentration has been pointed out.

  16. Post-combustion convection in an intermediate-scale vessel1

    International Nuclear Information System (INIS)

    Kempka, S.N.; Ratzel, A.C.; Reed, A.W.; Shepherd, J.E.

    1984-01-01

    A technique used to determine globally averaged total and radiative heat fluxes following constantvolume combustion is described. Fluxes are computed from experimentally measured pressure-time data and initial gas conditions. Results obtained using this technique are compared with local measurements for the combustion of hydrogen-air mixtures in the FITS facility at Sandia National Laboratories. These comparisons are quite favorable, indicating that this method can be used in analyzing data from experiments for comparison with predictive models used in reactor safety accident simulations

  17. Isotope enrichment by electron spin resonance transitions of the intermediate radical pair

    International Nuclear Information System (INIS)

    Okazaki, M.; Shiga, T.; Sakata, S.; Konaka, R.; Toriyama, K.

    1988-01-01

    Microwave effects on the spin adduct yield were observed in the photoreduction of menadione in micellar solutions with ordinary sodium dodecyl sulfate (SDS), deuterium-labeled SDS, and a mixture of them. A large isotope effect was found in the microwave modulation of the spin adduct yield, which is due to the ESR transitions of the transient radical pair in the reaction. It is demonstrated for the first time that the microwave field can be used to enrich one of the isotopes which coexist in the system

  18. Combustion

    CERN Document Server

    Glassman, Irvin

    1997-01-01

    This Third Edition of Glassman's classic text clearly defines the role of chemistry, physics, and fluid mechanics as applied to the complex topic of combustion. Glassman's insightful introductory text emphasizes underlying physical and chemical principles, and encompasses engine technology, fire safety, materials synthesis, detonation phenomena, hydrocarbon fuel oxidation mechanisms, and environmental considerations. Combustion has been rewritten to integrate the text, figures, and appendixes, detailing available combustion codes, making it not only an excellent introductory text but also an important reference source for professionals in the field. Key Features * Explains complex combustion phenomena with physical insight rather than extensive mathematics * Clarifies postulates in the text using extensive computational results in figures * Lists modern combustion programs indicating usage and availability * Relates combustion concepts to practical applications.

  19. Insertion of molecular oxygen into a palladium(II) methyl bond: a radical chain mechanism involving palladium(III) intermediates.

    Science.gov (United States)

    Boisvert, Luc; Denney, Melanie C; Hanson, Susan Kloek; Goldberg, Karen I

    2009-11-04

    The reaction of (bipy)PdMe(2) (1) (bipy = 2,2'-bipyridine) with molecular oxygen results in the formation of the palladium(II) methylperoxide complex (bipy)PdMe(OOMe) (2). The identity of the product 2 has been confirmed by independent synthesis. Results of kinetic studies of this unprecedented oxygen insertion reaction into a palladium alkyl bond support the involvement of a radical chain mechanism. Reproducible rates, attained in the presence of the radical initiator 2,2'-azobis(2-methylpropionitrile) (AIBN), reveal that the reaction is overall first-order (one-half-order in both [1] and [AIBN], and zero-order in [O(2)]). The unusual rate law (half-order in [1]) implies that the reaction proceeds by a mechanism that differs significantly from those for organic autoxidations and for the recently reported examples of insertion of O(2) into Pd(II) hydride bonds. The mechanism for the autoxidation of 1 is more closely related to that found for the autoxidation of main group and early transition metal alkyl complexes. Notably, the chain propagation is proposed to proceed via a stepwise associative homolytic substitution at the Pd center of 1 with formation of a pentacoordinate Pd(III) intermediate.

  20. Oxoferryl-Porphyrin Radical Catalytic Intermediate in Cytochrome bd Oxidases Protects Cells from Formation of Reactive Oxygen Species*

    Science.gov (United States)

    Paulus, Angela; Rossius, Sebastiaan Gijsbertus Hendrik; Dijk, Madelon; de Vries, Simon

    2012-01-01

    The quinol-linked cytochrome bd oxidases are terminal oxidases in respiration. These oxidases harbor a low spin heme b558 that donates electrons to a binuclear heme b595/heme d center. The reaction with O2 and subsequent catalytic steps of the Escherichia coli cytochrome bd-I oxidase were investigated by means of ultra-fast freeze-quench trapping followed by EPR and UV-visible spectroscopy. After the initial binding of O2, the O–O bond is heterolytically cleaved to yield a kinetically competent heme d oxoferryl porphyrin π-cation radical intermediate (compound I) magnetically interacting with heme b595. Compound I accumulates to 0.75–0.85 per enzyme in agreement with its much higher rate of formation (∼20,000 s−1) compared with its rate of decay (∼1,900 s−1). Compound I is next converted to a short lived heme d oxoferryl intermediate (compound II) in a phase kinetically matched to the oxidation of heme b558 before completion of the reaction. The results indicate that cytochrome bd oxidases like the heme-copper oxidases break the O–O bond in a single four-electron transfer without a peroxide intermediate. However, in cytochrome bd oxidases, the fourth electron is donated by the porphyrin moiety rather than by a nearby amino acid. The production of reactive oxygen species by the cytochrome bd oxidase was below the detection level of 1 per 1000 turnovers. We propose that the two classes of terminal oxidases have mechanistically converged to enzymes in which the O–O bond is broken in a single four-electron transfer reaction to safeguard the cell from the formation of reactive oxygen species. PMID:22287551

  1. Development of a Raman spectroscopy technique to detect alternate transportation fuel hydrocarbon intermediates in complex combustion environments.

    Energy Technology Data Exchange (ETDEWEB)

    Ekoto, Isaac W.; Barlow, Robert S.

    2012-12-01

    Spontaneous Raman spectra for important hydrocarbon fuels and combustion intermediates were recorded over a range of low-to-moderate flame temperatures using the multiscalar measurement facility located at Sandia/CA. Recorded spectra were extrapolated to higher flame temperatures and then converted into empirical spectral libraries that can readily be incorporated into existing post-processing analysis models that account for crosstalk from overlapping hydrocarbon channel signal. Performance testing of the developed libraries and reduction methods was conducted through an examination of results from well-characterized laminar reference flames, and was found to provide good agreement. The diagnostic development allows for temporally and spatially resolved flame measurements of speciated hydrocarbon concentrations whose parent is more chemically complex than methane. Such data are needed to validate increasingly complex flame simulations.

  2. A laminar flame investigation of 2-butanone, and the combustion-related intermediates formed through its oxidation

    KAUST Repository

    Hemken, Christian

    2016-06-28

    2-Butanone (methyl ethyl ketone) is a high-octane next-generation biofuel candidate synthesized through microbiological pathways from biomass. The flame structure and species formed in 2-butanone combustion are of interest when further considering this compound for use as a fuel. Thus species profiles within a fuel-rich laminar premixed flat flame of 2-butanone were measured. Two experiments which used different facilities and measurement techniques were combined i.e. the first using electron ionization molecular-beam mass spectrometry (MBMS) and the second relied on synchrotron-generated vacuum UV photoionization MBMS. Very good agreement between both measurements was obtained. The experiments identified the formation of a number of toxic oxygenated intermediates such as methyl vinyl ketone (MVK) acetaldehyde and formaldehyde. 2- Butanone showed the lowest overall concentrations for species that could contribute to potentially hazardous volatile emissions underlining its attraction as a fuel also from this perspective.

  3. A laminar flame investigation of 2-butanone, and the combustion-related intermediates formed through its oxidation

    KAUST Repository

    Hemken, Christian; Burke, Ultan; Graf, Isabelle; Ruwe, Lena; Park, Sungwoo; Sarathy, Mani; Heufer, K. Alexander; Kohse-Hö inghaus, Katharina

    2016-01-01

    2-Butanone (methyl ethyl ketone) is a high-octane next-generation biofuel candidate synthesized through microbiological pathways from biomass. The flame structure and species formed in 2-butanone combustion are of interest when further considering this compound for use as a fuel. Thus species profiles within a fuel-rich laminar premixed flat flame of 2-butanone were measured. Two experiments which used different facilities and measurement techniques were combined i.e. the first using electron ionization molecular-beam mass spectrometry (MBMS) and the second relied on synchrotron-generated vacuum UV photoionization MBMS. Very good agreement between both measurements was obtained. The experiments identified the formation of a number of toxic oxygenated intermediates such as methyl vinyl ketone (MVK) acetaldehyde and formaldehyde. 2- Butanone showed the lowest overall concentrations for species that could contribute to potentially hazardous volatile emissions underlining its attraction as a fuel also from this perspective.

  4. Dynamics of Peroxy and Alkenyl Radicals Undergoing Competing Rearrangements in Biodiesel Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Dibble, Theodore S. [State Univ. of New York (SUNY), Syracuse, NY (United States)

    2016-03-24

    Biodiesel fuel is increasingly being used worldwide. Although we have a fair understanding of the molecular details of the chemistry of peroxy radicals derived from alkanes, biodiesel fuels contain ester and olefin groups which significantly impact the thermodynamics and kinetics of biodiesel ignition. The broader goal of this research is to carry out systematic computational studies of the elementary kinetics of the chemistry of ROO•, QOOH and •OOQOOH compounds that are models for biodiesel ignition.

  5. Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

    International Nuclear Information System (INIS)

    Grodkowski, J.; Bobrowski, K.; Mehnert, R.; Brede, O.

    1989-01-01

    The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl 4 and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN +radical ) and the former to the known carbonium ion of malachite green dye (MG + ). Observation of the consecutive charge transfer via the schemes: DCE +radical → BPh +radical → MGCN +radical and DCE +radical → MGCN +radical → TMPD +radical , allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV MGCN +radical radical cation is located in the ''aniline'' part of the molecule. (author)

  6. Formation of an intermediate radical cation in the nanosecond pulse radiolysis of malachite green leucocyanide in organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Grodkowski, J; Bobrowski, K; Mehnert, R; Brede, O

    1989-01-01

    The malachite green leucocyanide (MGCN) was irradiated in argon or oxygen saturated solutions of n-butyl chloride, 1.2-DCE, CCl/sub 4/ and acetone with 13 ns electron pulses. Two species with absorption maxima at 620 and 480 nm were observed. The latter was attributed to the malachite green leucocyanide radical cation (MGCN/sup +radical/) and the former to the known carbonium ion of malachite green dye (MG/sup +/). Observation of the consecutive charge transfer via the schemes: DCE/sup +radical/ -> BPh/sup +radical/ -> MGCN/sup +radical/ and DCE/sup +radical/ -> MGCN/sup +radical/ -> TMPD/sup +radical/, allowed to estimate the ionization potential of MGCN molecule in the range 6.9 eV < Ip/sub MGCN/ < 8.27 eV. Presented results and literature data suggest that positive charge in MGCN/sup +radical/ radical cation is located in the ''aniline'' part of the molecule. (author).

  7. Primary photodissociation pathways of epichlorohydrin and analysis of the C-C bond fission channels from an O(3P)+allyl radical intermediate

    International Nuclear Information System (INIS)

    FitzPatrick, Benjamin L.; Alligood, Bridget W.; Butler, Laurie J.; Lee, Shih-Huang; Lin, Jim Jr-Min

    2010-01-01

    This study initially characterizes the primary photodissociation processes of epichlorohydrin, c-(H 2 COCH)CH 2 Cl. The three dominant photoproduct channels analyzed are c-(H 2 COCH)CH 2 +Cl, c-(H 2 COCH)+CH 2 Cl, and C 3 H 4 O+HCl. In the second channel, the c-(H 2 COCH) photofission product is a higher energy intermediate on C 2 H 3 O global potential energy surface and has a small isomerization barrier to vinoxy. The resulting highly vibrationally excited vinoxy radicals likely dissociate to give the observed signal at the mass corresponding to ketene, H 2 CCO. The final primary photodissociation pathway HCl+C 3 H 4 O evidences a recoil kinetic energy distribution similar to that of four-center HCl elimination in chlorinated alkenes, so is assigned to production of c-(H 2 COC)=CH 2 ; the epoxide product is formed with enough vibrational energy to isomerize to acrolein and dissociate. The paper then analyzes the dynamics of the C 3 H 5 O radical produced from C-Cl bond photofission. When the epoxide radical photoproduct undergoes facile ring opening, it is the radical intermediate formed in the O( 3 P)+allyl bimolecular reaction when the O atom adds to an end C atom. We focus on the HCO+C 2 H 4 and H 2 CO+C 2 H 3 product channels from this radical intermediate in this report. Analysis of the velocity distribution of the momentum-matched signals from the HCO+C 2 H 4 products at m/e=29 and 28 shows that the dissociation of the radical intermediate imparts a high relative kinetic energy, peaking near 20 kcal/mol, between the products. Similarly, the energy imparted to relative kinetic energy in the H 2 CO+C 2 H 3 product channel of the O( 3 P)+allyl radical intermediate also peaks at high-recoil kinetic energies, near 18 kcal/mol. The strongly forward-backward peaked angular distributions and the high kinetic energy release result from tangential recoil during the dissociation of highly rotationally excited nascent radicals formed photolytically in this experiment

  8. Primary photodissociation pathways of epichlorohydrin and analysis of the C-C bond fission channels from an O(3P)+allyl radical intermediate

    Science.gov (United States)

    FitzPatrick, Benjamin L.; Alligood, Bridget W.; Butler, Laurie J.; Lee, Shih-Huang; Lin, Jim-Min, Jr.

    2010-09-01

    This study initially characterizes the primary photodissociation processes of epichlorohydrin, c-(H2COCH)CH2Cl. The three dominant photoproduct channels analyzed are c-(H2COCH)CH2+Cl, c-(H2COCH)+CH2Cl, and C3H4O+HCl. In the second channel, the c-(H2COCH) photofission product is a higher energy intermediate on C2H3O global potential energy surface and has a small isomerization barrier to vinoxy. The resulting highly vibrationally excited vinoxy radicals likely dissociate to give the observed signal at the mass corresponding to ketene, H2CCO. The final primary photodissociation pathway HCl+C3H4O evidences a recoil kinetic energy distribution similar to that of four-center HCl elimination in chlorinated alkenes, so is assigned to production of c-(H2COC)=CH2; the epoxide product is formed with enough vibrational energy to isomerize to acrolein and dissociate. The paper then analyzes the dynamics of the C3H5O radical produced from C-Cl bond photofission. When the epoxide radical photoproduct undergoes facile ring opening, it is the radical intermediate formed in the O(P3)+allyl bimolecular reaction when the O atom adds to an end C atom. We focus on the HCO+C2H4 and H2CO+C2H3 product channels from this radical intermediate in this report. Analysis of the velocity distribution of the momentum-matched signals from the HCO+C2H4 products at m/e=29 and 28 shows that the dissociation of the radical intermediate imparts a high relative kinetic energy, peaking near 20 kcal/mol, between the products. Similarly, the energy imparted to relative kinetic energy in the H2CO+C2H3 product channel of the O(P3)+allyl radical intermediate also peaks at high-recoil kinetic energies, near 18 kcal/mol. The strongly forward-backward peaked angular distributions and the high kinetic energy release result from tangential recoil during the dissociation of highly rotationally excited nascent radicals formed photolytically in this experiment. The data also reveal substantial branching to an HCCH+H3

  9. Role of the reaction of stabilized Criegee intermediates with peroxy radicals in particle formation and growth in air.

    Science.gov (United States)

    Zhao, Yue; Wingen, Lisa M; Perraud, Véronique; Greaves, John; Finlayson-Pitts, Barbara J

    2015-05-21

    Ozonolysis of alkenes is an important source of secondary organic aerosol (SOA) in the atmosphere. However, the mechanisms by which stabilized Criegee intermediates (SCI) react to form and grow the particles, and in particular the contributions from oligomers, are not well understood. In this study, ozonolysis of trans-3-hexene (C6H12), as a proxy for small alkenes, was investigated with an emphasis on the mechanisms of particle formation and growth. Ozonolysis experiments were carried out both in static Teflon chambers (18-20 min reaction times) and in a glass flow reactor (24 s reaction time) in the absence and presence of OH or SCI scavengers, and under different relative humidity (RH) conditions. The chemical composition of polydisperse and size-selected SOA particles was probed using different mass spectrometric techniques and infrared spectroscopy. Oligomers having SCI as the chain unit are found to be the dominant components of such SOA particles. The formation mechanism for these oligomers suggested by our results follows the sequential addition of SCI to organic peroxy (RO2) radicals, in agreement with previous studies by Moortgat and coworkers. Smaller particles are shown to have a relatively greater contribution from longer oligomers. Higher O/C ratios are observed in smaller particles and are similar to those of oligomers resulting from RO2 + nSCI, supporting a significant role for longer oligomers in particle nucleation and early growth. Under atmospherically relevant RH of 30-80%, water vapor suppresses oligomer formation through scavenging SCI, but also enhances particle nucleation. Under humid conditions, or in the presence of formic or hydrochloric acid as SCI scavengers, peroxyhemiacetals are formed by the acid-catalyzed particle phase reaction between oligomers from RO2 + nSCI and a trans-3-hexene derived carbonyl product. In contrast to the ozonolysis of trans-3-hexene, oligomerization involving RO2 + nSCI does not appear to be prevalent in the

  10. Fundamental spectroscopic studies of carbenes and hydrocarbon radicals

    Energy Technology Data Exchange (ETDEWEB)

    Gottlieb, C.A.; Thaddeus, P. [Harvard Univ., Cambridge, MA (United States)

    1993-12-01

    Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.

  11. Pathological differences in radical prostatectomy specimens between low- and intermediate-risk prostate cancer patients. Indications for permanent seed implantation monotherapy

    International Nuclear Information System (INIS)

    Sakamoto, Naotaka; Monji, Keisuke; Yuuki, Kohei; Yoshikawa, Masahiro; Iguchi, Atsushi

    2010-01-01

    To clarify the indications for permanent seed implantation monotherapy in patients with intermediate-risk prostate cancer, pathological differences in radical prostatectomy specimens between low- and intermediate-risk prostate cancer were assessed. Fifty-three cases in the low-risk group and 96 cases in the intermediate-risk group had their radical prostatectomy specimens pathologically evaluated between April 2000 and January 2009. Patients with radical prostatectomy specimens of pT2 and Gleason score ≤3+4 were defined as the favorable group, while those with ≥pT3a and/or Gleason score ≥4+3 were defined as the unfavorable group. The favorable group was made up of 67.9%, 81.2%, 73.9%, 73.3%, 23.5% and 24.0% low-risk group cases, ≤T2a, GS 3+3 and 10< prostatic specific antigen (PSA)≤20 ng/ml cases, ≤T2a, GS 3+4 and PSA ≤10 ng/ml cases, ≤T2a, GS 3+4 and 10< PSA≤20 ng/ml cases, ≤T2a, GS 4+3 and PSA ≤20 ng/ml cases and T2b, GS ≤4+3 and PSA ≤20 ng/ml cases, respectively. The rate of unfavorable group in cases with ≤T2a, GS 4+3 and PSA ≤20 ng/ml, and cases with T2b, GS ≤4+3 and PSA ≤20 ng/ml was statistically higher than that in the low-risk group. Accordingly, cancer volume in cases with T2b, GS ≤4+3 and PSA ≤ 20 ng/ml was statistically larger than that in the low-risk group. Cancer volume in intermediate-risk groups other than ≤T2a, GS 3+4 and PSA ≤10 ng/ml tended to be larger than that in the low-risk group. As for radical prostatectomy specimens, the pathological findings of cases with ≤T2a, GS 3+4 and PSA ≤10 ng/ml were similar to those of cases in the low-risk group. The outcome for permanent seed implantation monotherapy with a conventional dose in cases with ≤T2a, GS 3+4 and PSA ≤10 ng/ml may be similar to that of cases in the low-risk group from a pathological aspect. (author)

  12. Delayed radical prostatectomy for intermediate-risk prostate cancer is associated with biochemical recurrence: possible implications for active surveillance from the SEARCH database.

    Science.gov (United States)

    Abern, Michael R; Aronson, William J; Terris, Martha K; Kane, Christopher J; Presti, Joseph C; Amling, Christopher L; Freedland, Stephen J

    2013-03-01

    Active surveillance (AS) is increasingly accepted as appropriate management for low-risk prostate cancer (PC) patients. It is unknown whether delaying radical prostatectomy (RP) is associated with increased risk of biochemical recurrence (BCR) for men with intermediate-risk PC. We performed a retrospective analysis of 1,561 low and intermediate-risk men from the Shared Equal Access Regional Cancer Hospital (SEARCH) database treated with RP between 1988 and 2011. Patients were stratified by interval between diagnosis and RP (≤ 3, 3-6, 6-9, or >9 months) and by risk using the D'Amico classification. Cox proportional hazard models were used to analyze BCR. Logistic regression was used to analyze positive surgical margins (PSM), extracapsular extension (ECE), and pathologic upgrading. Overall, 813 (52%) men were low-risk, and 748 (48%) intermediate-risk. Median follow-up among men without recurrence was 52.9 months, during which 437 men (38.9%) recurred. For low-risk men, RP delays were unrelated to BCR, ECE, PSM, or upgrading (all P > 0.05). For intermediate-risk men, however, delays >9 months were significantly related to BCR (HR: 2.10, P = 0.01) and PSM (OR: 4.08, P 9 months were associated with BCR in subsets of intermediate-risk men with biopsy Gleason score ≤ 3 + 4 (HR: 2.51, P 9 months predicted greater BCR and PSM risk. If confirmed in future studies, this suggests delayed RP for intermediate-risk PC may compromise outcomes. Copyright © 2012 Wiley Periodicals, Inc.

  13. Degradation and intermediates of diclofenac as instructive example for decomposition of recalcitrant pharmaceuticals by hydroxyl radicals generated with pulsed corona plasma in water.

    Science.gov (United States)

    Banaschik, Robert; Jablonowski, Helena; Bednarski, Patrick J; Kolb, Juergen F

    2018-01-15

    Seven recalcitrant pharmaceutical residues (diclofenac, 17α-ethinylestradiol, carbamazepine, ibuprofen, trimethoprim, diazepam, diatrizoate) were decomposed by pulsed corona plasma generated directly in water. The detailed degradation pathway was investigated for diclofenac and 21 intermediates could be identified in the degradation cascade. Hydroxyl radicals have been found primarily responsible for decomposition steps. By spin trap enhanced electron paramagnetic resonance spectroscopy (EPR), OH-adducts and superoxide anion radical adducts were detected and could be distinguished applying BMPO as a spin trap. The increase of concentrations of adducts follows qualitatively the increase of hydrogen peroxide concentrations. Hydrogen peroxide is eventually consumed in Fenton-like processes but the concentration is continuously increasing to about 2mM for a plasma treatment of 70min. Degradation of diclofenac is inversely following hydrogen peroxide concentrations. No qualitative differences between byproducts formed during plasma treatment or due to degradation via Fenton-induced processes were observed. Findings on degradation kinetics of diclofenac provide an instructive understanding of decomposition rates for recalcitrant pharmaceuticals with respect to their chemical structure. Accordingly, conclusions can be drawn for further development and a first risk assessment of the method which can also be applied towards other AOPs that rely on the generation of hydroxyl radicals. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Direct observation of unimolecular decay of CH{sub 3}CH{sub 2}CHOO Criegee intermediates to OH radical products

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Yi; Liu, Fang; Lester, Marsha I., E-mail: milester@sas.upenn.edu [Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323 (United States); Klippenstein, Stephen J. [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2016-07-28

    The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH{sub 3}CH{sub 2}CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice–Ramsperger–Kassel–Marcus calculations of the microcanonical unimolecular decay rate for CH{sub 3}CH{sub 2}CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantly to the decay rate. Infrared transitions of CH{sub 3}CH{sub 2}CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH{sub 3}CH{sub 2}CHOO of ca. 10{sup 7} s{sup −1}, which are slower than those obtained for syn-CH{sub 3}CHOO or (CH{sub 3}){sub 2}COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH{sub 3}CH{sub 2}CHOO under atmospheric conditions, giving a rate of 279 s{sup −1} at 298 K.

  15. Exploring the chemical kinetics of partially oxidized intermediates by combining experiments, theory, and kinetic modeling.

    Science.gov (United States)

    Hoyermann, Karlheinz; Mauß, Fabian; Olzmann, Matthias; Welz, Oliver; Zeuch, Thomas

    2017-07-19

    Partially oxidized intermediates play a central role in combustion and atmospheric chemistry. In this perspective, we focus on the chemical kinetics of alkoxy radicals, peroxy radicals, and Criegee intermediates, which are key species in both combustion and atmospheric environments. These reactive intermediates feature a broad spectrum of chemical diversity. Their reactivity is central to our understanding of how volatile organic compounds are degraded in the atmosphere and converted into secondary organic aerosol. Moreover, they sensitively determine ignition timing in internal combustion engines. The intention of this perspective article is to provide the reader with information about the general mechanisms of reactions initiated by addition of atomic and molecular oxygen to alkyl radicals and ozone to alkenes. We will focus on critical branching points in the subsequent reaction mechanisms and discuss them from a consistent point of view. As a first example of our integrated approach, we will show how experiment, theory, and kinetic modeling have been successfully combined in the first infrared detection of Criegee intermediates during the gas phase ozonolysis. As a second example, we will examine the ignition timing of n-heptane/air mixtures at low and intermediate temperatures. Here, we present a reduced, fuel size independent kinetic model of the complex chemistry initiated by peroxy radicals that has been successfully applied to simulate standard n-heptane combustion experiments.

  16. Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III Reaction Intermediate Models of Peroxidase Enzymes

    Directory of Open Access Journals (Sweden)

    Samuel Hernández Anzaldo

    2016-06-01

    Full Text Available The spectroscopic and kinetic characterization of two intermediates from the H2O2 oxidation of three dimethyl ester [(proto, (meso, (deuteroporphyrinato (picdien]Fe(III complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III quantum mixed spin (qms ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1–3 + guaiacol + H2O2 → oxidation guaiacol products. The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III and H2O2, resulting in only two types of kinetics that were developed during the first 0–4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III family with the ligand picdien [N,N’-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, 1H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

  17. 4-Amino-3H-pyrimidin-2-one ('isocytosine') is a short-lived non-radical intermediate formed in the pulse radiolysis of cytosine in aqueous solution

    International Nuclear Information System (INIS)

    Nien Schuchmann, Man; Naumov, Sergej; Schuchmann, Heinz-Peter; Sonntag, Justus von; Sonntag, Clemens von

    2005-01-01

    In the pulse radiolysis of 2'-deoxycytidine (dCyd) in N 2 O-saturated solutions containing 0.5M tertiary butanol to completely scavenge the water radicals, a short-lived intermediate (λmax=287nm) is observed by UV spectroscopy which is attributed to dCydH + , generated in the reaction of dCyd with H + formed during the pulse. By reacting with OH - , which is formed in the pulse in amounts matching that of H + , this intermediate disappears in the μs time range without a change of the spectrum. Similarly, cytosine (Cyt) gives rise to CytH + which, in contrast, in part transforms into another species (λmax=286nm) which can be assigned to isocytosine 1, 4-amino-3H-pyrimidin-2-one, a tautomer of Cyt which is formed by two routes (i) deprotonation of CytH + at N(1) by OH - and (ii) deprotonation of Cyt and reprotonation of the Cyt anion by water at N(3). Compared to Cyt, 1 is richer in Gibbs' free enthalpy by 14kJmol -1 . Its presence in low equilibrium concentrations has also been observed by conventional UV spectroscopy, making use of the increase of its equilibrium concentration with increasing temperature. From these data, an absorption coefficient of 3.3x10 4 dm 3 mol -1 cm -1 at 286nm has been calculated. Supporting quantum chemical calculations are also reported

  18. Experimental studies of the kinetics of small polyatomic free radicals in combustion reactions; Moniatomisten radikaalien kinetiikka palamisreaktioissa, kokeellinen tutkimus

    Energy Technology Data Exchange (ETDEWEB)

    Seetula, J. [Helsinki Univ. (Finland). Lab. of Physical Chemistry

    1996-12-01

    The kinetics of the reactions of CH{sub 2}Cl, CHClBr, CH{sub 3}CCl{sub 2} and CCl{sub 3}, with Cl{sub 2} has been investigated in a tubular reactor coupled to a photoionization mass spectrometer. The radicals of interest, R, were generated homogeneously in the reactor by pulse 248 nm exciplex laser photolysis. The decay of R was monitored as a function of Cl{sub 2} concentration under pseudo-first-order condition to determine the rate constant as a function of temperature pressure. The reactions were studied separately over a temperature range up to a temperature of 873 K. The rate constants of CH{sub 2}Cl, CHClBr and CH{sub 3}CCl{sub 2} radicals determined were fitted to three-parameter Arrhenius-type expression (with units of cm{sup 3} molecule{sup -1} s{sup -1}): k(CH{sub 2}Cl) = 1.05x10{sup -16} x (T){sup 1.4} x exp(-357 J mol{sup -1} / RT), k(CHClBr) = 5.83x10{sup -20} x (T){sup 2.3} x exp(-300 J mol{sup -1}/ RT) and k(CH{sub 3}CCl{sub 2}) 1.10x10{sup -}2{sup 6} x (T){sup 4.3} x exp(15000 J mol{sup -1}/ RT). The rate constants CCl{sub 3} radical were fitted to a two-parameter Arrhenius expression (units in cm{sup 3} molecule{sup -1} s{sup -1}): k(CCl{sub 3}) = (8.1 +- 6.7)10{sup -l3} exp[-(25.0 +- 8.7) kJ mol{sup -1}/ RT]. An Arrhenius expression for the reaction of Cl+CCl{sub 4} -> <- CCl{sub 3}+Cl{sub 2} is also obtained from the kinetics of the reaction of CCl{sub 3} radical with Cl{sub 2} combined with the known heat of formation and entropy values of CCl{sub 3} free radical to be as follows (in units cm{sup 3} molecule{sup -1-}5 s{sup -1}): k(Cl+CCl{sub 4}) = (3.9 + 3.2)10{sup -10} exp[-(71 + 9) kJ mol{sup -1}/ RT]. The error limits stated are l{sigma}+Student`s t and base on statistical uncertainties only. (author)

  19. Total free radical species and oxidation equivalent in polluted air.

    Science.gov (United States)

    Wang, Guoying; Jia, Shiming; Niu, Xiuli; Tian, Haoqi; Liu, Yanrong; Chen, Xuefu; Li, Lan; Zhang, Yuanhang; Shi, Gaofeng

    2017-12-31

    Free radicals are the most important chemical intermediate or agent of the atmosphere and influenced by thousands of reactants. The free radicals determine the oxidizing power of the polluted air. Various gases present in smog or haze are oxidants and induce organ and cellular damage via generation of free radical species. At present, however, the high variability of total free radicals in polluted air has prevented the detection of possible trends or distributions in the concentration of those species. The total free radicals are a kind of contaminants with colorless, tasteless characteristics, and almost imperceptible by human body. Here we present total free radical detection and distribution characteristics, and analyze the effects of total free radicals in polluted air on human health. We find that the total free radical values can be described by not only a linear dependence on ozone at higher temperature period, but also a linear delay dependence on particulate matter at lower temperature period throughout the measurement period. The total free radical species distribution is decrease from west to east in Lanzhou, which closely related to the distribution of the air pollutants. The total free radical oxidation capacity in polluted air roughly matches the effects of tobacco smoke produced by the incomplete combustion of a controlled amount of tobacco in a smoke chamber. A relatively unsophisticated chromatographic fingerprint similarity is used for indicating preliminarily the effect of total free radicals in polluted air on human health. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Kinetics and mechanisms of elementary chemical processes of importance in combustion

    International Nuclear Information System (INIS)

    Munk, J.; Pagsberg, P.; Ratajczak, E.; Sztuba, B.; Sillesen, A.

    1988-01-01

    The technique of pulse radiolysis combined with transient ultraviolet absorption spectrophotometry has been employed in spectrokinetic studies of shortlived free radical intermediates of importance in combustion. Various source reactions for vinyl, propargyl and carboxyl radicals have been investigated and the UV-spectra of these radicals have been recorded. The spectral features have been utilized in kinetic studies of the self-reactions of the radicals and the reactions with oxygen. Kinetic results on the reaction NO + NH 2 are also reported. 10 refs. (author)

  1. Persistent free radicals, heavy metals and PAHs generated in particulate soot emissions and residue ash from controlled combustion of common types of plastic

    International Nuclear Information System (INIS)

    Valavanidis, Athanasios; Iliopoulos, Nikiforos; Gotsis, George; Fiotakis, Konstantinos

    2008-01-01

    The production and use of polymeric materials worldwide has reached levels of 150 million tonnes per year, and the majority of plastic materials are discarded in waste landfills where are burned generating toxic emissions. In the present study we conducted laboratory experiments for batch combustion/burning of commercial polymeric materials, simulating conditions of open fire combustion, with the purpose to analyze their emissions for chemical characteristics of toxicological importance. We used common types of plastic materials: poly(vinyl chloride) (PVC), low and high density poly(ethylene) (LDPE, HDPE), poly(styrene) (PS), poly(propylene) (PP) and poly(ethylene terephthalate) (PET). Samples of particulate smoke (soot) collected on filters and residue solid ash produced by controlled burning conditions at 600-750 deg. C are used for analysis. Emissions of particulate matter, persistent free radicals embedded in the carbonaceous polymeric matrix, heavy metals, other elements and PAHs were determined in both types of samples. Results showed that all plastics burned easily generating charred residue solid ash and black airborne particulate smoke. Persistent carbon- and oxygen-centered radicals, known for their toxic effects in inhalable airborne particles, were detected in both particulate smoke emissions and residue solid ash. Concentrations of heavy metals and other elements (determined by Inductively Coupled Plasma Emission Spectrometry, ICP, method) were measured in the airborne soot and residue ash. Toxic heavy metals, such as Pb, Zn, Cr, Ni, and Cd were relatively at were found at low concentrations. High concentrations were found for some lithophilic elements, such as Na, Ca, Mg, Si and Al in particulate soot and residue solid ash. Measurements of PAHs showed that low molecular weight PAHs were at higher concentrations in the airborne particulate soot than in the residue solid ash for all types of plastic. Higher-ringed PAHs were detected at higher

  2. Persistent free radicals, heavy metals and PAHs generated in particulate soot emissions and residue ash from controlled combustion of common types of plastic.

    Science.gov (United States)

    Valavanidis, Athanasios; Iliopoulos, Nikiforos; Gotsis, George; Fiotakis, Konstantinos

    2008-08-15

    The production and use of polymeric materials worldwide has reached levels of 150 million tonnes per year, and the majority of plastic materials are discarded in waste landfills where are burned generating toxic emissions. In the present study we conducted laboratory experiments for batch combustion/burning of commercial polymeric materials, simulating conditions of open fire combustion, with the purpose to analyze their emissions for chemical characteristics of toxicological importance. We used common types of plastic materials: poly(vinyl chloride) (PVC), low and high density poly(ethylene) (LDPE, HDPE), poly(styrene) (PS), poly(propylene) (PP) and poly(ethylene terephthalate) (PET). Samples of particulate smoke (soot) collected on filters and residue solid ash produced by controlled burning conditions at 600-750 degrees C are used for analysis. Emissions of particulate matter, persistent free radicals embedded in the carbonaceous polymeric matrix, heavy metals, other elements and PAHs were determined in both types of samples. Results showed that all plastics burned easily generating charred residue solid ash and black airborne particulate smoke. Persistent carbon- and oxygen-centered radicals, known for their toxic effects in inhalable airborne particles, were detected in both particulate smoke emissions and residue solid ash. Concentrations of heavy metals and other elements (determined by Inductively Coupled Plasma Emission Spectrometry, ICP, method) were measured in the airborne soot and residue ash. Toxic heavy metals, such as Pb, Zn, Cr, Ni, and Cd were relatively at were found at low concentrations. High concentrations were found for some lithophilic elements, such as Na, Ca, Mg, Si and Al in particulate soot and residue solid ash. Measurements of PAHs showed that low molecular weight PAHs were at higher concentrations in the airborne particulate soot than in the residue solid ash for all types of plastic. Higher-ringed PAHs were detected at higher

  3. Broadband Microwave Study of Reaction Intermediates and Products Through the Pyrolysis of Oxygenated Biofuels

    Science.gov (United States)

    Abeysekera, Chamara; Hernandez-Castillo, Alicia O.; Fritz, Sean; Zwier, Timothy S.

    2017-06-01

    The rapidly growing list of potential plant-derived biofuels creates a challenge for the scientific community to provide a molecular-scale understanding of their combustion. Development of accurate combustion models rests on a foundation of experimental data on the kinetics and product branching ratios of their individual reaction steps. Therefore, new spectroscopic tools are necessary to selectively detect and characterize fuel components and reactive intermediates generated by pyrolysis and combustion. Substituted furans, including furanic ethers, are considered second-generation biofuel candidates. Following the work of the Ellison group, an 8-18 GHz microwave study was carried out on the unimolecular and bimolecular decomposition of the smallest furanic ether, 2-methoxy furan, and it`s pyrolysis intermediate, the 2-furanyloxy radical, formed in a high-temperature pyrolysis source coupled to a supersonic expansion. Details of the experimental setup and analysis of the spectrum of the radical will be discussed.

  4. Clinical Validation of the 2005 ISUP Gleason Grading System in a Cohort of Intermediate and High Risk Men Undergoing Radical Prostatectomy.

    Directory of Open Access Journals (Sweden)

    Sheila F Faraj

    Full Text Available In 2005, the International Society of Urological Pathology (ISUP introduced several modifications to the original Gleason system that were intended to enhance the prognostic power of Gleason score (GS. The objective of this study was to clinically validate the 2005 ISUP Gleason grading system for its ability to detect metastasis. We queried our institutional RP database for men with NCCN clinically localized intermediate to high-risk disease undergoing radical prostatectomy (RP between 1992 and 2010 with no additional treatment until the time of metastatic progression. A case-cohort design was utilized. A total of 333 available RP samples were re-reviewed and GS was reassigned per the 2005 ISUP Gleason system. Cumulative incidence of metastasis was 0%, 8.4%, 24.5% and 44.4% among specimens that were downgraded, unchanged, had one point GS increase and two point GS increase, respectively. The hazard ratio for metastasis raised in GS 8 and 9 compared to GS 7 from 2.77 and 5.91 to 3.49 and 9.31, respectively. The survival c-index of GS increased from 0.70 to 0.80 when samples were re-graded at 5 years post RP. The c-index of the reassigned GS was higher than the original GS (0.77 vs 0.64 for predicting PCSM at 10 years post RP. The regraded GS improved the prediction of metastasis and PCSM. This validates the updated Gleason grading system using an unambiguous clinical endpoint and highlights the need for reassignment of Gleason grading according to 2005 ISUP system when considering comparisons of novel biomarkers to clinicopathological variables in archival cohorts.

  5. Infrared absorption spectroscopy and chemical kinetics of free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Curl, R.F.; Glass, G.P. [Rice Univ., Houston, TX (United States)

    1993-12-01

    This research is directed at the detection, monitoring, and study of chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. During the last year, infrared kinetic spectroscopy using excimer laser flash photolysis and color-center laser probing has been employed to study the high resolution spectrum of HCCN, the rate constant of the reaction between ethynyl (C{sub 2}H) radical and H{sub 2} in the temperature region between 295 and 875 K, and the recombination rate of propargyl (CH{sub 2}CCH) at room temperature.

  6. Utility of Risk Models in Decision Making After Radical Prostatectomy: Lessons from a Natural History Cohort of Intermediate- and High-Risk Men.

    Science.gov (United States)

    Ross, Ashley E; Yousefi, Kasra; Davicioni, Elai; Ghadessi, Mercedeh; Johnson, Michael H; Sundi, Debasish; Tosoian, Jeffery J; Han, Misop; Humphreys, Elizabeth B; Partin, Alan W; Walsh, Patrick C; Trock, Bruce J; Schaeffer, Edward M

    2016-03-01

    Current guidelines suggest adjuvant radiation therapy for men with adverse pathologic features (APFs) at radical prostatectomy (RP). We examine at-risk men treated only with RP until the time of metastasis. To evaluate whether clinicopathologic risk models can help guide postoperative therapeutic decision making. Men with National Comprehensive Cancer Network intermediate- or high-risk localized prostate cancer undergoing RP in the prostate-specific antigen (PSA) era were identified (n=3089). Only men with initial undetectable PSA after surgery and who received no therapy prior to metastasis were included. APFs were defined as pT3 disease or positive surgical margins. Area under the receiver operating characteristic curve (AUC) for time to event data was used to measure the discrimination performance of the risk factors. Cumulative incidence curves were constructed using Fine and Gray competing risks analysis to estimate the risk of biochemical recurrence (BCR) or metastasis, taking censoring and death due to other causes into consideration. Overall, 43% of the cohort (n=1327) had APFs at RP. Median follow-up for censored patients was 5 yr. Cumulative incidence of metastasis was 6% at 10 yr after RP for all patients. Cumulative incidence of metastasis among men with APFs was 7.5% at 10 yr after RP. Among men with BCR, the incidence of metastasis was 38% 5 yr after BCR. At 10 yr after RP, time-dependent AUC for predicting metastasis by Cancer of the Prostate Risk Assessment Postsurgical or Eggener risk models was 0.81 (95% confidence interval [CI], 0.72-0.97) and 0.78 (95% CI, 0.67-0.97) in the APF population, respectively. At 5 yr after BCR, these values were lower (0.58 [95% CI, 0.50-0.66] and 0.70 [95% CI, 0.63-0.76]) among those who developed BCR. Use of risk model cut points could substantially reduce overtreatment while minimally increasing undertreatment (ie, use of an Eggener cut point of 2.5% for treatment of men with APFs would spare 46% from treatment

  7. Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions.

    Science.gov (United States)

    Williams, Peggy E; Marshall, David L; Poad, Berwyck L J; Narreddula, Venkateswara R; Kirk, Benjamin B; Trevitt, Adam J; Blanksby, Stephen J

    2018-06-04

    In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions. Graphical Abstract.

  8. An investigation of late-combustion soot burnout in a DI diesel engine using simultaneous planar imaging of soot and OH radical

    Energy Technology Data Exchange (ETDEWEB)

    John E. Dec; Peter L. Kelly-Zion

    1999-10-01

    Diesel engine design continues to be driven by the need to improve performance while at the same time achieving further reductions in emissions. The development of new designs to accomplish these goals requires an understanding of how the emissions are produced in the engine. Laser-imaging diagnostics are uniquely capable of providing this information, and the understanding of diesel combustion and emissions formation has been advanced considerably in recent years by their application. However, previous studies have generally focused on the early and middle stages of diesel combustion. These previous laser-imaging studies do provide important insight into the soot formation and oxidation processes during the main combustion event. They indicate that prior to the end of injection, soot formation is initiated by fuel-rich premixed combustion (equivalence ratio > 4) near the upstream limit of the luminous portion of the reacting fuel jet. The soot is then oxidized at the diffusion flame around the periphery of the luminous plume. Under typical diesel engine conditions, the diffusion flame does not burn the remaining fuel and soot as rapidly as it is supplied, resulting in an expanding region of rich combustion products and soot. This is evident in natural emission images by the increasing size of the luminous soot cloud prior to the end of injection. Hence, the amount of soot in the combustion chamber typically increases until shortly after the end of fuel injection, at which time the main soot formation period ends and the burnout phase begins. Sampling valve and two-color pyrometry data indicate that the vast majority (more than 90%) of the soot formed is oxidized before combustion ends; however, it is generally thought that a small fraction of this soot from the main combustion zones is not consumed and is the source of tail pipe soot emissions.

  9. Fifteenth combustion research conference

    International Nuclear Information System (INIS)

    1993-01-01

    The BES research efforts cover chemical reaction theory, experimental dynamics and spectroscopy, thermodynamics of combustion intermediates, chemical kinetics, reaction mechanisms, combustion diagnostics, and fluid dynamics and chemically reacting flows. 98 papers and abstracts are included. Separate abstracts were prepared for the papers

  10. Oxidation of SO2 by stabilized Criegee intermediate (sCI radicals as a crucial source for atmospheric sulfuric acid concentrations

    Directory of Open Access Journals (Sweden)

    M. Boy

    2013-04-01

    Full Text Available The effect of increased reaction rates of stabilized Criegee intermediates (sCIs with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012 increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO with SO2 according to the values recommended by Welz et al. (2012 increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

  11. Photodissociation spectroscopy and dynamics of free radicals, clusters, and ions

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Hyeon [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    The photodissociation spectroscopy and dynamics of free radicals and ions is studied to characterize the dissociative electronic states in these species. To accomplish this, a special method of radical production, based on the photodetachment of the corresponding negative ion, has been combined with the technique of fast beam photofragment translational spectroscopy. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states. Branching ratios to various product channels, the translational energy distributions of the fragments, and bond dissociation energies are then determined at selected photon energies. The detailed picture of photodissociation dynamics is provided with the aid of ab initio calculations and a statistical model to interpret the observed data. Important reaction intermediates in combustion reactions have been studied: CCO, C2H5O, and linear Cn (n = 4--6).

  12. Fuels and Combustion

    KAUST Repository

    Johansson, Bengt

    2016-08-17

    This chapter discusses the combustion processes and the link to the fuel properties that are suitable for them. It describes the basic three concepts, including spark ignition (SI) and compression ignition (CI), and homogeneous charge compression ignition (HCCI). The fuel used in a CI engine is vastly different from that in an SI engine. In an SI engine, the fuel should sustain high pressure and temperature without autoignition. Apart from the dominating SI and CI engines, it is also possible to operate with a type of combustion: autoignition. With HCCI, the fuel and air are fully premixed before combustion as in the SI engine, but combustion is started by the increased pressure and temperature during the compression stroke. Apart from the three combustion processes, there are also a few combined or intermediate concepts, such as Spark-Assisted Compression Ignition (SACI). Those concepts are discussed in terms of the requirements of fuel properties.

  13. Fuels and Combustion

    KAUST Repository

    Johansson, Bengt

    2016-01-01

    This chapter discusses the combustion processes and the link to the fuel properties that are suitable for them. It describes the basic three concepts, including spark ignition (SI) and compression ignition (CI), and homogeneous charge compression ignition (HCCI). The fuel used in a CI engine is vastly different from that in an SI engine. In an SI engine, the fuel should sustain high pressure and temperature without autoignition. Apart from the dominating SI and CI engines, it is also possible to operate with a type of combustion: autoignition. With HCCI, the fuel and air are fully premixed before combustion as in the SI engine, but combustion is started by the increased pressure and temperature during the compression stroke. Apart from the three combustion processes, there are also a few combined or intermediate concepts, such as Spark-Assisted Compression Ignition (SACI). Those concepts are discussed in terms of the requirements of fuel properties.

  14. Particle size-dependent radical generation from wildland fire smoke

    International Nuclear Information System (INIS)

    Leonard, Stephen S.; Castranova, Vince; Chen, Bean T.; Schwegler-Berry, Diane; Hoover, Mark; Piacitelli, Chris; Gaughan, Denise M.

    2007-01-01

    Firefighting, along with construction, mining and agriculture, ranks among the most dangerous occupations. In addition, the work environment of firefighters is unlike that of any other occupation, not only because of the obvious physical hazards but also due to the respiratory and systemic health hazards of smoke inhalation resulting from combustion. A significant amount of research has been devoted to studying municipal firefighters; however, these studies may not be useful in wildland firefighter exposures, because the two work environments are so different. Not only are wildland firefighters exposed to different combustion products, but their exposure profiles are different. The combustion products wildland firefighters are exposed to can vary greatly in characteristics due to the type and amount of material being burned, soil conditions, temperature and exposure time. Smoke inhalation is one of the greatest concerns for firefighter health and it has been shown that the smoke consists of a large number of particles. These smoke particles contain intermediates of hydrogen, carbon and oxygen free radicals, which may pose a potential health risk. Our investigation looked into the involvement of free radicals in smoke toxicity and the relationship between particle size and radical generation. Samples were collected in discrete aerodynamic particle sizes from a wildfire in Alaska, preserved and then shipped to our laboratory for analysis. Electron spin resonance was used to measure carbon-centered as well as hydroxyl radicals produced by a Fenton-like reaction with wildfire smoke. Further study of reactive oxygen species was conducted using analysis of cellular H 2 O 2 generation, lipid peroxidation of cellular membranes and DNA damage. Results demonstrate that coarse size-range particles contained more carbon radicals per unit mass than the ultrafine particles; however, the ultrafine particles generated more ·OH radicals in the acellular Fenton-like reaction. The

  15. Photoisomerization and photodissociation dynamics of reactive free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Bise, Ryan T. [Univ. of California, Berkeley, CA (United States)

    2000-08-01

    The photofragmentation pathways of chemically reactive free radicals have been examined using the technique of fast beam photofragment translational spectroscopy. Measurements of the photodissociation cross-sections, product branching ratios, product state energy distributions, and angular distributions provide insight into the excited state potential energy surfaces and nonadiabatic processes involved in the dissociation mechanisms. Photodissociation spectroscopy and dynamics of the predissociative $\\tilde{A}$2A1 and $\\tilde{B}$2A2 states of CH3S have been investigated. At all photon energies, CH3 + S(3Pj), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH3 umbrella mode and the S(3Pj) fine-structure distribution from which the nature of the coupled repulsive surfaces is inferred. Dissociation rates are deduced from the photofragment angular distributions, which depend intimately on the degree of vibrational excitation in the C-S stretch. Nitrogen combustion radicals, NCN, CNN and HNCN have also been studied. For all three radicals, the elimination of molecular nitrogen is the primary reaction channel. Excitation to linear excited triplet and singlet electronic states of the NCN radical generates resolved vibrational structure of the N2 photofragment. The relatively low fragment rotational excitation suggests dissociation via a symmetric C2V transition state. Resolved vibrational structure of the N2 photofragment is also observed in the photodissociation of the HNCN radical. The fragment vibrational and rotational distributions broaden with increased excitation energy. Simple dissociation models suggest that the HNCN radical isomerizes to a cyclic intermediate (c-HCNN) which then dissociates via a tight cyclic

  16. Intermediate treatments

    Science.gov (United States)

    John R. Jones; Wayne D. Shepperd

    1985-01-01

    Intermediate treatments are those applied after a new stand is successfully established and before the final harvest. These include not only intermediate cuttings - primarily thinning - but also fertilization, irrigation, and protection of the stand from damaging agents.

  17. 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.

  18. A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds-Low Temperature Growth of Polycyclic Aromatic Hydrocarbons.

    Science.gov (United States)

    Thomas, Aaron M; Lucas, Michael; Yang, Tao; Kaiser, Ralf I; Fuentes, Luis; Belisario-Lara, Daniel; Mebel, Alexander M

    2017-08-05

    The hydrogen-abstraction/acetylene-addition mechanism has been fundamental to unravelling the synthesis of polycyclic aromatic hydrocarbons (PAHs) detected in combustion flames and carbonaceous meteorites like Orgueil and Murchison. However, the fundamental reaction pathways accounting for the synthesis of complex PAHs, such as the tricyclic anthracene and phenanthrene along with their dihydrogenated counterparts, remain elusive to date. By investigating the hitherto unknown chemistry of the 1-naphthyl radical with 1,3-butadiene, we reveal a facile barrierless synthesis of dihydrophenanthrene adaptable to low temperatures. These aryl-type radical additions to conjugated hydrocarbons via resonantly stabilized free-radical intermediates defy conventional wisdom that PAH growth is predominantly a high-temperature phenomenon and thus may represent an overlooked path to PAHs as complex as coronene and corannulene in cold regions of the interstellar medium like in the Taurus Molecular Cloud. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals. Final Performance Report, August 1, 1985--July 31, 1994

    Science.gov (United States)

    Curl, R. F.; Glass, G. P.

    1995-06-01

    This research was directed at the detection, monitoring, and study (by infrared absorption spectroscopy) of the chemical kinetic behavior of small free radical species thought to be important intermediates in combustion. The work typically progressed from the detection and analysis of the infrared spectrum of combustion radical to the utilization of the infrared spectrum thus obtained in the investigation of chemical kinetics of the radical species. The methodology employed was infrared kinetic spectroscopy. In this technique the radical is produced by UV flash photolysis using an excimer laser and then its transient infrared absorption is observed using a single frequency cw laser as the source of the infrared probe light. When the probe laser frequency is near the center of an absorption line of the radical produced by the flash, the transient infrared absorption rises rapidly and then decays as the radical reacts with the precursor or with substances introduced for the purpose of studying the reaction kinetics or with itself. The decay times observed in these studies varied from less than one microsecond to more than one millisecond. By choosing appropriate time windows after the flash and the average infrared detector signal in a window as data channels, the infrared spectrum of the radical may be obtained. By locking the infrared probe laser to the center of the absorption line and measuring the rate of decay of the transient infrared absorption signal as the chemical composition of the gas mixture is varied, the chemical kinetics of the radical may be investigated. In what follows the systems investigated and the results obtained are outlined.

  20. Studies of combustion kinetics and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Gutman, D. [Catholic Univ. of America, Washington, DC (United States)

    1993-12-01

    The objective of the current research is to gain new quantitative knowledge of the kinetics and mechanisms of polyatomic free radicals which are important in hydrocarbon combustion processes. The special facility designed and built for these (which includes a heatable tubular reactor coupled to a photoionization mass spectrometer) is continually being improved. Where possible, these experimental studies are coupled with theoretical ones, sometimes conducted in collaboration with others, to obtain an improved understanding of the factors determining reactivity. The decomposition of acetyl radicals, isopropyl radicals, and n-propyl radicals have been studied as well as the oxidation of methylpropargyl radicals.

  1. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals

    Energy Technology Data Exchange (ETDEWEB)

    Curl, Robert F; Glass, Graham

    2004-11-01

    This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

  2. Manifold methods for methane combustion

    Energy Technology Data Exchange (ETDEWEB)

    Yang, B.; Pope, S.B. [Cornell Univ., Ithaca, NY (United States)

    1995-10-01

    Great progresses have been made in combustion research, especially, the computation of laminar flames and the probability density function (PDF) method in turbulent combustion. For one-dimensional laminar flames, by considering the transport mechanism, the detailed chemical kinetic mechanism and the interactions between these two basic processes, today it is a routine matter to calculate flame velocities, extinction, ignition, temperature, and species distributions from the governing equations. Results are in good agreement with those obtained for experiments. However, for turbulent combustion, because of the complexities of turbulent flow, chemical reactions, and the interaction between them, in the foreseeable future, it is impossible to calculate the combustion flow field by directly integrating the basic governing equations. So averaging and modeling are necessary in turbulent combustion studies. Averaging, on one hand, simplifies turbulent combustion calculations, on the other hand, it introduces the infamous closure problems, especially the closure problem with chemical reaction terms. Since in PDF calculations of turbulent combustion, the averages of the chemical reaction terms can be calculated, PDF methods overcome the closure problem with the reaction terms. It has been shown that the PDF method is a most promising method to calculate turbulent combustion. PDF methods have been successfully employed to calculate laboratory turbulent flames: they can predict phenomena such as super equilibrium radical levels, and local extinction. Because of these advantages, PDF methods are becoming used increasingly in industry combustor codes.

  3. The Rise of Radicals in Bioinorganic Chemistry

    OpenAIRE

    Gray, Harry B.; Winkler, Jay R.

    2016-01-01

    Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O_2 are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) a...

  4. Combustion engineering

    CERN Document Server

    Ragland, Kenneth W

    2011-01-01

    Introduction to Combustion Engineering The Nature of Combustion Combustion Emissions Global Climate Change Sustainability World Energy Production Structure of the Book   Section I: Basic Concepts Fuels Gaseous Fuels Liquid Fuels Solid Fuels Problems Thermodynamics of Combustion Review of First Law Concepts Properties of Mixtures Combustion StoichiometryChemical EnergyChemical EquilibriumAdiabatic Flame TemperatureChemical Kinetics of CombustionElementary ReactionsChain ReactionsGlobal ReactionsNitric Oxide KineticsReactions at a Solid SurfaceProblemsReferences  Section II: Combustion of Gaseous and Vaporized FuelsFlamesLaminar Premixed FlamesLaminar Flame TheoryTurbulent Premixed FlamesExplosion LimitsDiffusion FlamesGas-Fired Furnaces and BoilersEnergy Balance and EfficiencyFuel SubstitutionResidential Gas BurnersIndustrial Gas BurnersUtility Gas BurnersLow Swirl Gas BurnersPremixed-Charge Engine CombustionIntroduction to the Spark Ignition EngineEngine EfficiencyOne-Zone Model of Combustion in a Piston-...

  5. Intermediate species measurement during iso-butanol auto-ignition

    KAUST Repository

    Ji, Weiqi

    2015-10-01

    © 2015 The Combustion Institute.Published by Elsevier Inc. All rights reserved. This work presents the time histories of intermediate species during the auto-ignition of iso-butanol at high pressure and intermediate temperature conditions obtained using a rapid compression machine and recently developed fast sampling system. Iso-butanol ignition delays were acquired for iso-butanol/O2 mixture with an inert/O2 ratio of 7.26, equivalence ratio of 0.4, in the temperature range of 840-950 K and at pressure of 25 bar. Fast sampling and gas chromatography were used to acquire and quantify the intermediate species during the ignition delay of the same mixture at P = 25.3 bar and T = 905 K. The ignition delay times and quantitative measurements of the mole fraction time histories of methane, ethene, propene, iso-butene, iso-butyraldehyde, iso-butanol, and carbon monoxide were compared with predictions from the detailed mechanisms developed by Sarathy et al., Merchant et al., and Cai et al. It is shown that while the Sarathy mechanism well predicts the overall ignition delay time, it overpredicts ethene by a factor of 6-10, underpredicts iso-butene by a factor of 2, and overpredicts iso-butyraldehyde by a factor of 2. Reaction path and sensitivity analyses were carried out to identify the reactions responsible for the observed inadequacy. The rates of iso-butanol hydrogen atom abstraction by OH radical and the beta-scission reactions of hydroxybutyl radicals were updated based on recently published quantum calculation results. Significant improvements were achieved in predicting ignition delay at high pressures (25 and 30 bar) and the species concentrations of ethene and iso-butene. However, the updated mechanism still overpredicts iso-butyraldehyde concentrations. Also, the updated mechanism degrades the prediction in ignition delay at lower pressure (15 bar) compared to the original mechanism developed by Sarathy et al.

  6. Intermediate species measurement during iso-butanol auto-ignition

    KAUST Repository

    Ji, Weiqi; Zhang, Peng; He, Tanjin; Wang, Zhi; Tao, Ling; He, Xin; Law, Chung K.

    2015-01-01

    © 2015 The Combustion Institute.Published by Elsevier Inc. All rights reserved. This work presents the time histories of intermediate species during the auto-ignition of iso-butanol at high pressure and intermediate temperature conditions obtained using a rapid compression machine and recently developed fast sampling system. Iso-butanol ignition delays were acquired for iso-butanol/O2 mixture with an inert/O2 ratio of 7.26, equivalence ratio of 0.4, in the temperature range of 840-950 K and at pressure of 25 bar. Fast sampling and gas chromatography were used to acquire and quantify the intermediate species during the ignition delay of the same mixture at P = 25.3 bar and T = 905 K. The ignition delay times and quantitative measurements of the mole fraction time histories of methane, ethene, propene, iso-butene, iso-butyraldehyde, iso-butanol, and carbon monoxide were compared with predictions from the detailed mechanisms developed by Sarathy et al., Merchant et al., and Cai et al. It is shown that while the Sarathy mechanism well predicts the overall ignition delay time, it overpredicts ethene by a factor of 6-10, underpredicts iso-butene by a factor of 2, and overpredicts iso-butyraldehyde by a factor of 2. Reaction path and sensitivity analyses were carried out to identify the reactions responsible for the observed inadequacy. The rates of iso-butanol hydrogen atom abstraction by OH radical and the beta-scission reactions of hydroxybutyl radicals were updated based on recently published quantum calculation results. Significant improvements were achieved in predicting ignition delay at high pressures (25 and 30 bar) and the species concentrations of ethene and iso-butene. However, the updated mechanism still overpredicts iso-butyraldehyde concentrations. Also, the updated mechanism degrades the prediction in ignition delay at lower pressure (15 bar) compared to the original mechanism developed by Sarathy et al.

  7. Intermediate Fragment

    DEFF Research Database (Denmark)

    Kruse Aagaard, Anders

    2015-01-01

    This text and its connected exhibition are aiming to reflect both on the thoughts, the processes and the outcome of the design and production of the artefact ‘Intermediate Fragment’ and making as a contemporary architectural tool in general. Intermediate Fragment was made for the exhibition ‘Enga...... of realising an exhibition object was conceived, but expanded, refined and concretised through this process. The context of the work shown here is an interest in a tighter, deeper connection between experimentally obtained material knowledge and architectural design....

  8. Radical Evil

    Directory of Open Access Journals (Sweden)

    Carlos Manrique

    2007-12-01

    Full Text Available There is an aporia in Kant’s analysis of evil: he defines radical evilas an invisible disposition of the will, but he also demands an inferential connection between visible evil actions and this invisible disposition. This inference,however, undermines the radical invisibility of radical evil according to Kant’s own definition of the latter. Noting how this invisibility of moral worth is a distinctive feature of Kant’s approach to the moral problem, the paper then asks why, in the Groundwork, he nonetheless forecloses a question about evil that seems to be consistent with this approach. It is argued that to account for this aporia and this foreclosure, one has to interrogate the way in which the category of religion orients Kant’s incipient philosophy of history in Die Religion.

  9. Photoionization of the OH radical

    International Nuclear Information System (INIS)

    Dehmer, P.M.

    1985-01-01

    The hydroxyl radical (OH) is one of the most thoroughly studied free radicals because of its importance in atmospheric chemistry, combustion processes, and the interstellar medium. Detailed experimental and theoretical studies have been performed on the ground electronic state (X 2 PI/sub i/) and on the four lowest bound excited electronic states (A 2 Σ + , B 2 Σ + , D 2 Σ - , and C 2 Σ + ). However, because it is difficult to distinguish the spectrum of OH from the spectra of the various radical precursors, the absorption spectrum in the wavelength region below 1200 A has not been well characterized. In the present work, the spectrum of OH has been determined in the wavelength region from 750 to 950 A using the technique of photoionization mass spectrometry. This technique allows complete separation of the spectrum of OH from that of the other components of the discharge and permits the unambiguous determination of the spectrum of OH

  10. 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.

  11. An assessment of the dual-mode reactivity controlled compression ignition/conventional diesel combustion capabilities in a EURO VI medium-duty diesel engine fueled with an intermediate ethanol-gasoline blend and biodiesel

    International Nuclear Information System (INIS)

    Benajes, Jesús; García, Antonio; Monsalve-Serrano, Javier; Balloul, Iyad; Pradel, Gérard

    2016-01-01

    Highlights: • Reactivity controlled compression ignition regime utilized from 25% to 35% load. • Dual-mode reduces the regeneration periods of the diesel particulate filter. • The use of near-term available biofuels allows good performance and emissions. • Dual-mode leads to 2% greater efficiency than diesel combustion at high engine speeds. - Abstract: This work investigates the capabilities of the dual-mode reactivity controlled compression ignition/conventional diesel combustion engine operation to cover the full operating range of a EURO VI medium-duty diesel engine with compression ratio of 17.5:1. This concept is based on covering all the engine map switching between the reactivity controlled compression ignition and the conventional diesel combustion operating modes. Specifically, the benefits of reactivity controlled compression ignition combustion are exploited whenever possible according to certain restrictions, while the conventional diesel combustion operation is used to cover the zones of the engine map in which the reactivity controlled compression ignition operation is limited. The experiments were conducted using a single-cylinder research diesel engine derived from the multi-cylinder production engine. In addition, considering the mandatory presence of biofuels in the future context of road transport and the ability of ethanol to be blended with gasoline, the low reactivity fuel used in the study is a blend of 20% ethanol by volume with 80% of 95 octane number gasoline. Moreover, a diesel containing 7% of biodiesel has been used as high reactivity fuel. Firstly, a reactivity controlled compression ignition mapping is performed to check the operational limits of the concept in this engine platform. Later, based on the results, the potential of the dual-mode concept is discussed. Results suggest that, under the constraints imposed, reactivity controlled compression ignition combustion can be utilized between 25% and 35% load. In this region

  12. Pyrimidine nucleobase radical reactivity in DNA and RNA

    Science.gov (United States)

    Greenberg, Marc M.

    2016-11-01

    Nucleobase radicals are major products of the reactions between nucleic acids and hydroxyl radical, which is produced via the indirect effect of ionizing radiation. The nucleobase radicals also result from hydration of cation radicals that are produced via the direct effect of ionizing radiation. The role that nucleobase radicals play in strand scission has been investigated indirectly using ionizing radiation to generate them. More recently, the reactivity of nucleobase radicals resulting from formal hydrogen atom or hydroxyl radical addition to pyrimidines has been studied by independently generating the reactive intermediates via UV-photolysis of synthetic precursors. This approach has provided control over where the reactive intermediates are produced within biopolymers and facilitated studying their reactivity. The contributions to our understanding of pyrimidine nucleobase radical reactivity by this approach are summarized.

  13. Combustion physics

    Science.gov (United States)

    Jones, A. R.

    1985-11-01

    Over 90% of our energy comes from combustion. By the year 2000 the figure will still be 80%, even allowing for nuclear and alternative energy sources. There are many familiar examples of combustion use, both domestic and industrial. These range from the Bunsen burner to large flares, from small combustion chambers, such as those in car engines, to industrial furnaces for steel manufacture or the generation of megawatts of electricity. There are also fires and explosions. The bountiful energy release from combustion, however, brings its problems, prominent among which are diminishing fuel resources and pollution. Combustion science is directed towards finding ways of improving efficiency and reducing pollution. One may ask, since combustion is a chemical reaction, why physics is involved: the answer is in three parts. First, chemicals cannot react unless they come together. In most flames the fuel and air are initially separate. The chemical reaction in the gas phase is very fast compared with the rate of mixing. Thus, once the fuel and air are mixed the reaction can be considered to occur instantaneously and fluid mechanics limits the rate of burning. Secondly, thermodynamics and heat transfer determine the thermal properties of the combustion products. Heat transfer also plays a role by preheating the reactants and is essential to extracting useful work. Fluid mechanics is relevant if work is to be performed directly, as in a turbine. Finally, physical methods, including electric probes, acoustics, optics, spectroscopy and pyrometry, are used to examine flames. The article is concerned mainly with how physics is used to improve the efficiency of combustion.

  14. Staged combustion - main method for suppressing nitrogen oxides in pulverized-coal fired boilers

    Energy Technology Data Exchange (ETDEWEB)

    Kotler, V.R. (Vsesoyuznyi Teplotekhnicheskii Institut (USSR))

    1989-08-01

    Describes principles behind staged combustion, which is based on organizing furnace operations so that only part of the air from the fuel is taken into the furnace. The remaining air, which is needed for combustion, is fed as a tertiary blast jet into the intermediate flame zone. Following inflammation and combustion of the volatile matter, the oxygen concentration in the flame drops sharply causing a retardation of the oxidation reactions forming NO and an intensification of the reactions causing the nitrogen-containing radicals NH{sub i} and CN to be converted into N{sub 2}. When the reducing agents CO, H{sub 2} and CH{sub 4} are present in certain flame zones, even the nitrogen oxide is reduced to N{sub 2}. The NO concentrations in the flame are reduced until the jet of tertiary air is introduced. Discusses with reference to practice in the USA and Western Europe how to achieve maximum effect of this method for different types of boiler and presents the results of observations of the introduction of staged combustion to the BKZ-210-140 boiler burning Kuznetsk gassy coal. 5 refs.

  15. Radical fashion and radical fashion innovation

    NARCIS (Netherlands)

    Zhang, D.; Benedetto, Di A.C.

    2010-01-01

    This is a study of the related concepts of radical fashion and radical fashion innovation. Radical fashions are defined here as those that may never enter the market at all, and exist primarily on runway shows, in exhibitions and in publicity; by contrast, radical fashion innovations may be very

  16. Intermediate uveitis

    Directory of Open Access Journals (Sweden)

    Babu B

    2010-01-01

    Full Text Available Intermediate uveitis (IU is described as inflammation in the anterior vitreous, ciliary body and the peripheral retina. In the Standardization of Uveitis Nomenclature (SUN working group′s international workshop for reporting clinical data the consensus reached was that the term IU should be used for that subset of uveitis where the vitreous is the major site of the inflammation and if there is an associated infection (for example, Lyme disease or systemic disease (for example, sarcoidosis. The diagnostic term pars planitis should be used only for that subset of IU where there is snow bank or snowball formation occurring in the absence of an associated infection or systemic disease (that is, "idiopathic". This article discusses the clinical features, etiology, pathogenesis, investigations and treatment of IU.

  17. A method for determining the completeness of fuel combustion

    Energy Technology Data Exchange (ETDEWEB)

    Tavger, M.D.; Chepkin, V.M.; Gruzdev, V.N.; Talantov, A.V.

    1982-01-01

    The current of conductivity (ionization) of gaseous combustion products, which forms with feeding of electric voltage to a special probe, is proposed for determining the completeness of fuel combustion. Here, the charged particles are formed from substances which form in the intermediate stages of the combustion reaction. The volume of charged particles is proportional to the volume of the intermediate substances, whose presence attests to the incompleteness of the combustion reaction. The fullness of fuel combustion is determined from a formula which includes the stoichiometric coefficient, a gas constant, the energy of activation, the characteristics of the chemical activity of the intermediate substances, the coefficient of air excess, the temperature of the combustion products and the conductivity current.

  18. Biofuels combustion.

    Science.gov (United States)

    Westbrook, Charles K

    2013-01-01

    This review describes major features of current research in renewable fuels derived from plants and from fatty acids. Recent and ongoing fundamental studies of biofuel molecular structure, oxidation reactions, and biofuel chemical properties are reviewed, in addition to combustion applications of biofuels in the major types of engines in which biofuels are used. Biofuels and their combustion are compared with combustion features of conventional petroleum-based fuels. Two main classes of biofuels are described, those consisting of small, primarily alcohol, fuels (particularly ethanol, n-butanol, and iso-pentanol) that are used primarily to replace or supplement gasoline and those derived from fatty acids and used primarily to replace or supplement conventional diesel fuels. Research efforts on so-called second- and third-generation biofuels are discussed briefly.

  19. Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

    Science.gov (United States)

    De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

    2005-01-21

    Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

  20. Mixture preparation and combustion in an optically-accessible HCCI, diesel engine; La preparation du melange et de la combustion dans un moteur Diesel, HCCI a acces optique

    Energy Technology Data Exchange (ETDEWEB)

    Kashdan, J.; Bruneaux, G. [Institut Francais du Petrole, 92 - Rueil-Malmaison (France)

    2006-07-01

    Planar laser-induced fluorescence (LIF) imaging techniques have been applied in order to study the mixture preparation and combustion process in a single cylinder, optically-accessible homogeneous charge, compression ignition (HCCI) engine. In particular, the influence of piston bowl geometry on the in-cylinder mixture distribution and subsequent combustion process has been investigated. A new optically-accessible piston design enabled the application of LIF diagnostics directly within the combustion chamber bowl. Firstly, laser-induced exciplex fluorescence (LIEF) was exploited in order to characterise the in-cylinder fuel spray and vapour distribution. Subsequently a detailed study of the two-stage HCCI combustion process was conducted by a combination of direct chemiluminescence imaging, laser-induced fluorescence (LIF) of the intermediate species formaldehyde (CH{sub 2}O) which is present during the cool flame and LIF of the OH radical which is subsequently present in the reaction and burned gas zones at higher temperature. Finally, spectrometry measurements were performed with the objective of determining the origin of the emitting species of the chemiluminescence signal. The experiments were performed on a single cylinder optical engine equipped with a direct-injection, common rail injection system and narrow angle injector. The experimental results presented reveal the significant role of the combustion chamber geometry on the mixture preparation and combustion characteristics for late HCCI injection strategies particularly in such cases where liquid impingement is unavoidable. Planar LIF 355 imaging revealed the presence of the intermediate species formaldehyde allowing the temporal and spatial detection of auto-ignition precursors prior to the signal observed by chemiluminescence in the early stages of the cool flame. Formaldehyde was then rapidly consumed at the start of main combustion which was marked not only by the increase in the main heat release

  1. Spray combustion of biomass-based renewable diesel fuel using multiple injection strategy in a constant volume combustion chamber

    KAUST Repository

    Jing, Wei

    2016-05-26

    Effect of a two-injection strategy associated with a pilot injection on the spray combustion process was investigated under conventional diesel combustion conditions (1000 K and 21% O2 concentration) for a biomass-based renewable diesel fuel, i.e., biomass to liquid (BTL), and a regular No. 2 diesel in a constant volume combustion chamber using multiband flame measurement and two-color pyrometry. The spray combustion flame structure was visualized by using multiband flame measurement to show features of soot formation, high temperature and low temperature reactions, which can be characterized by the narrow-band emissions of radicals or intermediate species such as OH, HCHO, and CH. The objective of this study was to identify the details of multiple injection combustion, including a pilot and a main injection, and to provide further insights on how the two injections interact. For comparison, three injection strategies were considered for both fuels including a two-injection strategy (Case TI), single injection strategy A (Case SA), and single injection strategy B (Case SB). Multiband flame results show a strong interaction, indicated by OH emissions between the pilot injection and the main injection for Case TI while very weak connection is found for the narrow-band emissions acquired through filters with centerlines of 430 nm and 470 nm. A faster flame development is found for the main injection of Case TI compared to Cases SA and SB, which could be due to the high temperature environment and large air entrainment from the pilot injection. A lower soot level is observed for the BTL flame compared to the diesel flame for all three injection types. Case TI has a lower soot level compared to Cases SA and SB for the BTL fuel, while the diesel fuel maintains a similar soot level among all three injection strategies. Soot temperature of Case TI is lower for both fuels, especially for diesel. Based on these results, it is expected that the two-injection strategy could be

  2. Effect of Variant End of Injection Period on Combustion Process of Biodiesel Combustion

    Directory of Open Access Journals (Sweden)

    Khalid Amir

    2016-01-01

    Full Text Available Biodiesel is an alternative fuel as a replacement to the standard diesel fuel in combustion diesel engine. The biodiesel fuel has a significantly influences throughout the combustion process and exhaust emission. The purpose of this research is to investigate the combustion process behavior during the End of Injection (EOI period and operates under variant conditions using Rapid Compression Machine (RCM. Experimental of RCM is used to simulate a combustion process and combustion characteristics of diesel engine combustion. Three types of biodiesel blend which are B5, B10 and B15 were tested at several injection pressures of 80 MPa, 90 MPa and 130 MPa under different ambient temperatures, 750 K to 1100 K. The results of this study showed that the ignition delay slightly reduced with increasing the content of biodiesel blends from B5, B10 and B15 and became more shorten as the injection pressure been enhanced. As the injection pressure increased, the behavior of combustion pressure at end of injection is reduced, radically increased the NOX emission. It is noted that the process of combustion at the end of injection increased as the ambient temperature is rising. In fact, higher initial ambient temperature improved the fuel atomization and mixing process. Under the biodiesel combustion with higher ambient temperature condition, the exhaust emission of CO, O2, and HC became less but increased in NOX emission. Besides, increased in blends of biodiesel ratio are found to enhance the combustion process, resulted a decreased in HC emissions.

  3. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals, Final Technical Report

    Science.gov (United States)

    Curl, Robert F.; Glass, Graham P.

    2004-11-01

    This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

  4. Tubular combustion

    CERN Document Server

    Ishizuka, Satoru

    2014-01-01

    Tubular combustors are cylindrical tubes where flame ignition and propagation occur in a spatially confined, highly controlled environment, in a nearly flat, elongated geometry. This allows for some unique advantages where extremely even heat dispersion is required over a large surface while still maintaining fuel efficiency. Tubular combustors also allow for easy flexibility in type of fuel source, allowing for quick changeover to meet various needs and changing fuel pricing. This new addition to the MP sustainable energy series will provide the most up-to-date research on tubular combustion--some of it only now coming out of private proprietary protection. Plentiful examples of current applications along with a good explanation of background theory will offer readers an invaluable guide on this promising energy technology. Highlights include: * An introduction to the theory of tubular flames * The "how to" of maintaining stability of tubular flames through continuous combustion * Examples of both small-scal...

  5. Advanced Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Holcomb, Gordon R. [NETL

    2013-03-11

    The activity reported in this presentation is to provide the mechanical and physical property information needed to allow rational design, development and/or choice of alloys, manufacturing approaches, and environmental exposure and component life models to enable oxy-fuel combustion boilers to operate at Ultra-Supercritical (up to 650{degrees}C & between 22-30 MPa) and/or Advanced Ultra-Supercritical conditions (760{degrees}C & 35 MPa).

  6. Degradation of carbonyl hydroperoxides in the atmosphere and in combustion

    KAUST Repository

    Xing, Lili

    2017-10-12

    Oxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autooxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere, the degradation of carbonyl hydroperoxides leads to low-vapor-pressure polyfunctional species that be taken into in cloud and fog droplets or to the formation of secondary organic aerosols (SOAs). In combustion, the fate of carbonyl hydroperoxides is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the carbonyl hydroperoxides is reac-tion with OH radicals, for which kinetics data are experimentally unavailable. Here, we study 4-hydroperoxy-2-pentanone (CH3C(=O)CH2CH(OOH)CH3) as a model compound to clarify the kinetics of OH reactions with carbonyl hydroperoxides, in par-ticular H-atom abstraction and OH addition reactions. With a combination of electronic structure calculations, we determine previ-ously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunnel-ing (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in atmospheric and combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for the addition reaction are computed using system-specific quantum RRK theory. The calculated temperature range is 298-2400 K, and the pressure range is 0.01–100 atm. The accu-rate thermodynamic and kinetics data determined in this work are indispensable in the global modeling of SOAs in atmospheric science and in the detailed understanding and prediction of ignition properties of hydrocarbons

  7. Generation and propagation of radical reactions on proteins

    DEFF Research Database (Denmark)

    Hawkins, C L; Davies, Michael Jonathan

    2001-01-01

    The oxidation of proteins by free radicals is thought to play a major role in many oxidative processes within cells and is implicated in a number of human diseases as well as ageing. This review summarises information on the formation of radicals on peptides and proteins and how radical damage may...... be propagated and transferred within protein structures. The emphasis of this article is primarily on the deleterious actions of radicals generated on proteins, and their mechanisms of action, rather than on enzymatic systems where radicals are deliberately formed as transient intermediates. The final section...

  8. Formation and spectroscopy of {alpha}-muoniated radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W

    2003-02-01

    Several novel {alpha}-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In {alpha}-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a {beta}-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison.

  9. Formation and spectroscopy of α-muoniated radicals

    International Nuclear Information System (INIS)

    McKenzie, I.; Brodovitch, J.C.; Ghandi, K.; Kecman, S.; Percival, P.W.

    2003-01-01

    Several novel α-muoniated radicals have been produced by the reaction of muonium with compounds containing diazo, isocyanate or carbene functional groups. In α-muoniated radicals the muon is attached directly to the radical centre; they can be formed either directly or indirectly via a β-muoniated radical intermediate. The hyperfine coupling constants of the resulting radicals have been measured by transverse field muon spin rotation and muon avoided level-crossing resonance. The effect of muonium substitution was investigated for cases where ESR data are available for comparison

  10. Reactions of melatonin with radicals in deoxygenated aqueous solution

    International Nuclear Information System (INIS)

    Stasica, P.; Ulanski, P.; Rosiak, J.M.

    1998-01-01

    Reactions of melatonin (N-acetyl-5-methoxytryptamine) with radiolytically generated radicals were studied. Reaction of melatonin with OH radicals is diffusion-controlled (k=1.2 x 10 10 dm 3 mol -1 x s -1 ), the main (but not the only one) intermediate being the indolyl-type radical, while the rate constant for the reaction with hydrated electrons is k=4.3 x 10 8 dm 3 x mol -1 x s -1 . Melatonin is capable of scavenging tert-butanol radicals, while its reactivity towards polymer radicals of poly(acrylic acid) and poly(vinyl pyrrolidone) is very low. (author)

  11. Quantitative laser diagnostic and modeling study of C2 and CH chemistry in combustion.

    Science.gov (United States)

    Köhler, Markus; Brockhinke, Andreas; Braun-Unkhoff, Marina; Kohse-Höinghaus, Katharina

    2010-04-15

    Quantitative concentration measurements of CH and C(2) have been performed in laminar, premixed, flat flames of propene and cyclopentene with varying stoichiometry. A combination of cavity ring-down (CRD) spectroscopy and laser-induced fluorescence (LIF) was used to enable sensitive detection of these species with high spatial resolution. Previously, CH and C(2) chemistry had been studied, predominantly in methane flames, to understand potential correlations of their formation and consumption. For flames of larger hydrocarbon fuels, however, quantitative information on these small intermediates is scarce, especially under fuel-rich conditions. Also, the combustion chemistry of C(2) in particular has not been studied in detail, and although it has often been observed, its role in potential build-up reactions of higher hydrocarbon species is not well understood. The quantitative measurements performed here are the first to detect both species with good spatial resolution and high sensitivity in the same experiment in flames of C(3) and C(5) fuels. The experimental profiles were compared with results of combustion modeling to reveal details of the formation and consumption of these important combustion molecules, and the investigation was devoted to assist the further understanding of the role of C(2) and of its potential chemical interdependences with CH and other small radicals.

  12. Free radicals in biology. Volume II

    International Nuclear Information System (INIS)

    Pryor, W.A.

    1976-01-01

    This volume continues the treatment of topics in free radical biology and free radical pathology from Volume I. In the first chapter, pyridinyl radicals, radicals which are models for those derived from NAD, are discussed. Pyridinyl radicals can be synthesized and isolated and directly studied in a number of chemical systems. The next chapter treats the role of glutathione in the cell. It is becoming even more apparent that this vital thiol controls a large number of important cellular functions. The GSH/GSSG balance has recently been implicated as a control for cellular development; this balance also may be important in relaying the effects of oxidants from one site to another in the body. The next chapter outlines the reactions of singlet oxygen; some of these involve free radicals and some do not. This reactive intermediate appears to be important both in photochemical smog and in cellular chemistry where singlet oxygen is produced by nonphotochemical processes. The production of free radicals from dry tissues, a controversial area with conflicting claims is reviewed. The next chapter outlines the current status of the studies of photochemical smog. The next two chapters treat specific reactive materials which are present in smog. The first discusses the chemistry of nitrogen oxides and ozone. The second chapter treats the chemistry of the peroxyacyl nitrites. These compounds, although present in only small concentration, are among the most toxic components of smog. The last two chapters treat radiation damage to proteins and radiation protection and radical reactions produced by radiation in nucleic acids

  13. The attractive quartet potential energy surface for the CH(a{sup 4}{sigma}{sup {minus}}) + CO reaction: A role for the a {sup 4}A`` state of the ketenyl radical in combustion?

    Energy Technology Data Exchange (ETDEWEB)

    Schaefer, H.F. III [Univ. of Georgia, Athens (United States)

    1993-12-01

    Ab initio quantum mechanical techniques, including the self-consistent field (SCF), single and double excitation configuration interaction (CISD), single and double excitation double cluster (CCSD), and the single, double and perturbative triple excitation coupled cluster [CCSD(T)] methods have been applied to study the HCCO(a {sup 4}A{open_quotes}) energy hypersurface. Rate constant measurements suggest an attractive potential for the reaction of CH(a {sup 4}{sigma}{sup -}) with CO, and a vanishingly small energy barrier is predicted here in the CH(a {sup 4}{sigma}{sup -}) + CO reaction channel. The {sup 4}A{open_quotes} state of HCCO is predicted to be bound by about 30 kcal/mol with respect to separated CH(a {sup 4}{sigma}{sup -}) + CO. The authors propose that a spin-forbidden electronic deactivation of CH(a {sup 4}{sigma}{sup -}) might occur through through an intersystem crossing involving the {sup 4}A{open_quotes} state of HCCO. The energetics and the geometries of the reactants and products on both quartet and doublet energy surfaces are presented. The relationship between this research and experimental combustion chemistry has been explored.

  14. Combustion modeling and kinetic rate calculations for a stoichiometric cyclohexane flame. 1. Major reaction pathways.

    Science.gov (United States)

    Zhang, Hongzhi R; Huynh, Lam K; Kungwan, Nawee; Yang, Zhiwei; Zhang, Shaowen

    2007-05-17

    The Utah Surrogate Mechanism was extended in order to model a stoichiometric premixed cyclohexane flame (P = 30 Torr). Generic rates were assigned to reaction classes of hydrogen abstraction, beta scission, and isomerization, and the resulting mechanism was found to be adequate in describing the combustion chemistry of cyclohexane. Satisfactory results were obtained in comparison with the experimental data of oxygen, major products and important intermediates, which include major soot precursors of C2-C5 unsaturated species. Measured concentrations of immediate products of fuel decomposition were also successfully reproduced. For example, the maximum concentrations of benzene and 1,3-butadiene, two major fuel decomposition products via competing pathways, were predicted within 10% of the measured values. Ring-opening reactions compete with those of cascading dehydrogenation for the decomposition of the conjugate cyclohexyl radical. The major ring-opening pathways produce 1-buten-4-yl radical, molecular ethylene, and 1,3-butadiene. The butadiene species is formed via beta scission after a 1-4 internal hydrogen migration of 1-hexen-6-yl radical. Cascading dehydrogenation also makes an important contribution to the fuel decomposition and provides the exclusive formation pathway of benzene. Benzene formation routes via combination of C2-C4 hydrocarbon fragments were found to be insignificant under current flame conditions, inferred by the later concentration peak of fulvene, in comparison with benzene, because the analogous species series for benzene formation via dehydrogenation was found to be precursors with regard to parent species of fulvene.

  15. Radical Change by Entrepreneurial Design

    National Research Council Canada - National Science Library

    Roberts, Nancy C

    1998-01-01

    .... How radical change in public policy has occurred in the past is then documented. We find examples of radical change by chance, radical change by consensus, radical change by learning, and radical change by entrepreneurial design...

  16. Iron and iron derived radicals

    International Nuclear Information System (INIS)

    Borg, D.C.; Schaich, K.M.

    1987-04-01

    We have discussed some reactions of iron and iron-derived oxygen radicals that may be important in the production or treatment of tissue injury. Our conclusions challenge, to some extent, the usual lines of thought in this field of research. Insofar as they are born out by subsequent developments, the lessons they teach are two: Think fast! Think small! In other words, think of the many fast reactions that can rapidly alter the production and fate of highly reactive intermediates, and when considering the impact of competitive reactions on such species, think how they affect the microenvironment (on the molecular scale) ''seen'' by each reactive molecule. 21 refs., 3 figs., 1 tab

  17. Quantum Chemical Study of Supercritical Carbon Dioxide Effects on Combustion Kinetics.

    Science.gov (United States)

    Masunov, Artëm E; Wait, Elizabeth E; Atlanov, Arseniy A; Vasu, Subith S

    2017-05-18

    In oxy-fuel combustion, the pure oxygen (O 2 ), diluted with CO 2 is used as oxidant instead air. Hence, the combustion products (CO 2 and H 2 O) are free from pollution by nitrogen oxides. Moreover, high pressures result in the near-liquid density of CO 2 at supercritical state (sCO 2 ). Unfortunately, the effects of sCO 2 on the combustion kinetics are far from being understood. To assist in this understanding, in this work we are using quantum chemistry methods. Here we investigate potential energy surfaces of important combustion reactions in the presence of the carbon dioxide molecule. All transition states and reactant and product complexes are reported for three reactions: H 2 CO + HO 2 → HCO + H 2 O 2 (R1), 2HO 2 → H 2 O 2 + O 2 (R2), and CO + OH → CO 2 + H (R3). In reaction R3, covalent binding of CO 2 to the OH radical and then the CO molecule opens a new pathway, including hydrogen transfer from oxygen to carbon atoms followed by CH bond dissociation. Compared to the bimolecular OH + CO mechanism, this pathway reduces the activation barrier by 5 kcal/mol and is expected to accelerate the reaction. In the case of hydroperoxyl self-reaction 2HO 2 → H 2 O 2 + O 2 the intermediates, containing covalent bonds to CO 2 are found not to be competitive. However, the spectator CO 2 molecule can stabilize the cyclic transition state and lower the barrier by 3 kcal/mol. Formation of covalent intermediates is also discovered in the H 2 CO + HO 2 → HCO + H 2 O 2 reaction, but these species lead to substantially higher activation barriers, which makes them unlikely to play a role in hydrogen transfer kinetics. The van der Waals complexation with carbon dioxide also stabilizes the transition state and reduces the reaction barrier. These results indicate that the CO 2 environment is likely to have a catalytic effect on combustion reactions, which needs to be included in kinetic combustion mechanisms in supercritical CO 2 .

  18. High Combustion Research Facility

    Data.gov (United States)

    Federal Laboratory Consortium — At NETL's High-Pressure Combustion Research Facility in Morgantown, WV, researchers can investigate new high-pressure, high-temperature hydrogen turbine combustion...

  19. Combustion Research Laboratory

    Data.gov (United States)

    Federal Laboratory Consortium — The Combustion Research Laboratory facilitates the development of new combustion systems or improves the operation of existing systems to meet the Army's mission for...

  20. Combustion chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Brown, N.J. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    This research is concerned with the development and use of sensitivity analysis tools to probe the response of dependent variables to model input variables. Sensitivity analysis is important at all levels of combustion modeling. This group`s research continues to be focused on elucidating the interrelationship between features in the underlying potential energy surface (obtained from ab initio quantum chemistry calculations) and their responses in the quantum dynamics, e.g., reactive transition probabilities, cross sections, and thermal rate coefficients. The goals of this research are: (i) to provide feedback information to quantum chemists in their potential surface refinement efforts, and (ii) to gain a better understanding of how various regions in the potential influence the dynamics. These investigations are carried out with the methodology of quantum functional sensitivity analysis (QFSA).

  1. Neutrophil Leukocyte: Combustive Microbicidal Action and Chemiluminescence

    Directory of Open Access Journals (Sweden)

    Robert C. Allen

    2015-01-01

    Full Text Available Neutrophil leukocytes protect against a varied and complex array of microbes by providing microbicidal action that is simple, potent, and focused. Neutrophils provide such action via redox reactions that change the frontier orbitals of oxygen (O2 facilitating combustion. The spin conservation rules define the symmetry barrier that prevents direct reaction of diradical O2 with nonradical molecules, explaining why combustion is not spontaneous. In burning, the spin barrier is overcome when energy causes homolytic bond cleavage producing radicals capable of reacting with diradical O2 to yield oxygenated radical products that further participate in reactive propagation. Neutrophil mediated combustion is by a different pathway. Changing the spin quantum state of O2 removes the symmetry restriction to reaction. Electronically excited singlet molecular oxygen (O2*1 is a potent electrophilic reactant with a finite lifetime that restricts its radius of reactivity and focuses combustive action on the target microbe. The resulting exergonic dioxygenation reactions produce electronically excited carbonyls that relax by light emission, that is, chemiluminescence. This overview of neutrophil combustive microbicidal action takes the perspectives of spin conservation and bosonic-fermionic frontier orbital considerations. The necessary principles of particle physics and quantum mechanics are developed and integrated into a fundamental explanation of neutrophil microbicidal metabolism.

  2. Unimolecular reaction dynamics of free radicals

    International Nuclear Information System (INIS)

    Terry A. Miller

    2006-01-01

    Free radical reactions are of crucial importance in combustion and in atmospheric chemistry. Reliable theoretical models for predicting the rates and products of these reactions are required for modeling combustion and atmospheric chemistry systems. Unimolecular reactions frequently play a crucial role in determining final products. The dissociations of vinyl, CH2= CH, and methoxy, CH3O, have low barriers, about 13,000 cm-1 and 8,000 cm-1, respectively. Since barriers of this magnitude are typical of free radicals these molecules should serve as benchmarks for this important class of reactions. To achieve this goal, a detailed understanding of the vinyl and methoxy radicals is required. Results for dissociation dynamics of vinyl and selectively deuterated vinyl radical are reported. Significantly, H-atom scrambling is shown not to occur in this reaction. A large number of spectroscopic experiments for CH3O and CHD2O have been performed. Spectra recorded include laser induced fluorescence (LIF), laser excited dispersed fluorescence (LEDF), fluorescence dip infrared (FDIR) and stimulated emission pumping (SEP). Such results are critical for implementing dynamics experiments involving the dissociation of methoxy

  3. Scattering of State-Selected and Oriented Hydroxyl Radicals by Halogen Hydrides and Xenon

    NARCIS (Netherlands)

    Moise, A.V.

    2007-01-01

    The interaction of the OH radical with atoms and other molecules is relevant for many physical and chemical processes involved in atmospheric, combustion and interstellar chemistry. Various experimental and theoretical studies have revealed information concerning the interaction of the hydroxyl

  4. Laser-Based Optical System for Reactive Radical Concentration Measurements in Plasmas and Flames

    National Research Council Canada - National Science Library

    Fridman, Alexander

    2006-01-01

    Defense University Research Instrumentation Program (DURIP) funding was used to assemble a multi-purpose optical diagnostic system for in-situ radical concentration measurements in plasma and combustion systems...

  5. An experimental and theoretical kinetic study of the reaction of OH radicals with tetrahydrofuran

    KAUST Repository

    Giri, Binod

    2016-06-24

    Tetrahydrofuran (CHO, THF) and its alkylated derivatives of the cyclic ether family are considered to be promising future biofuels. They appear as important intermediates during the low-temperature oxidation of conventional hydrocarbon fuels and of heavy biofuels such as long-chain fatty acid methyl esters. The reaction of tetrahydrofuran with OH radicals was investigated in a shock tube, over a temperature range of 800-1340 K and at pressures near 1.5 bar. Hydroxyl radicals were generated by the rapid thermal decomposition of tert-butyl hydroperoxide, and a UV laser absorption technique was used to monitor the mole fraction of OH radicals. High-level CCSD(T)/cc-pV(D,T)Z//MP2/aug-cc-pVDZ quantum chemical calculations were performed to explore the chemistry of the THF+OH reaction system. Our calculations reveal that the THF+OH (R1) reaction proceeds via either direct or indirect H-abstraction from various sites, leading to the formation of tetrahydrofuran-2-yl (THF-R2) or tetrahydrofuran-3-yl (THF-R3) radicals and water. Theoretical kinetic analysis revealed that both channels are important under conditions relevant to combustion. To our knowledge, this is the first direct experimental and theoretical kinetic study of the reaction of tetrahydrofuran with OH radicals at high temperatures. The following theoretical rate expressions (in units of cmmols) are recommended for combustion modeling in the temperature range 800-1350 K: . k1(T)=4.11×1040.16em0ex(TK)2.69exp(1316.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→Products) . k2(T)=6.930.16em0ex×10110.16em0ex(TK)0.41exp(-106.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R20.16em0ex+H2O) . k3(T)=4.120.16em0ex×1030.16em0ex(TK)3.02exp(456.90.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R30.16em0ex+H2O) . .

  6. Leghemoglobin-derived radicals. Evidence for multiple protein-derived radicals and the initiation of peribacteroid membrane damage

    DEFF Research Database (Denmark)

    Moreau, S; Davies, Michael Jonathan; Mathieu, C

    1996-01-01

    , with the consequent generation of lipid-derived radicals. The formation of such radicals may result in the depletion of membrane antioxidants and the initiation of lipid peroxidation. This transfer of damage from the heme center via the protein surface to neighboring membranes may be of considerable biological......-derived phenoxyl radical present at Tyr-133 in the soybean protein and Tyr-138 in the lupin protein. To obtain further information on these protein radicals and their potential interaction with the physiologically important peribacteroid membrane (which surrounds the microsymbiont in vivo), EPR spin trapping......); these radicals may be side chain- or alpha-carbon-derived, their exact sites have not been determined. Some of these radicals are on the protein surface and may be key intermediates in the formation of protein dimers. These radicals have been shown to be capable of reacting with peribacteroid membrane fractions...

  7. Method of making metal oxide ceramic powders by using a combustible amino acid compound

    Science.gov (United States)

    Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

    1992-01-01

    This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

  8. Quantitative Detection of Combustion Species using Ultra-Violet Diode Lasers

    Science.gov (United States)

    Pilgrim, J. S.; Peterson, K. A.

    2001-01-01

    Southwest Sciences is developing a new microgravity combustion diagnostic based on UV diode lasers. The instrument will allow absolute concentration measurements of combustion species on a variety of microgravity combustion platforms including the Space Station. Our approach uses newly available room temperature UV diode lasers, thereby keeping the instrument compact, rugged and energy efficient. The feasibility of the technique was demonstrated by measurement of CH radicals in laboratory flames. Further progress in fabrication technology of UV diode lasers at shorter wavelengths and higher power will result in detection of transient species in the deeper UV. High sensitivity detection of combustion radicals is provided with wavelength modulation absorption spectroscopy.

  9. A radical approach to radical innovation

    NARCIS (Netherlands)

    D. Deichmann (Dirk); J.C.M. van den Ende (Jan)

    2014-01-01

    textabstractInnovation pays. Amazon, Apple, Facebook, Google – nearly every one of today’s most successful companies has a talent for developing radical new ideas. But how best to encourage radical initiative taking from employees, and does their previous success or failure at it play a role?

  10. Configuration of a pulse radiolysis system for the study of gas-phase reactions and kinetic investigations of the reactions of hydroxyl radicals with methyl and ethyl radicals

    International Nuclear Information System (INIS)

    Fagerstroem, K.

    1993-01-01

    The work that is presented in this thesis deals with the assembling and testing of a pulse radiolysis system for kinetic studies of gas-phase reactions as well as with the kinetics of the gas-phase reactions of hydroxyl radicals with methyl and ethyl radicals. These radicals are very important as these are formed at an early stage in hydrocarbon combustion processes. The two studied reactions are key reactions in those processes. (6 refs., 4 figs., 2 tabs.)

  11. Rotary combustion device

    NARCIS (Netherlands)

    2008-01-01

    Rotary combustion device (1) with rotary combustion chamber (4). Specific measures are taken to provide ignition of a combustible mixture. It is proposed that a hollow tube be provided coaxially with the axis of rotation (6), so that a small part of the mixture is guided into the combustion chamber.

  12. Free radical inactivation of trypsin

    International Nuclear Information System (INIS)

    Cudina, Ivana; Jovanovic, S.V.

    1988-01-01

    Reactivities of free radical oxidants, radical OH, Br2-anion radical and Cl 3 COO radical and a reductant, CO2-anion radical, with trypsin and reactive protein components were determined by pulse radiolysis of aqueous solutions at pH 7, 20 0 C. Highly reactive free radicals, radical OH, Br2-anion radical and CO2-anion radical, react with trypsin at diffusion controlled rates. Moderately reactive trichloroperoxy radical, k(Cl 3 COO radical + trypsin) preferentially oxidizes histidine residues. The efficiency of inactivation of trypsin by free radicals is inversely proportional to their reactivity. The yields of inactivation of trypsin by radical OH, Br2-anion radical and CO2-anion radical are low, G(inactivation) = 0.6-0.8, which corresponds to ∼ 10% of the initially produced radicals. In contrast, Cl 3 COO radical inactivates trypsin with ∼ 50% efficiency, i.e. G(inactivation) = 3.2. (author)

  13. Transverse flow reactor studies of the dynamics of radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Macdonald, R.G. [Argonne National Laboratory, IL (United States)

    1993-12-01

    Radical reactions are in important in combustion chemistry; however, little state-specific information is available for these reactions. A new apparatus has been constructed to measure the dynamics of radical reactions. The unique feature of this apparatus is a transverse flow reactor in which an atom or radical of known concentration will be produced by pulsed laser photolysis of an appropriate precursor molecule. The time dependence of individual quantum states or products and/or reactants will be followed by rapid infrared laser absorption spectroscopy. The reaction H + O{sub 2} {yields} OH + O will be studied.

  14. Effect of the methyl substitution on the combustion of two methylheptane isomers: Flame chemistry using vacuum-ultraviolet (VUV) photoionization mass spectrometry

    KAUST Repository

    Selim, Hatem

    2015-04-16

    Alkanes with one or more methyl substitutions are commonly found in liquid transportation fuels, so a fundamental investigation of their combustion chemistry is warranted. In the present work, stoichiometric low-pressure (20 Torr) burner-stabilized flat flames of 2-methylheptane and 3-methylheptane were investigated. Flame species were measured via time-of-flight molecular-beam mass spectrometry, with vacuum-ultraviolet (VUV) synchrotron radiation as the ionization source. Mole fractions of major end-products and intermediate species (e.g., alkanes, alkenes, alkynes, aldehydes, and dienes) were quantified axially above the burner surface. Mole fractions of several free radicals were also measured (e.g., CH3, HCO, C2H3, C3H3, and C3H5). Isomers of different species were identified within the reaction pool by an energy scan between 8 and 12 eV at a distance of 2.5 mm away from the burner surface. The role of methyl substitution location on the alkane chain was determined via comparisons of similar species trends obtained from both flames. The results revealed that the change in CH3 position imposed major differences on the combustion of both fuels. Comparison with numerical simulations was performed for kinetic model testing. The results provide a comprehensive set of data about the combustion of both flames, which can enhance the erudition of both fuels combustion chemistry and also improve their chemical kinetic reaction mechanisms. © 2015 American Chemical Society.

  15. Recent contributions of flame-sampling molecular-beam mass spectrometry to a fundamental understanding of combustion chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Nils [Combustion Research Facility, Sandia National Laboratories, Livermore, CA 94551 (United States); Cool, Terrill A. [School of Applied and Engineering Physics, Cornell University, Ithaca, NY 14853 (United States); Westmoreland, Phillip R. [Department of Chemical Engineering, University of Massachusetts, Amherst, MA 01003 (United States); Kohse-Hoeinghaus, Katharina [Department of Chemistry, Bielefeld University, D-33615 Bielefeld (Germany)

    2009-04-15

    Flame-sampling molecular-beam mass spectrometry of premixed, laminar, low-pressure flat flames has been demonstrated to be an efficient tool to study combustion chemistry. In this technique, flame gases are sampled through a small opening in a quartz probe, and after formation of a molecular beam, all flame species are separated using mass spectrometry. The present review focuses on critical aspects of the experimental approach including probe sampling effects, different ionization processes, and mass separation procedures. The capability for isomer-resolved flame species measurements, achievable by employing tunable vacuum-ultraviolet radiation for single-photon ionization, has greatly benefited flame-sampling molecular-beam mass spectrometry. This review also offers an overview of recent combustion chemistry studies of flames fueled by hydrocarbons and oxygenates. The identity of a variety of intermediates in hydrocarbon flames, including resonantly stabilized radicals and closed-shell intermediates, is described, thus establishing a more detailed understanding of the fundamentals of molecular-weight growth processes. Finally, molecular-beam mass-spectrometric studies of reaction paths in flames of alcohols, ethers, and esters, which have been performed to support the development and validation of kinetic models for bio-derived alternative fuels, are reviewed. (author)

  16. Combustion 2000

    Energy Technology Data Exchange (ETDEWEB)

    A. Levasseur; S. Goodstine; J. Ruby; M. Nawaz; C. Senior; F. Robson; S. Lehman; W. Blecher; W. Fugard; A. Rao; A. Sarofim; P. Smith; D. Pershing; E. Eddings; M. Cremer; J. Hurley; G. Weber; M. Jones; M. Collings; D. Hajicek; A. Henderson; P. Klevan; D. Seery; B. Knight; R. Lessard; J. Sangiovanni; A. Dennis; C. Bird; W. Sutton; N. Bornstein; F. Cogswell; C. Randino; S. Gale; Mike Heap

    2001-06-30

    . To achieve these objectives requires a change from complete reliance of coal-fired systems on steam turbines (Rankine cycles) and moving forward to a combined cycle utilizing gas turbines (Brayton cycles) which offer the possibility of significantly greater efficiency. This is because gas turbine cycles operate at temperatures well beyond current steam cycles, allowing the working fluid (air) temperature to more closely approach that of the major energy source, the combustion of coal. In fact, a good figure of merit for a HIPPS design is just how much of the enthalpy from coal combustion is used by the gas turbine. The efficiency of a power cycle varies directly with the temperature of the working fluid and for contemporary gas turbines the optimal turbine inlet temperature is in the range of 2300-2500 F (1260-1371 C). These temperatures are beyond the working range of currently available alloys and are also in the range of the ash fusion temperature of most coals. These two sets of physical properties combine to produce the major engineering challenges for a HIPPS design. The UTRC team developed a design hierarchy to impose more rigor in our approach. Once the size of the plant had been determined by the choice of gas turbine and the matching steam turbine, the design process of the High Temperature Advanced Furnace (HITAF) moved ineluctably to a down-fired, slagging configuration. This design was based on two air heaters: one a high temperature slagging Radiative Air Heater (RAH) and a lower temperature, dry ash Convective Air Heater (CAH). The specific details of the air heaters are arrived at by an iterative sequence in the following order:-Starting from the overall Cycle requirements which set the limits for the combustion and heat transfer analysis-The available enthalpy determined the range of materials, ceramics or alloys, which could tolerate the temperatures-Structural Analysis of the designs proved to be the major limitation-Finally the commercialization

  17. Free radicals in chemical carcinogenesis.

    Science.gov (United States)

    Clemens, M R

    1991-12-15

    charge but do possess a single unpaired electron, making the radical extremely reactive. That such forms may be important in the introduction of neoplastic transformation by chemicals from two lines of evidence. (1) Various molecules that inhibit the formation of free radicals, many of which are termed antioxidants, can inhibit the carcinogenic action of a variety of chemical carcinogens. (2) There are relatively specific metabolic reactions of certain chemical carcinogens, particularly of polycyclic hydrocarbons, for which it has been shown to proceed through free radical intermediates. In conclusion, free radical processes with direct effects on DNA can be proposed for a variety of human and animal carcinogens.(ABSTRACT TRUNCATED AT 400 WORDS)

  18. Reduced NOX combustion method

    International Nuclear Information System (INIS)

    Delano, M.A.

    1991-01-01

    This patent describes a method for combusting fuel and oxidant to achieve reduced formation of nitrogen oxides. It comprises: It comprises: heating a combustion zone to a temperature at least equal to 1500 degrees F.; injecting into the heated combustion zone a stream of oxidant at a velocity within the range of from 200 to 1070 feet per second; injecting into the combustion zone, spaced from the oxidant stream, a fuel stream at a velocity such that the ratio of oxidant stream velocity to fuel stream velocity does not exceed 20; aspirating combustion gases into the oxidant stream and thereafter intermixing the aspirated oxidant stream and fuel stream to form a combustible mixture; combusting the combustible mixture to produce combustion gases for the aspiration; and maintaining the fuel stream substantially free from contact with oxidant prior to the intermixture with aspirated oxidant

  19. Terahertz Rotational Spectroscopy of the so Radical

    Science.gov (United States)

    Martin-Drumel, M. A.; Cuisset, A.; Eliet, S.; Mouret, G.; Hindle, F.; Pirali, O.

    2013-06-01

    Sulfur monoxide SO (X^3Σ^-) is a well-known interstellar radical identified in a wide variety of astrophysical environments. Due to its high reactivity and its role in chemical reactions involving O and S atoms, SO is also a reaction intermediate in combustion processes and chemistry of the Earth atmosphere. We have recorded pure rotational transitions of SO in the THz spectral range using synchrotron-based Fourier-Transform (FT) FIR and continous wave (CW) THz techniques. A FT-FIR spectrum of SO has been recorded at the AILES beamline of SOLEIL synchrotron in the spectral range 44-93 wn using a resolution of 0.001 wn allowing an accuracy on line position of 0.00007 wn (≃ 2 MHz). A multipass absorption discharge cell aligned to an absorption path length of 24 m has been used. A continuous electrical discharge (1 A / 980 V) in a flowing mixture of H_2S, He, H_2 and air (respectively at pressure of 0.01, 1.15, 0.14 and 0.06 mbar) was used to produce SO. On this spectrum, 102 transitions of SO have been identified with N=31 to 65. Among the observed lines, 99 are detected for the first time (22 new transitions belong to the HIFI spectral windows). Due to our limited instrumental resolution, transitions involving N ranging from 31 to 43 show unresolved fine structure triplets. Recently, in order to observe all fine structure components in the HIFI spectral windows, we have recorded a high resolution CW-THz spectrum of SO. At the time of the writing, this spectrum was under analysis. C. A. Gottlieb and J. A. Ball, Astrophys. J. 184, L59 (1973) G.A. Blake et al., Astrophys. J. 315, 621 (1987) J. B. Burkholder et al., J. Mol. Spectrosc. 124, 379 (1987) M. A. Martin-Drumel et al., Rev. Sci. Instrum. 82, 113106 (2011) S. Eliet et al., J. Mol. Struct. 1006, 13 (2011)

  20. Numerical simulation of combustion and soot under partially premixed combustion of low-octane gasoline

    KAUST Repository

    An, Yanzhao

    2017-09-23

    In-cylinder combustion visualization and engine-out soot particle emissions were investigated in an optical diesel engine fueled with low octane gasoline. Single injection strategy with an early injection timing (−30 CAD aTDC) was employed to achieve partially premixed combustion (PPC) condition. A high-speed color camera was used to record the combustion images for 150 cycles. The regulated emission of carbon dioxide, carbon monoxide, nitrogen oxides and soot mass concentration were measured experimentally. Full cycle engine simulations were performed using CONVERGE™ and the simulation results matched with the experimental results. The in-cylinder soot particle evolution was performed by coupling a reduced toluene reference fuel mechanism including the PAHs formation/oxidation reactions with particulate size mimic model. The results showed that PPC presents typical stratified combustion characteristics, which is significantly different from the conventional diesel spray-driven combustion. The in-cylinder temperature and equivalence ratio overlaid with soot-NO formation regime revealed that PPC operating condition under study mostly avoided the main sooting conditions throughout the entire combustion. The evaluation of temperature distribution showed formaldehyde could be regarded as an indicator for low temperature reactions, while hydroxyl group represents the high temperature reactions. Soot evolution happened during the combustion process, hydroxyl radicals promoted the soot oxidation.

  1. Numerical simulation of combustion and soot under partially premixed combustion of low-octane gasoline

    KAUST Repository

    An, Yanzhao; Jaasim, Mohammed; Vallinayagam, R.; Vedharaj, S.; Im, Hong G.; Johansson, Bengt.

    2017-01-01

    In-cylinder combustion visualization and engine-out soot particle emissions were investigated in an optical diesel engine fueled with low octane gasoline. Single injection strategy with an early injection timing (−30 CAD aTDC) was employed to achieve partially premixed combustion (PPC) condition. A high-speed color camera was used to record the combustion images for 150 cycles. The regulated emission of carbon dioxide, carbon monoxide, nitrogen oxides and soot mass concentration were measured experimentally. Full cycle engine simulations were performed using CONVERGE™ and the simulation results matched with the experimental results. The in-cylinder soot particle evolution was performed by coupling a reduced toluene reference fuel mechanism including the PAHs formation/oxidation reactions with particulate size mimic model. The results showed that PPC presents typical stratified combustion characteristics, which is significantly different from the conventional diesel spray-driven combustion. The in-cylinder temperature and equivalence ratio overlaid with soot-NO formation regime revealed that PPC operating condition under study mostly avoided the main sooting conditions throughout the entire combustion. The evaluation of temperature distribution showed formaldehyde could be regarded as an indicator for low temperature reactions, while hydroxyl group represents the high temperature reactions. Soot evolution happened during the combustion process, hydroxyl radicals promoted the soot oxidation.

  2. Comprehensive mechanisms for combustion chemistry: Experiment, modeling, and sensitivity analysis

    Energy Technology Data Exchange (ETDEWEB)

    Dryer, F.L.; Yetter, R.A. [Princeton Univ., NJ (United States)

    1993-12-01

    This research program is an integrated experimental/numerical effort to study pyrolysis and oxidation reactions and mechanisms for small-molecule hydrocarbon structures under conditions representative of combustion environments. The experimental aspects of the work are conducted in large diameter flow reactors, at pressures from one to twenty atmospheres, temperatures from 550 K to 1200 K, and with observed reaction times from 10{sup {minus}2} to 5 seconds. Gas sampling of stable reactant, intermediate, and product species concentrations provides not only substantial definition of the phenomenology of reaction mechanisms, but a significantly constrained set of kinetic information with negligible diffusive coupling. Analytical techniques used for detecting hydrocarbons and carbon oxides include gas chromatography (GC), and gas infrared (NDIR) and FTIR methods are utilized for continuous on-line sample detection of light absorption measurements of OH have also been performed in an atmospheric pressure flow reactor (APFR), and a variable pressure flow (VPFR) reactor is presently being instrumented to perform optical measurements of radicals and highly reactive molecular intermediates. The numerical aspects of the work utilize zero and one-dimensional pre-mixed, detailed kinetic studies, including path, elemental gradient sensitivity, and feature sensitivity analyses. The program emphasizes the use of hierarchical mechanistic construction to understand and develop detailed kinetic mechanisms. Numerical studies are utilized for guiding experimental parameter selections, for interpreting observations, for extending the predictive range of mechanism constructs, and to study the effects of diffusive transport coupling on reaction behavior in flames. Modeling using well defined and validated mechanisms for the CO/H{sub 2}/oxidant systems.

  3. Combustion Research Facility

    Data.gov (United States)

    Federal Laboratory Consortium — For more than 30 years The Combustion Research Facility (CRF) has served as a national and international leader in combustion science and technology. The need for a...

  4. Alcohol combustion chemistry

    KAUST Repository

    Sarathy, Mani; Oß wald, Patrick; Hansen, Nils; Kohse-Hö inghaus, Katharina

    2014-01-01

    . While biofuel production and its use (especially ethanol and biodiesel) in internal combustion engines have been the focus of several recent reviews, a dedicated overview and summary of research on alcohol combustion chemistry is still lacking. Besides

  5. Maximal combustion temperature estimation

    International Nuclear Information System (INIS)

    Golodova, E; Shchepakina, E

    2006-01-01

    This work is concerned with the phenomenon of delayed loss of stability and the estimation of the maximal temperature of safe combustion. Using the qualitative theory of singular perturbations and canard techniques we determine the maximal temperature on the trajectories located in the transition region between the slow combustion regime and the explosive one. This approach is used to estimate the maximal temperature of safe combustion in multi-phase combustion models

  6. Impacts of Combustion Conditions and Photochemical Processing on the Light Absorption of Biomass Combustion Aerosol.

    Science.gov (United States)

    Martinsson, J; Eriksson, A C; Nielsen, I Elbæk; Malmborg, V Berg; Ahlberg, E; Andersen, C; Lindgren, R; Nyström, R; Nordin, E Z; Brune, W H; Svenningsson, B; Swietlicki, E; Boman, C; Pagels, J H

    2015-12-15

    The aim was to identify relationships between combustion conditions, particle characteristics, and optical properties of fresh and photochemically processed emissions from biomass combustion. The combustion conditions included nominal and high burn rate operation and individual combustion phases from a conventional wood stove. Low temperature pyrolysis upon fuel addition resulted in "tar-ball" type particles dominated by organic aerosol with an absorption Ångström exponent (AAE) of 2.5-2.7 and estimated Brown Carbon contributions of 50-70% to absorption at the climate relevant aethalometer-wavelength (520 nm). High temperature combustion during the intermediate (flaming) phase was dominated by soot agglomerates with AAE 1.0-1.2 and 85-100% of absorption at 520 nm attributed to Black Carbon. Intense photochemical processing of high burn rate flaming combustion emissions in an oxidation flow reactor led to strong formation of Secondary Organic Aerosol, with no or weak absorption. PM1 mass emission factors (mg/kg) of fresh emissions were about an order of magnitude higher for low temperature pyrolysis compared to high temperature combustion. However, emission factors describing the absorption cross section emitted per kg of fuel consumed (m(2)/kg) were of similar magnitude at 520 nm for the diverse combustion conditions investigated in this study. These results provide a link between biomass combustion conditions, emitted particle types, and their optical properties in fresh and processed plumes which can be of value for source apportionment and balanced mitigation of biomass combustion emissions from a climate and health perspective.

  7. The chemistry of amine radical cations produced by visible light photoredox catalysis

    Directory of Open Access Journals (Sweden)

    Jie Hu

    2013-10-01

    Full Text Available Amine radical cations are highly useful reactive intermediates in amine synthesis. They have displayed several modes of reactivity leading to some highly sought-after synthetic intermediates including iminium ions, α-amino radicals, and distonic ions. One appealing method to access amine radical cations is through one-electron oxidation of the corresponding amines under visible light photoredox conditions. This approach and subsequent chemistries are emerging as a powerful tool in amine synthesis. This article reviews synthetic applications of amine radical cations produced by visible light photocatalysis.

  8. Covalent functionalization of graphene with reactive intermediates.

    Science.gov (United States)

    Park, Jaehyeung; Yan, Mingdi

    2013-01-15

    Graphene, a material made exclusively of sp(2) carbon atoms with its π electrons delocalized over the entire 2D network, is somewhat chemically inert. Covalent functionalization can enhance graphene's properties including opening its band gap, tuning conductivity, and improving solubility and stability. Covalent functionalization of pristine graphene typically requires reactive species that can form covalent adducts with the sp(2) carbon structures in graphene. In this Account, we describe graphene functionalization reactions using reactive intermediates of radicals, nitrenes, carbenes, and arynes. These reactive species covalently modify graphene through free radical addition, CH insertion, or cycloaddition reactions. Free radical additions are among the most common reaction, and these radicals can be generated from diazonium salts and benzoyl peroxide. Electron transfer from graphene to aryl diazonium ion or photoactivation of benzoyl peroxide yields aryl radicals that subsequently add to graphene to form covalent adducts. Nitrenes, electron-deficient species generated by thermal or photochemical activation of organic azides, can functionalize graphene very efficiently. Because perfluorophenyl nitrenes show enhanced bimolecular reactions compared with alkyl or phenyl nitrenes, perfluorophenyl azides are especially effective. Carbenes are used less frequently than nitrenes, but they undergo CH insertion and C═C cycloaddition reactions with graphene. In addition, arynes can serve as a dienophile in a Diels-Alder type reaction with graphene. Further study is needed to understand and exploit the chemistry of graphene. The generation of highly reactive intermediates in these reactions leads to side products that complicate the product composition and analysis. Fundamental questions remain about the reactivity and regioselectivity of graphene. The differences in the basal plane and the undercoordinated edges of graphene and the zigzag versus arm-chair configurations

  9. Radicals derived from acetaldehyde and vinyl alcohol.

    Science.gov (United States)

    Estep, Marissa L; Morgan, W James; Winkles, Alexander T; Abbott, Adam S; Villegas-Escobar, Nery; Mullinax, J Wayne; Turner, Walter E; Wang, Xiao; Turney, Justin M; Schaefer, Henry F

    2017-10-18

    Vinyl alcohol and acetaldehyde are isoelectronic products of incomplete butanol combustion. Along with the radicals resulting from the removal of atomic hydrogen or the hydroxyl radical, these species are studied here using ab initio methods as complete as coupled cluster theory with single, double, triple, and perturbative quadruple excitations [CCSDT(Q)], with basis sets as large as cc-pV5Z. The relative energies provided herein are further refined by including corrections for relativistic effects, the frozen core approximation, and the Born-Oppenheimer approximation. The effects of anharmonic zero-point vibrational energies are also treated. The syn conformer of vinyl alcohol is predicted to be lower in energy than the anti conformer by 1.1 kcal mol -1 . The alcoholic hydrogen of syn-vinyl alcohol is found to be the easiest to remove, requiring 84.4 kcal mol -1 . Five other radicals are also carefully considered, with four conformers investigated for the 1-hydroxyvinyl radical. Beyond energetics, we have conducted an overhaul of the spectroscopic literature for these species. Our results also provide predictions for fundamental modes yet to be reported experimentally. To our knowledge, the ν 3 (3076 cm -1 ) and ν 4 (2999 cm -1 ) C-H stretches for syn-vinyl alcohol and all but one of the vibrational modes for anti-vinyl alcohol (ν 1 -ν 14 ) are yet to be observed experimentally. For the acetyl radical, ν 6 (1035 cm -1 ), ν 11 (944 cm -1 ), ν 12 (97 cm -1 ), and accounting for our changes to the assignment of the 1419.9 cm -1 experimental mode, ν 10 (1441 cm -1 ), are yet to be observed. We have predicted these unobserved fundamentals and reassigned the experimental 1419.9 cm -1 frequency in the acetyl radical to ν 4 rather than to ν 10 . Our work also strongly supports reassignment of the ν 10 and ν 11 fundamentals of the vinoxy radical. We suggest that the bands assigned to the overtones of these fundamentals were in fact combination bands. Our

  10. Intermediality and media change

    OpenAIRE

    2012-01-01

    This book is about intermediality as an approach to analysing and understanding media change. Intermediality and Media Change is critical of technological determinism that characterises 'new media discourse' about the ongoing digitalization, framed as a revolution and creating sharp contrasts between old and new media. Intermediality instead emphasises paying attention to continuities between media of all types and privileges a comparative perspective on technological changes in media over ti...

  11. Kinetics and mechanisms of reactions involving small aromatic reactive intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Lin, M.C. [Emory Univ., Atlanta, GA (United States)

    1993-12-01

    Small aromatic radicals such as C{sub 6}H{sub 5}, C{sub 6}H{sub 5}O and C{sub 6}H{sub 4} are key prototype species of their homologs. C{sub 6}H{sub 5} and its oxidation product, C{sub 6}H{sub 5}O are believed to be important intermediates which play a pivotal role in hydrocarbon combustion, particularly with regard to soot formation. Despite their fundamental importance, experimental data on the reaction mechanisms and reactivities of these species are very limited. For C{sub 6}H{sub 5}, most kinetic data except its reactions with NO and NO{sub 2}, were obtained by relative rate measurements. For C{sub 6}H{sub 5}O, the authors have earlier measured its fragmentation reaction producing C{sub 5}H{sub 5} + CO in shock waves. For C{sub 6}H{sub 4}, the only rate constant measured in the gas phase is its recombination rate at room temperature. The authors have proposed to investigate systematically the kinetics and mechanisms of this important class of molecules using two parallel laser diagnostic techniques--laser resonance absorption (LRA) and resonance enhanced multiphoton ionization mass spectrometry (REMPI/MS). In the past two years, study has been focused on the development of a new multipass adsorption technique--the {open_quotes}cavity-ring-down{close_quotes} technique for kinetic applications. The preliminary results of this study appear to be quite good and the sensitivity of the technique is at least comparable to that of the laser-induced fluorescence method.

  12. Uncertainties in hydrogen combustion

    International Nuclear Information System (INIS)

    Stamps, D.W.; Wong, C.C.; Nelson, L.S.

    1988-01-01

    Three important areas of hydrogen combustion with uncertainties are identified: high-temperature combustion, flame acceleration and deflagration-to-detonation transition, and aerosol resuspension during hydrogen combustion. The uncertainties associated with high-temperature combustion may affect at least three different accident scenarios: the in-cavity oxidation of combustible gases produced by core-concrete interactions, the direct containment heating hydrogen problem, and the possibility of local detonations. How these uncertainties may affect the sequence of various accident scenarios is discussed and recommendations are made to reduce these uncertainties. 40 references

  13. Vibronic Spectroscopy of the Phenylcyanomethyl Radical

    Science.gov (United States)

    Mehta, Deepali N.; Kidwell, Nathanael M.; Zwier, Timothy S.

    2011-06-01

    Resonance stabilized radicals (RSRs) are thought to be key intermediates in the formation of larger molecules in planetary atmospheres. Given the nitrogen-rich atmosphere of Titan, and the prevalence of nitriles there, it is likely that nitrile and isonitrile RSRs could be especially important in pathways leading to the formation of more complex nitrogen-containing compounds and the aerosols ("tholins") that are ultimately produced. In this talk, the results of a gas phase, jet-cooled vibronic spectroscopy study of the phenylcyanomethyl radical (C_6H_5.{C}HCN), the nitrogen-containing analog of the 1-phenylpropargyl radical, will be presented. A resonant two color photon ionization spectrum over the range 21,350-22,200 Cm-1 (450.0-468.0 nm) has been recorded, and the D_0-D_1 origin band has been tentatively identified at 21,400 Cm-1. Studies identifying the ionization threshold, and characterizing the vibronic structure will also be presented. An analogous study of the phenylisocyanomethyl radical, C_6H_5.{C}HNC, is currently being pursued for comparison with that of phenylcyanomethyl radical.

  14. Orgasm after radical prostatectomy

    NARCIS (Netherlands)

    Koeman, M; VanDriel, MF; Schultz, WCMW; Mensink, HJA

    Objective To evaluate the ability to obtain and the quality of orgasm after radical prostatectomy, Patients and methods The orgasms experienced after undergoing radical prostatectomy were evaluated in 20 men (median age 65 years, range 56-76) using a semi-structured interview and a self-administered

  15. Physiology of free radicals

    Directory of Open Access Journals (Sweden)

    Stevanović Jelka

    2011-01-01

    Full Text Available Free radicals imply that every atom, molecule, ion, group of atoms, or molecules with one or several non-paired electrons in outer orbital. Among these are: nitrogenoxide (NO•, superoxide-anion-radical (O2•-, hydroxyl radical (OH•, peroxyl radical (ROO•, alcoxyl radical (RO• and hydroperoxyl radical (HO2•. However, reactive oxygen species also include components without non-paired electrons in outer orbital (so-called reactive non-radical agents, such as: singlet oxygen (1O2, peroxynitrite (ONOO-, hydrogen-peroxide (H2O2, hypochloric acid (eg. HOCl and ozone (O3. High concentrations of free radicals lead to the development of oxidative stress which is a precondition for numerous pathological effects. However, low and moderate concentrations of these matter, which occur quite normally during cell metabolic activity, play multiple significant roles in many reactions. Some of these are: regulation of signal pathways within the cell and between cells, the role of chemoattractors and leukocyte activators, the role in phagocytosis, participation in maintaining, changes in the position and shape of the cell, assisting the cell during adaption and recovery from damage (e.g.caused by physical effort, the role in normal cell growth, programmed cell death (apoptosis and cell ageing, in the synthesis of essential biological compounds and energy production, as well as the contribution to the regulation of the vascular tone, actually, tissue vascularization.

  16. Radicals in arithmetic

    NARCIS (Netherlands)

    W.J. Palenstijn (Willem Jan)

    2014-01-01

    htmlabstractLet K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement

  17. Radicals in arithmetic

    NARCIS (Netherlands)

    Palenstijn, Willem Jan

    2014-01-01

    Let K be a field. A radical is an element of the algebraic closure of K of which a power is contained in K. In this thesis we develop a method for determining what we call entanglement. This describes unexpected additive relations between radicals, and is encoded in an entanglement group. We give

  18. Muonium and muonic radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Geeson, D.; Symons, M.C.R.

    1985-01-01

    An energetic positive muon which is injected in a liquid sample of substrate molecules (S) creates an ionization track consisting of substrate cations (S + ) and electrons. Near the end of this track the muon may combine with an electron to form muonium (Mu) which is observable in inert liquids, but which reacts by addition to form a radical. Alternatively, the electron can add to S to form S - , which then combines with the muon to form the radical. Furthermore, instead of ending up in Mu or in a radical the muon may stay in a diamagnetic environment as a solvated muon, or as a muon substituting a proton in a molecule. Of interest in these schemes are the mechanisms and rates of formation of muonated radicals and in particular the rate constants for their reactions to products. Investigations are based on the observation of Mu and the radical by means of the μSR technique in transverse magnetic fields. (Auth.)

  19. New class of combustion processes

    International Nuclear Information System (INIS)

    Merzhanov, A.G.; Borovinskaya, I.P.

    1975-01-01

    A short review is given of the results of work carried out since 1967 on studying the combustion processes caused by the interaction of chemical elements in the condensed phase and leading to the formation of refractory compounds. New phenomena and processes are described which are revealed when investigating the combustion of the systems of this class, viz solid-phase combustion, fast combustion in the condensed phase, filtering combustion, combustion in liquid nitrogen, spinning combustion, self-oscillating combustion, and repeated combustion. A new direction in employment of combustion processes is discussed, viz. a self-propagating high-temperature synthesis of refractory nitrides, carbides, borides, silicides and other compounds

  20. Intermediate temperature heat release in an HCCI engine fueled by ethanol/n-heptane mixtures: An experimental and modeling study

    KAUST Repository

    Vuilleumier, David

    2014-03-01

    This study examines intermediate temperature heat release (ITHR) in homogeneous charge compression ignition (HCCI) engines using blends of ethanol and n-heptane. Experiments were performed over the range of 0-50% n-heptane liquid volume fractions, at equivalence ratios 0.4 and 0.5, and intake pressures from 1.4bar to 2.2bar. ITHR was induced in the mixtures containing predominantly ethanol through the addition of small amounts of n-heptane. After a critical threshold, additional n-heptane content yielded low temperature heat release (LTHR). A method for quantifying the amount of heat released during ITHR was developed by examining the second derivative of heat release, and this method was then used to identify trends in the engine data. The combustion process inside the engine was modeled using a single-zone HCCI model, and good qualitative agreement of pre-ignition pressure rise and heat release rate was found between experimental and modeling results using a detailed n-heptane/ethanol chemical kinetic model. The simulation results were used to identify the dominant reaction pathways contributing to ITHR, as well as to verify the chemical basis behind the quantification of the amount of ITHR in the experimental analysis. The dominant reaction pathways contributing to ITHR were found to be H-atom abstraction from n-heptane by OH and the addition of fuel radicals to O2. © 2013 The Combustion Institute.

  1. Intermediate temperature heat release in an HCCI engine fueled by ethanol/n-heptane mixtures: An experimental and modeling study

    KAUST Repository

    Vuilleumier, David; Kozarac, Darko; Mehl, Marco; Saxena, Samveg; Pitz, William J.; Dibble, Robert W.; Chen, Jyhyuan; Sarathy, Mani

    2014-01-01

    This study examines intermediate temperature heat release (ITHR) in homogeneous charge compression ignition (HCCI) engines using blends of ethanol and n-heptane. Experiments were performed over the range of 0-50% n-heptane liquid volume fractions, at equivalence ratios 0.4 and 0.5, and intake pressures from 1.4bar to 2.2bar. ITHR was induced in the mixtures containing predominantly ethanol through the addition of small amounts of n-heptane. After a critical threshold, additional n-heptane content yielded low temperature heat release (LTHR). A method for quantifying the amount of heat released during ITHR was developed by examining the second derivative of heat release, and this method was then used to identify trends in the engine data. The combustion process inside the engine was modeled using a single-zone HCCI model, and good qualitative agreement of pre-ignition pressure rise and heat release rate was found between experimental and modeling results using a detailed n-heptane/ethanol chemical kinetic model. The simulation results were used to identify the dominant reaction pathways contributing to ITHR, as well as to verify the chemical basis behind the quantification of the amount of ITHR in the experimental analysis. The dominant reaction pathways contributing to ITHR were found to be H-atom abstraction from n-heptane by OH and the addition of fuel radicals to O2. © 2013 The Combustion Institute.

  2. Combustion Sensors: Gas Turbine Applications

    Science.gov (United States)

    Human, Mel

    2002-01-01

    This report documents efforts to survey the current research directions in sensor technology for gas turbine systems. The work is driven by the current and future requirements on system performance and optimization. Accurate real time measurements of velocities, pressure, temperatures, and species concentrations will be required for objectives such as combustion instability attenuation, pollutant reduction, engine health management, exhaust profile control via active control, etc. Changing combustor conditions - engine aging, flow path slagging, or rapid maneuvering - will require adaptive responses; the effectiveness of such will be only as good as the dynamic information available for processing. All of these issues point toward the importance of continued sensor development. For adequate control of the combustion process, sensor data must include information about the above mentioned quantities along with equivalence ratios and radical concentrations, and also include both temporal and spatial velocity resolution. Ultimately these devices must transfer from the laboratory to field installations, and thus must become low weight and cost, reliable and maintainable. A primary conclusion from this study is that the optics-based sensor science will be the primary diagnostic in future gas turbine technologies.

  3. Crossed-beam studies of the dynamics of radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Liu, K. [Argonne National Laboratory, IL (United States)

    1993-12-01

    The objective of this program is to characterize the detailed dynamics of elementary radical reactions and to provide a better understanding of radical reactivity in general. The radical beam is typically generated by a laser photolysis method. After colliding with the reacting molecule in a crossed-beam apparatus, the reaction product state distribution is interrogated by laser spectroscopic techniques. Several radicals of combustion significance, such as O, CH, OH, CN and NCO have been successfully generated and their collisional behavior at the state-to-state integral cross section level of detail has been studied in this manner. During the past year, the detection system has been converted from LIF to REMPI schemes, and the emphasis of this program shifted to investigate the product angular distributions. Both inelastic and reactive processes have been studied.

  4. The release of nitrogen in coal combustion and pyrolysis

    International Nuclear Information System (INIS)

    Varey, J.E.; Hindmarsh, C.J.; Thomas, K.M.

    1994-01-01

    Environmental aspects of coal utilization are a major concern. Recent advances in the development of low NO x burners and the emerging technologies of fluidized bed combustion have led to the identification of coal char nitrogen as the major contributor to the nitrogen oxides released during combustion. The temperature programmed combustion and pyrolysis of a series of coals covering a wide range of rank have been investigated. In addition, maceral concentrates have been investigated to assess the variation in the combustion behavior and the release of nitrogen in the pyrolysis and combustion of macerals. This investigation has involved the use of thermogravimetric analysis - mass spectrometry (TG-MS) with two sampling options: (1) ∼1cm from the sample and (2) at the exit of the TG. The former allows reactive species to be identified in the combustion of the coals. These temperature programmed combustion results have been compared with similar measurements carried out at the exit of the TG where the products are at equilibrium. In addition, pyrolysis studies have been carried out under similar conditions. The results show that reactive intermediate species such as HCN, (CN) 2 , COS etc. can be detected in the combustion products. The evolution of these species during combustion are compared with the pyrolysis products of the coal. The results are discussed in relation to the structure of the coals and the conversion of volatile species and char nitrogen to nitrogen oxides

  5. Combustion modeling in internal combustion engines

    Science.gov (United States)

    Zeleznik, F. J.

    1976-01-01

    The fundamental assumptions of the Blizard and Keck combustion model for internal combustion engines are examined and a generalization of that model is derived. The most significant feature of the model is that it permits the occurrence of unburned hydrocarbons in the thermodynamic-kinetic modeling of exhaust gases. The general formulas are evaluated in two specific cases that are likely to be significant in the applications of the model.

  6. Combustion kinetics and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  7. Flame structure and NO generation in oxy-fuel combustion at high pressures

    International Nuclear Information System (INIS)

    Seepana, Sivaji; Jayanti, Sreenivas

    2009-01-01

    A numerical study of oxy-fuel combustion has been carried out in the pressure range of 0.1-3 MPa with methane as the fuel and carbondioxide-diluted oxygen with trace amount of nitrogen (termed here as c a ir) as the oxidant. The flame structure and NO generation rate have been calculated using the flamelet model with the detailed GRI 3.0 mechanism for two oxygen concentrations of 23.3% and 20% by weight in the oxidant at a strain rate of 40 s -1 (corresponding to a scalar dissipation rate of 1 s -1 ). It is observed that, for the reference case of 23.3 wt.% of oxygen, as the pressure increases, the peak temperature of the flame increases rapidly up to a pressure of 0.5 MPa, and more gradually at higher pressures. The concentrations of important intermediate radicals such as CH 3 , H and OH decrease considerably with increasing pressure while NO concentration follows the same trend as the temperature. Reducing the oxygen concentration to 20% by weight leads to an order of magnitude reduction in NO concentration. Also, for pressures greater than 0.3 MPa, the NO concentration decreases with increasing pressure in spite of the increasing peak flame temperatures. This can be attributed to the increasing domination of recombination reactions leading to less availability of the intermediate radicals H and OH which are necessary for the formation of NO by the thermal route. It is concluded that a stable, low NO x oxy-fuel flame can be obtained at high pressures at slightly increased dilution of oxygen

  8. Flame structure and NO generation in oxy-fuel combustion at high pressures

    Energy Technology Data Exchange (ETDEWEB)

    Seepana, Sivaji; Jayanti, Sreenivas [Department of Chemical Engineering, IIT Madras, Chennai 600 036 (India)

    2009-04-15

    A numerical study of oxy-fuel combustion has been carried out in the pressure range of 0.1-3 MPa with methane as the fuel and carbondioxide-diluted oxygen with trace amount of nitrogen (termed here as c{sub a}ir) as the oxidant. The flame structure and NO generation rate have been calculated using the flamelet model with the detailed GRI 3.0 mechanism for two oxygen concentrations of 23.3% and 20% by weight in the oxidant at a strain rate of 40 s{sup -1} (corresponding to a scalar dissipation rate of 1 s{sup -1}). It is observed that, for the reference case of 23.3 wt.% of oxygen, as the pressure increases, the peak temperature of the flame increases rapidly up to a pressure of 0.5 MPa, and more gradually at higher pressures. The concentrations of important intermediate radicals such as CH{sub 3}, H and OH decrease considerably with increasing pressure while NO concentration follows the same trend as the temperature. Reducing the oxygen concentration to 20% by weight leads to an order of magnitude reduction in NO concentration. Also, for pressures greater than 0.3 MPa, the NO concentration decreases with increasing pressure in spite of the increasing peak flame temperatures. This can be attributed to the increasing domination of recombination reactions leading to less availability of the intermediate radicals H and OH which are necessary for the formation of NO by the thermal route. It is concluded that a stable, low NO{sub x} oxy-fuel flame can be obtained at high pressures at slightly increased dilution of oxygen. (author)

  9. Boiler using combustible fluid

    Science.gov (United States)

    Baumgartner, H.; Meier, J.G.

    1974-07-03

    A fluid fuel boiler is described comprising a combustion chamber, a cover on the combustion chamber having an opening for introducing a combustion-supporting gaseous fluid through said openings, means to impart rotation to the gaseous fluid about an axis of the combustion chamber, a burner for introducing a fluid fuel into the chamber mixed with the gaseous fluid for combustion thereof, the cover having a generally frustro-conical configuration diverging from the opening toward the interior of the chamber at an angle of between 15/sup 0/ and 55/sup 0/; means defining said combustion chamber having means defining a plurality of axial hot gas flow paths from a downstream portion of the combustion chamber to flow hot gases into an upstream portion of the combustion chamber, and means for diverting some of the hot gas flow along paths in a direction circumferentially of the combustion chamber, with the latter paths being immersed in the water flow path thereby to improve heat transfer and terminating in a gas outlet, the combustion chamber comprising at least one modular element, joined axially to the frustro-conical cover and coaxial therewith. The modular element comprises an inner ring and means of defining the circumferential, radial, and spiral flow paths of the hot gases.

  10. Salvage robotic radical prostatectomy

    Directory of Open Access Journals (Sweden)

    Samuel D Kaffenberger

    2014-01-01

    Full Text Available Failure of non-surgical primary treatment for localized prostate cancer is a common occurrence, with rates of disease recurrence ranging from 20% to 60%. In a large proportion of patients, disease recurrence is clinically localized and therefore potentially curable. Unfortunately, due to the complex and potentially morbid nature of salvage treatment, radical salvage surgery is uncommonly performed. In an attempt to decrease the morbidity of salvage therapy without sacrificing oncologic efficacy, a number of experienced centers have utilized robotic assistance to perform minimally invasive salvage radical prostatectomy. Herein, we critically evaluate the existing literature on salvage robotic radical prostatectomy with a focus on patient selection, perioperative complications and functional and early oncologic outcomes. These results are compared with contemporary and historical open salvage radical prostatectomy series and supplemented with insights we have gained from our experience with salvage robotic radical prostatectomy. The body of evidence by which conclusions regarding the efficacy and safety of robotic salvage radical prostatectomy can be drawn comprises fewer than 200 patients with limited follow-up. Preliminary results are promising and some outcomes have been favorable when compared with contemporary open salvage prostatectomy series. Advantages of the robotic platform in the performance of salvage radical prostatectomy include decreased blood loss, short length of stay and improved visualization. Greater experience is required to confirm the long-term oncologic efficacy and functional outcomes as well as the generalizability of results achieved at experienced centers.

  11. Relative stability of radicals derived from artemisinin: A semiempirical and DFT study

    Science.gov (United States)

    Arantes, C.; de Araujo, M. T.; Taranto, A. G.; de M. Carneiro, J. W.

    The semiempirical AM1 and PM3 methods, as well as the density functional (DFT/B3LYP) approach using the 6-31g(d) basis set, were employed to calculate the relative stability of intermediate radicals derived from artemisinin, a sesquiterpene lactone having an endoperoxide bridge that is essential for its antimalarial activity. The compounds studied have their nonperoxidic oxygen atom of the trioxane ring and/or the carbonyl group replaced by a CH2 unit. Relative stabilities were calculated by means of isodesmic equations using artemisinin as reference. It was found that replacement of oxygen atoms decreases the relative stability of the anionic radical intermediates. In contrast, for compounds with inverted stereochemistry the intermediate radicals were found to be more stable than those with the artemisinin-like stereochemistry. These relative stabilities may modulate the antimalarial potency. Radicals centered on carbon are always more stable than the corresponding radicals centered on oxygen.

  12. Avaliação das propriedades do Ba0,50Sr0,50Co0,80Fe0,20O3-d para células a combustível de óxido sólido de temperatura intermediária obtido pelo método citratos-EDTA Evaluation of the properties of Ba0,50Sr0.50Co0.80Fe0.20O3-d obtained by the citrate-EDTA method for intermediate temperature solid oxide fuel cell

    Directory of Open Access Journals (Sweden)

    E. Bonturim

    2013-03-01

    Full Text Available Ba0,50Sr0,50Co0,80Fe0,20O3-d (BSCF apresenta propriedades físicas, químicas e microestruturais adequadas para compor o cátodo de uma célula a combustível de óxido sólido de temperatura intermediária (ITSOFC. Este trabalho tem por objetivo a síntese e a caracterização do BSCF obtido pelo método dos citrados-EDTA. Os resultados obtidos por difração de raios X (DRX indicaram fases secundárias para o material calcinado a 700 e 800 ºC e fase única com estrutura cristalina do tipo perovskita para 900 ºC. As micrografias obtidas por microscopia eletrônica de varredura dos particulados evidenciou a formação de aglomerados de tamanho Ba0.50Sr0.50Co0.80Fe0.20O3-d (BSCF presents physical, chemical and microstructural properties suitable to form the cathode of Intermediate Temperature Solid Oxide Fuel Cell (ITSOFC. This work aims the synthesis and characterization of BSCF, obtained by the citrate-EDTA method. The X-ray diffraction results indicate secondary phases for the material calcined at 700 and 800 °C and single phase with perovskite crystalline structure at 900 °C. The SEM-FEG particles micrographs show the formation of < 20 µm clusters. The dilatometric analysis of pellets indicates the sintering temperature at ~ 1050 °C. XRD results of the sintered samples show perovskite single phase. The SEM micrographs confirmed the formation of higher porosity in the samples sintered at 1000 °C/1 h using powders calcined at 900 °C.

  13. Radiation-induced polymerisation of 2,3-dihydrofuran: free-radical or cationic mechanism?

    International Nuclear Information System (INIS)

    Janovsky, Igor; Naumov, Sergej; Knolle, Wolfgang; Mehnert, Reiner

    2005-01-01

    Concentrated (10 mol%) solutions of 2,3-dihydrofuran in CFCl 2 CF 2 Cl matrix were irradiated at 77 K and several intermediates (dimer radical cation, dihydrofuryl radical, and polymer radicals) were observed by low-temperature EPR spectroscopy. The irradiated solutions yielded after melting a polymeric product, which was characterised by IR spectroscopy and gel permeation chromatography. The polydisperse polymer is assumed to be formed mainly by a cationic process initiated by a dimer carbocation. The free-radical mechanism via the dihydrofuryl radical leads to low molecular weight oligomers only. Quantum chemical calculations support the interpretation of the experimental results

  14. Gnosticism and Radical Feminism

    DEFF Research Database (Denmark)

    Cahana, Jonathan

    2016-01-01

    and radical feminism would easily fall under this definition. There is, however, one major difference: since radical feminism is a relatively recent phenomenon which also benefited from modern modes of text production and preservation, almost all of the sources are still with us. This, in turn, may allow us...... to use radical feminism to make certain aspects of ancient Gnosticism re-emerge from their long submersion, provided that enough similarities can be independently drawn between the two phenomena to merit such a comparison. This paper therefore presents a comparison between concepts and positions...

  15. Homegrown religious radicalization

    DEFF Research Database (Denmark)

    Khawaja, Iram

    It has been reported that a growing number of youngsters from Western Europe are engaging in conflicts motivated by religious and political conflicts in the Middle East. This paper explores the reasons behind this seemingly religious radicalization from the point of view of the youngsters...... youngsters and parents of youngsters who have chosen a radicalized path in life. The paper will shed light on how the sense of and yearning for belonging and recognition have to be taken into account in our understanding of homegrown religious radicalization...

  16. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2011-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  17. Radical chemistry of artemisinin

    Science.gov (United States)

    Denisov, Evgenii T.; Solodova, S. L.; Denisova, Taisa G.

    2010-12-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  18. Radical chemistry of artemisinin

    International Nuclear Information System (INIS)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G

    2010-01-01

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  19. Radical's view of sciences

    International Nuclear Information System (INIS)

    Mittal, J.P.

    2004-01-01

    Full text: General concept in radiation biology is that free radicals are highly reactive and they can damage vital cellular molecules leading to injurious effects. However, in this talk, evidence will be presented through the techniques of electron paramagnetic resonance ( EPR ) and pulse radiolysis that free radicals can be highly selective in their reaction with the target molecules. In addition, attempts will be made to present a brief account of emerging scenario of free radical generation, identification and their involvement in radiation damage mechanisms in chemical and biological systems

  20. Radical chemistry of artemisinin

    Energy Technology Data Exchange (ETDEWEB)

    Denisov, Evgenii T; Solodova, S L; Denisova, Taisa G [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)

    2010-12-29

    The review summarizes physicochemical characteristics of the natural sesquiterpene peroxide artemisinin. The kinetic schemes of transformations of artemisinin radicals under anaerobic conditions are presented and analyzed. The sequence of radical reactions of artemisinin in the presence of oxygen is considered in detail. Special emphasis is given to the intramolecular chain oxidation resulting in the transformation of artemisinin into polyatomic hydroperoxide. The kinetic characteristics of elementary reaction steps involving alkyl, alkoxyl, and peroxyl radicals generated from artemisinin are discussed. The results of testing of artemisinin and its derivatives for the antimalarial activity and the scheme of the biochemical synthesis of artemisinin in nature are considered.

  1. Combustion Chemistry of Fuels: Quantitative Speciation Data Obtained from an Atmospheric High-temperature Flow Reactor with Coupled Molecular-beam Mass Spectrometer.

    Science.gov (United States)

    Köhler, Markus; Oßwald, Patrick; Krueger, Dominik; Whitside, Ryan

    2018-02-19

    This manuscript describes a high-temperature flow reactor experiment coupled to the powerful molecular beam mass spectrometry (MBMS) technique. This flexible tool offers a detailed observation of chemical gas-phase kinetics in reacting flows under well-controlled conditions. The vast range of operating conditions available in a laminar flow reactor enables access to extraordinary combustion applications that are typically not achievable by flame experiments. These include rich conditions at high temperatures relevant for gasification processes, the peroxy chemistry governing the low temperature oxidation regime or investigations of complex technical fuels. The presented setup allows measurements of quantitative speciation data for reaction model validation of combustion, gasification and pyrolysis processes, while enabling a systematic general understanding of the reaction chemistry. Validation of kinetic reaction models is generally performed by investigating combustion processes of pure compounds. The flow reactor has been enhanced to be suitable for technical fuels (e.g. multi-component mixtures like Jet A-1) to allow for phenomenological analysis of occurring combustion intermediates like soot precursors or pollutants. The controlled and comparable boundary conditions provided by the experimental design allow for predictions of pollutant formation tendencies. Cold reactants are fed premixed into the reactor that are highly diluted (in around 99 vol% in Ar) in order to suppress self-sustaining combustion reactions. The laminar flowing reactant mixture passes through a known temperature field, while the gas composition is determined at the reactors exhaust as a function of the oven temperature. The flow reactor is operated at atmospheric pressures with temperatures up to 1,800 K. The measurements themselves are performed by decreasing the temperature monotonically at a rate of -200 K/h. With the sensitive MBMS technique, detailed speciation data is acquired and

  2. Lump wood combustion process

    Science.gov (United States)

    Kubesa, Petr; Horák, Jiří; Branc, Michal; Krpec, Kamil; Hopan, František; Koloničný, Jan; Ochodek, Tadeáš; Drastichová, Vendula; Martiník, Lubomír; Malcho, Milan

    2014-08-01

    The article deals with the combustion process for lump wood in low-power fireplaces (units to dozens of kW). Such a combustion process is cyclical in its nature, and what combustion facility users are most interested in is the frequency, at which fuel needs to be stoked to the fireplace. The paper defines the basic terms such as burnout curve and burning rate curve, which are closely related to the stocking frequency. The fuel burning rate is directly dependent on the immediate thermal power of the fireplace. This is also related to the temperature achieved in the fireplace, magnitude of flue gas losses and the ability to generate conditions favouring the full burnout of the fuel's combustible component, which, at once ensures the minimum production of combustible pollutants. Another part of the paper describes experiments conducted in traditional fireplaces with a grate, at which well-dried lump wood was combusted.

  3. 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.

  4. Investigation of the combustion kinetics and polycyclic aromatic hydrocarbon emissions from polycaprolactone combustion.

    Science.gov (United States)

    Chien, Y C; Yang, S H

    2013-01-01

    Polycaprolactone (PCL) is one of the most attractive biodegradable plastics that has been widely used in medicine and agriculture fields. Because of the large increase in biodegradable plastics usage, the production of waste biodegradable plastics will be increasing dramatically, producing a growing environmental problem. Generally, waste PCL is collected along with municipal solid wastes and then incinerated. This study investigates the combustion kinetics and emission factors of 16 US Environmental Protection Agency (EPA) priority polycyclic aromatic hydrocarbons (PAHs) in the PCL combustion. Experimentally, two reactions are involved in the PCL combustion process, possibly resulting in the emission of carbon dioxide, propanal, protonated caprolactone and very small amounts of PAH produced by incomplete combustion. The intermediate products may continuously be oxidized to form CO2. The emission factors for 16 US EPA priority PAHs are n.d. -2.95 microg/g, which are much lower than those of poly lactic acid and other plastics combustion. The conversion of PCL is 100%. Results from this work suggest that combustion is a good choice for the waste PCL disposal.

  5. Investigation of Spark Ignition and Autoignition in Methane and Air Using Computational Fluid Dynamics and Chemical Reaction Kinetics. A numerical Study of Ignition Processes in Internal Combustion Engines

    Energy Technology Data Exchange (ETDEWEB)

    Nordrik, R.

    1993-12-01

    The processes in the combustion chamber of internal combustion engines have received increased attention in recent years because their efficiencies are important both economically and environmentally. This doctoral thesis studies the ignition phenomena by means of numerical simulation methods. The fundamental physical relations include flow field conservation equations, thermodynamics, chemical reaction kinetics, transport properties and spark modelling. Special attention is given to the inclusion of chemical kinetics in the flow field equations. Using his No Transport of Radicals Concept method, the author reduces the computational efforts by neglecting the transport of selected intermediate species. The method is validated by comparison with flame propagation data. A computational method is described and used to simulate spark ignition in laminar premixed methane-air mixtures and the autoignition process of a methane bubble surrounded by hot air. The spark ignition simulation agrees well with experimental results from the literature. The autoignition simulation identifies the importance of diffusive and chemical processes acting together. The ignition delay times exceed the experimental values found in the literature for premixed ignition delay, presumably because of the mixing process and lack of information on low temperature reactions in the skeletal kinetic mechanism. Transient turbulent methane jet autoignition is simulated by means of the KIVA-II code. Turbulent combustion is modelled by the Eddy Dissipation Concept. 90 refs., 81 figs., 3 tabs.

  6. Moderate and Radical Islam

    National Research Council Canada - National Science Library

    Rabasa, Angel

    2005-01-01

    This report presents the statement of Angel Rabasa, PhD, Senior Policy Analyst, The RAND Corporation, to the Committee on Armed Services, Defense Review Terrorism and Radical Islam Gap Panel, United...

  7. Exploring the negative temperature coefficient behavior of acetaldehyde based on detailed intermediate measurements in a jet-stirred reactor

    KAUST Repository

    Tao, Tao

    2018-03-20

    Acetaldehyde is an observed emission species and a key intermediate produced during the combustion and low-temperature oxidation of fossil and bio-derived fuels. Investigations into the low-temperature oxidation chemistry of acetaldehyde are essential to develop a better core mechanism and to better understand auto-ignition and cool flame phenomena. Here, the oxidation of acetaldehyde was studied at low-temperatures (528–946 K) in a jet-stirred reactor (JSR) with the corrected residence time of 2.7 s at 700 Torr. This work describes a detailed set of experimental results that capture the negative temperature coefficient (NTC) behavior in the low-temperature oxidation of acetaldehyde. The mole fractions of 28 species were measured as functions of the temperature by employing a vacuum ultra-violet photoionization molecular-beam mass spectrometer. To explain the observed NTC behavior, an updated mechanism was proposed, which well reproduces the concentration profiles of many observed peroxide intermediates. The kinetic analysis based on the updated mechanism reveals that the NTC behavior of acetaldehyde oxidation is caused by the competition between the O-addition to and the decomposition of the CHCO radical.

  8. Exploring the negative temperature coefficient behavior of acetaldehyde based on detailed intermediate measurements in a jet-stirred reactor

    KAUST Repository

    Tao, Tao; Sun, Wenyu; Hansen, Nils; Jasper, Ahren W.; Moshammer, Kai; Chen, Bingjie; Wang, Zhandong; Huang, Can; Dagaut, Philippe; Yang, Bin

    2018-01-01

    Acetaldehyde is an observed emission species and a key intermediate produced during the combustion and low-temperature oxidation of fossil and bio-derived fuels. Investigations into the low-temperature oxidation chemistry of acetaldehyde are essential to develop a better core mechanism and to better understand auto-ignition and cool flame phenomena. Here, the oxidation of acetaldehyde was studied at low-temperatures (528–946 K) in a jet-stirred reactor (JSR) with the corrected residence time of 2.7 s at 700 Torr. This work describes a detailed set of experimental results that capture the negative temperature coefficient (NTC) behavior in the low-temperature oxidation of acetaldehyde. The mole fractions of 28 species were measured as functions of the temperature by employing a vacuum ultra-violet photoionization molecular-beam mass spectrometer. To explain the observed NTC behavior, an updated mechanism was proposed, which well reproduces the concentration profiles of many observed peroxide intermediates. The kinetic analysis based on the updated mechanism reveals that the NTC behavior of acetaldehyde oxidation is caused by the competition between the O-addition to and the decomposition of the CHCO radical.

  9. Violent Radicalization in Europe

    DEFF Research Database (Denmark)

    Dalgaard-Nielsen, Anja

    2010-01-01

    When, why, and how do people living in a democracy become radicalized to the point of being willing to use or directly support the use of terrorist violence against fellow citizens? This question has been at the center of academic and public debate over the past years as terrorist attacks...... within this field and to answer the question: From an empirical point of view, what is known and what is not known about radicalization connected to militant Islamism in Europe?...

  10. Flameless Combustion Workshop

    National Research Council Canada - National Science Library

    Gutmark, Ephraim

    2005-01-01

    .... "Flameless Combustion" is characterized by high stability levels with virtually no thermoacoustic instabilities, very low lean stability limits and therefore extremely low NOx production, efficient...

  11. Research Combustion Laboratory (RCL)

    Data.gov (United States)

    Federal Laboratory Consortium — The Research Combustion Laboratory (RCL) develops aerospace propulsion technology by performing tests on propulsion components and materials. Altitudes up to 137,000...

  12. Combustion Byproducts Recycling Consortium

    Energy Technology Data Exchange (ETDEWEB)

    Paul Ziemkiewicz; Tamara Vandivort; Debra Pflughoeft-Hassett; Y. Paul Chugh; James Hower

    2008-08-31

    Ashlines: To promote and support the commercially viable and environmentally sound recycling of coal combustion byproducts for productive uses through scientific research, development, and field testing.

  13. an intermediate moisture meat

    African Journals Online (AJOL)

    STORAGESEVER

    2008-07-04

    Jul 4, 2008 ... traditional SM muscle without compromising quality. ... technique is intermediate moisture food processing. ... Traditionally, most tsire suya producers use ..... quality of Chinese purebred and European X Chinese crossbred ...

  14. Bacterial intermediate filaments

    DEFF Research Database (Denmark)

    Charbon, Godefroid; Cabeen, M.; Jacobs-Wagner, C.

    2009-01-01

    Crescentin, which is the founding member of a rapidly growing family of bacterial cytoskeletal proteins, was previously proposed to resemble eukaryotic intermediate filament (IF) proteins based on structural prediction and in vitro polymerization properties. Here, we demonstrate that crescentin...

  15. Mapping Intermediality in Performance

    NARCIS (Netherlands)

    2010-01-01

    Mapping Intermediality in Performance benadert het vraagstuk van intermedialiteit met betrekking tot performance (vooral theater) vanuit vijf verschillende invalshoeken: performativiteit en lichaam; tijd en ruimte; digitale cultuur en posthumanisme; netwerken; pedagogiek en praxis. In deze boeiende

  16. Hydroxyl radical induced degradation of ibuprofen

    Energy Technology Data Exchange (ETDEWEB)

    Illés, Erzsébet, E-mail: erzsebet.illes@chem.u-szeged.hu [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Takács, Erzsébet [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Dombi, András [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Gajda-Schrantz, Krisztina [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Department of Inorganic and Analytical Chemistry, University of Szeged, Szeged (Hungary); EMPA, Laboratory for High Performance Ceramics, Duebendorf (Switzerland); Rácz, Gergely; Gonter, Katalin; Wojnárovits, László [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary)

    2013-03-01

    Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1 mmol dm{sup −3}. For end product characterization {sup 60}Co γ-irradiation was used and the samples were evaluated either by taking their UV–vis spectra or by HPLC with UV or MS detection. The reactions of {sup ·}OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose. Highlights: ► In hydroxyl radical attack on the ring mainly hydroxylated products form ► The hydrated electron attacks the carboxyl group. ► Oxidative conditions are more effective in ibuprofen decomposition than reductive. ► Ecotoxicity of ibuprofen solution first increases then decreases with irradiation.

  17. Hydroxyl radical induced degradation of ibuprofen

    International Nuclear Information System (INIS)

    Illés, Erzsébet; Takács, Erzsébet; Dombi, András; Gajda-Schrantz, Krisztina; Rácz, Gergely; Gonter, Katalin; Wojnárovits, László

    2013-01-01

    Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1 mmol dm −3 . For end product characterization 60 Co γ-irradiation was used and the samples were evaluated either by taking their UV–vis spectra or by HPLC with UV or MS detection. The reactions of · OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose. Highlights: ► In hydroxyl radical attack on the ring mainly hydroxylated products form ► The hydrated electron attacks the carboxyl group. ► Oxidative conditions are more effective in ibuprofen decomposition than reductive. ► Ecotoxicity of ibuprofen solution first increases then decreases with irradiation

  18. Combustion Stratification for Naphtha from CI Combustion to PPC

    KAUST Repository

    Vallinayagam, R.; Vedharaj, S.; An, Yanzhao; Dawood, Alaaeldin; Izadi Najafabadi, Mohammad; Somers, Bart; Johansson, Bengt

    2017-01-01

    This study demonstrates the combustion stratification from conventional compression ignition (CI) combustion to partially premixed combustion (PPC). Experiments are performed in an optical CI engine at a speed of 1200 rpm for diesel and naphtha (RON

  19. Intermediate algebra & analytic geometry

    CERN Document Server

    Gondin, William R

    1967-01-01

    Intermediate Algebra & Analytic Geometry Made Simple focuses on the principles, processes, calculations, and methodologies involved in intermediate algebra and analytic geometry. The publication first offers information on linear equations in two unknowns and variables, functions, and graphs. Discussions focus on graphic interpretations, explicit and implicit functions, first quadrant graphs, variables and functions, determinate and indeterminate systems, independent and dependent equations, and defective and redundant systems. The text then examines quadratic equations in one variable, system

  20. Emissions of NO and CO from counterflow combustion of CH4 under MILD and oxyfuel conditions

    International Nuclear Information System (INIS)

    Cheong, Kin-Pang; Li, Pengfei; Wang, Feifei; Mi, Jianchun

    2017-01-01

    This paper reports on the NO and CO emission characteristics of counterflow combustion of methane simulated under MILD or/and oxyfuel conditions. Simulations using CHEMKIN are conducted for various injection conditions of fuel and oxidizer. Note that the terms “oxyfuel”, “MILD-N 2 ” and “MILD-CO 2 ” combustion adopted hereafter represent the conventional oxy-combustion and those MILD combustions diluted by N 2 and CO 2 , respectively. It is observed that the NO emission of MILD-CO 2 combustion is ultra-low for all cases of investigation, even when increasing the combustion temperature up to 2000 K or adding more N 2 (up to 20%) to either the fuel stream (to simulate nitrogen-containing fuels like biomass) or the oxidizer stream (to simulate the air-ingress). A higher temperature allowed under MILD-CO 2 combustion suggests the improvement of energy efficiency for the MILD combustion technology. Moreover, the presence of steam in the oxidant reduces both NO and CO emissions of combustion for all cases. The relative importance analysis reveals that the N 2 O-intermediate mechanism for producing NO prevails in MILD-CO 2 combustion while the prompt and thermal mechanisms predominate MILD-N 2 and oxyfuel combustion, respectively. In addition, the sensitivity analysis identifies those main reactions that play important roles for the NO emission under these combustion conditions. - Highlights: • Assessing the NO and CO emissions from MILD combustion diluted by CO 2 . • Examining the possibility of higher combustion intensity in MILD-CO 2 combustion than in MILD-N 2 combustion. • Differentiating the contributions from each NO mechanism to the total NO emission. • Revealing major NO mechanisms under different combustion conditions. • Better understanding the NO formation mechanisms under MILD combustion.

  1. Research concerning ionic and free radical reactions in radiation chemistry. Progress report, September 15, 1976--September 15, 1977

    International Nuclear Information System (INIS)

    Williams, T.F.

    1977-01-01

    Progress is reported on ESR studies of fluorocarbon radicals and intermediate radicals. A detailed study was made of the dimethyl, diethyl, and di-n-propyl carbonates. Studies were continued on hydrogen-atom abstraction reactions at low temperatures with view to evaluating the contribution from quantum-mechanical tunneling. Detection of the transient dimer radical anion of acetonitrile in the upper crystalline phase at -50 0 C is reported. Abstracts of current reports are included on electron attachment to fluorocarbons hydrogen atom abstraction by methyl radicals. EPR spectra of the tetrafluoroethylene radical anion, and addition of tetrafluoroethylene to the tetrafluoroethylene radical anion

  2. Radiochemistry - Applications in the study of radical mechanisms of biological interest

    International Nuclear Information System (INIS)

    Foos, Jacques

    1982-01-01

    In biology, oxygen reducing processes give rise to the formation of intermediate radicals. One of the major breakthroughs of radiation chemistry of aqueous solutions is the identification of these compounds. The author describes the techniques used to study the reaction of these radicals (of radiolytic origin) with biological molecules [fr

  3. Intermediates of radiolytic transformations of 6-aminophenalenone in ethanol

    International Nuclear Information System (INIS)

    Semenova, G.V.; Ponomarev, A.V.; Kartasheva, L.I.; Pikaev, A.K.

    1992-01-01

    Pulsed radiolysis method is used to study transformations intermediates of 6-aminophenalenone in ethanol. In alkaline medium the main product is radical-anion of 6-aminophenalenone, which optical absorption spectrum contains two bands with maxima at 355 and 400 nm. The particle precursors are e s , CH 3 CHOH and CH 3 CHO - radicals. In neutral and acid medium radical-anions are protonated in reactions with alcohol and hydrogen ions. The resulting H-adduct of 6-aminophenalenone has optical absorption maxima at 350 and 390 nm. Availability of two maxima is related to two various product structures. Molar extinction coefficients of radical-anions and H-adducts of 6-aminophenalenone and rate constants of reactions with their participation are estimated

  4. Intermediate products of radiolytic conversions of 6-aminophenalenone in ethanol

    International Nuclear Information System (INIS)

    Semenova, G.V.; Ponomarev, A.V.; Kartasheva, L.I.; Pikaev, A.K.

    1992-01-01

    Intermediate products of the conversions of 6-aminophenalenone in ethanol were investigated by pulse radiolysis. In alkaline medium the main product is the 6-aminophenalenone radical cation, the optical absorption spectrum of which contains two bands with maxima at 355 and 400 nm. The precursors of this particle are e s , CH 3 CHOH and CH 3 CHO - radicals. In neutral and acid medium, radical cations are protonated in reactions with alcohol and hydrogen ions. The H-adduct of 6-aminophenalenone that arises has optical absorption maxima at 350 and 390 nm. The presence of two maxima is due to two different structures of the product. The molar extinction coefficients of the radical anions and H-adducts of 6-aminophenalenone and the rate constants of the reactions involving them were estimated. 6 refs., 4 figs., 2 tabs

  5. Strobes: An oscillatory combustion

    NARCIS (Netherlands)

    Corbel, J.M.L.; Lingen, J.N.J. van; Zevenbergen, J.F.; Gijzeman, O.L.J.; Meijerink, A.

    2012-01-01

    Strobe compositions belong to the class of solid combustions. They are mixtures of powdered ingredients. When ignited, the combustion front evolves in an oscillatory fashion, and flashes of light are produced by intermittence. They have fascinated many scientists since their discovery at the

  6. Catalytically enhanced combustion process

    International Nuclear Information System (INIS)

    Rodriguez, C.

    1992-01-01

    This patent describes a fuel having improved combustion efficiency. It comprises a petroleum based liquid hydrocarbon; and a combustion catalyst comprising from about 18 to about 21 weight percent naphthalene, from about 75 to about 80 weight percent toluene, and from about 2.8 to about 3.2 weight percent benzyl alcohol

  7. Prediction of the combustion process and emission formation of a bi-fuel s.i. engine

    International Nuclear Information System (INIS)

    D'Errico, Gianluca

    2008-01-01

    A thermodynamic model is developed and validated for the prediction of the combustion process and pollutant formation in s.i. engines, fuelled by gasoline and compressed natural gas. Attention is focused on the main physical and chemical phenomena to allow a reliable evaluation of the burning rate and of the specie concentrations, including intermediates such as CO, O, H, and OH. A new correlation for laminar flame speed of methane-air mixtures is derived by interpolating more than 1000 different conditions at high pressure and temperature, computed by a detailed chemical approach. Successively an extended dissertation about the fundamental mechanisms which govern the pollutant formation in the turbulent premixed combustion which characterizes the s.i. engines is given. The conclusion of such analysis is the definition of a new reduced chemical scheme, based on the application of partial-equilibrium and steady-state assumptions for the radicals and the solution of a transport equation for each specie which is kinetically controlled. Finally the proposed schemes and formulations were embedded into the developed quasi-D model and into a CFD code, to simulate a s.i. engine fuelled by gasoline and CNG, allowing a deeper understanding of the reliability of the simplifications made in the quasi-dimensional model and a comprehensive investigation of several physical and chemical properties, whose experimental measurement is not usually available. Computed results were compared with the available experimental data of in-cylinder pressure histories and engine emissions for two different engine configurations

  8. NOx removal characteristics of corona radical shower with ammonia and methylamine radical injections

    Energy Technology Data Exchange (ETDEWEB)

    Urashima, K.; Ara, M.; Chang, J.S. [McMaster Univ., Hamilton, ON (Canada). Dept. of Engineering Physics; Uchida, Y. [Aichi Inst. of Technology, (Japan). Dept. of Engineering

    2010-07-01

    Air pollutants such as nitrogen oxides (NOx) and sulfur oxides (SOx) are the major cause of acid rain. There are different types of NOx and SOx conversion techniques such as wet scrubber, selective catalytic reactor, sorbent injection, and low NOx burner. Non-thermal plasma techniques have also been utilized in commercial plants, but the energy efficiency of the non-thermal plasma reactors have not yet been optimized. The direct plasma treatments of flue gases including, the electron beam, barrier discharge and pulsed corona reactors, may lose input energy to activate unwanted components of flue gases such as carbon dioxide (CO{sub 2}) and nitrogen (N{sub 2}). The corona discharge ammonia radical shower system has demonstrated significant NOx removal with higher energy efficiency for large bench scale and pilot plant tests for combustion exhausts. An experiment has also demonstrated that methane can replace ammonia as an injection gas with less NOx removal efficiency. This paper presented an experimental investigation that compared methylamine radical injection with traditional ammonia and methane radical injections. The paper discussed the bench scale test facilities and corona radical shower plasma reactor. It was concluded that the processes to form ammonium nitrate could be observed from trace white solid particles deposited on the reactor wall as observed by scanning electron microscopy pictures. 10 refs., 5 figs., 2 appendices.

  9. Laparoscopic radical trachelectomy.

    Science.gov (United States)

    Rendón, Gabriel J; Ramirez, Pedro T; Frumovitz, Michael; Schmeler, Kathleen M; Pareja, Rene

    2012-01-01

    The standard treatment for patients with early-stage cervical cancer has been radical hysterectomy. However, for women interested in future fertility, radical trachelectomy is now considered a safe and feasible option. The use of minimally invasive surgical techniques to perform this procedure has recently been reported. We report the first case of a laparoscopic radical trachelectomy performed in a developing country. The patient is a nulligravid, 30-y-old female with stage IB1 adenocarcinoma of the cervix who desired future fertility. She underwent a laparoscopic radical trachelectomy and bilateral pelvic lymph node dissection. The operative time was 340 min, and the estimated blood loss was 100mL. There were no intraoperative or postoperative complications. The final pathology showed no evidence of residual disease, and all pelvic lymph nodes were negative. At 20 mo of follow-up, the patient is having regular menses but has not yet attempted to become pregnant. There is no evidence of recurrence. Laparoscopic radical trachelectomy with pelvic lymphadenectomy in a young woman who desires future fertility may also be an alternative technique in the treatment of early cervical cancer in developing countries.

  10. PDF Modeling of Turbulent Combustion

    National Research Council Canada - National Science Library

    Pope, Stephen B

    2006-01-01

    .... The PDF approach to turbulent combustion has the advantages of fully representing the turbulent fluctuations of species and temperature, and of allowing realistic combustion chemistry to be implemented...

  11. Studies of radiation-produced radicals and radical ions. Progress report, June 1, 1981-August 31, 1982

    International Nuclear Information System (INIS)

    Williams, T.F.

    1982-01-01

    The discovery and characterization of novel radical ions produced by the γ irradiation of solids continues to be a fertile field for investigation. This Progress Report describes the generation and ESR identification of several new paramagnetic species, some of which have long been sought as important intermediates in radiation chemistry. We have also contributed to a general theoretical problem in ESR spectroscopy. Solid-state studies of electron attachment reactions, both non-dissociative and dissociative, reveal interesting structural and chemical information about the molecular nature of these processes for simple compounds. In particular, ESR measurements of the spin distribution in the products allow a fairly sharp distinction to be drawn between radical anions and radical-anion pairs or adducts. Dimer radical anion formation can also take place but the crystal structure plays a role in this process, as expected. Some radical anions undergo photolysis to give radical-anion pairs which may then revert back to the original radical anion by a thermal reaction. The chemistry of these reversible processes is made more intricate by a competing reaction in which the radical abstracts a hydrogen atom from a neighboring molecule. However, the unraveling of this complication has also served to extend our knowledge of the role of quantum tunneling in chemical reactions. The results of this investigation testify to the potential of solid-state techniques for the study of novel and frangible radical ions. Progress in this field shows no sign of abating, as witness the recent discovery of perfluorocycloalkane radical anions and alkane radical cations

  12. [Therapy of intermediate uveitis].

    Science.gov (United States)

    Doycheva, D; Deuter, C; Zierhut, M

    2014-12-01

    Intermediate uveitis is a form of intraocular inflammation in which the vitreous body is the major site of inflammation. Intermediate uveitis is primarily treated medicinally and systemic corticosteroids are the mainstay of therapy. When recurrence of uveitis or side effects occur during corticosteroid therapy an immunosuppressive treatment is required. Cyclosporine A is the only immunosuppressive agent that is approved for therapy of uveitis in Germany; however, other immunosuppressive drugs have also been shown to be effective and well-tolerated in patients with intermediate uveitis. In severe therapy-refractory cases when conventional immunosuppressive therapy has failed, biologics can be used. In patients with unilateral uveitis or when the systemic therapy is contraindicated because of side effects, an intravitreal steroid treatment can be carried out. In certain cases a vitrectomy may be used.

  13. Investigating radical cation chain processes in the electrocatalytic Diels-Alder reaction.

    Science.gov (United States)

    Imada, Yasushi; Okada, Yohei; Chiba, Kazuhiro

    2018-01-01

    Single electron transfer (SET)-triggered radical ion-based reactions have proven to be powerful options in synthetic organic chemistry. Although unique chain processes have been proposed in various photo- and electrochemical radical ion-based transformations, the turnover number, also referred to as catalytic efficiency, remains unclear in most cases. Herein, we disclose our investigations of radical cation chain processes in the electrocatalytic Diels-Alder reaction, leading to a scalable synthesis. A gram-scale synthesis was achieved with high current efficiency of up to 8000%. The reaction monitoring profiles showed sigmoidal curves with induction periods, suggesting the involvement of intermediate(s) in the rate determining step.

  14. Standard Gibbs free energies of reactions of ozone with free radicals in aqueous solution: quantum-chemical calculations.

    Science.gov (United States)

    Naumov, Sergej; von Sonntag, Clemens

    2011-11-01

    Free radicals are common intermediates in the chemistry of ozone in aqueous solution. Their reactions with ozone have been probed by calculating the standard Gibbs free energies of such reactions using density functional theory (Jaguar 7.6 program). O(2) reacts fast and irreversibly only with simple carbon-centered radicals. In contrast, ozone also reacts irreversibly with conjugated carbon-centered radicals such as bisallylic (hydroxycylohexadienyl) radicals, with conjugated carbon/oxygen-centered radicals such as phenoxyl radicals, and even with nitrogen- oxygen-, sulfur-, and halogen-centered radicals. In these reactions, further ozone-reactive radicals are generated. Chain reactions may destroy ozone without giving rise to products other than O(2). This may be of importance when ozonation is used in pollution control, and reactions of free radicals with ozone have to be taken into account in modeling such processes.

  15. Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

    Science.gov (United States)

    Wink, David A.; Desrosiers, Marc F.

    The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3,5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant ( .Br -2). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive intermediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide radical. Unexpectedly, addition of DBNBS to a solution containing dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented.

  16. Mobile communication and intermediality

    DEFF Research Database (Denmark)

    Helles, Rasmus

    2013-01-01

    communicative affordances of mobile devices in order to understand how people choose between them for different purposes. It is argued that mobile communication makes intermediality especially central, as the choice of medium is detached from the location of stationary media and begins to follow the user across......The article argues the importance of intermediality as a concept for research in mobile communication and media. The constant availability of several, partially overlapping channels for communication (texting, calls, email, Facebook, etc.) requires that we adopt an integrated view of the various...

  17. Money distribution with intermediation

    OpenAIRE

    Teles, Caio Augusto Colnago

    2013-01-01

    This pap er analyzes the distribution of money holdings in a commo dity money search-based mo del with intermediation. Intro ducing heterogeneity of costs to the Kiyotaki e Wright ( 1989 ) mo del, Cavalcanti e Puzzello ( 2010) gives rise to a non-degenerated distribution of money. We extend further this mo del intro ducing intermediation in the trading pro cess. We show that the distribution of money matters for savings decisions. This gives rises to a xed p oint problem for the ...

  18. Radical dematerialization and degrowth

    Science.gov (United States)

    Kallis, Giorgos

    2017-05-01

    The emission targets agreed in Paris require a radical reduction of material extraction, use and disposal. The core claim of this article is that a radical dematerialization can only be part and parcel of degrowth. Given that capitalist economies are designed to grow, this raises the question of whether, and under what circumstances, the inevitable `degrowth' can become socially sustainable. Three economic policies are discussed in this direction: work-sharing, green taxes and public money. This article is part of the themed issue 'Material demand reduction'.

  19. Muon substituted free radicals

    International Nuclear Information System (INIS)

    Burkhard, P.; Fischer, H.; Roduner, E.; Strub, W.; Gygax, F.N.; Brinkman, G.A.; Louwrier, P.W.F.; McKenna, D.; Ramos, M.; Webster, B.C.

    1984-01-01

    Spin polarized energetic positive muons are injected as magnetic probes into unsaturated organic liquids. They are implemented via fast chemical processes ( -10 s) in various molecules. Of particular interest among these are muonium substituted free radicals. The technique allows determination of accurate rate coefficients for fast chemical reactions of radicals. Furthermore, radiochemical processes occuring in picoseconds after injection of the muon are studied. Of fundamental interest are also the structural and dynamical implications of substituting a proton by a muon, or in other terms, a hydrogen atom by a muonium atom. Selected examples for each of these three types of experiments are given. (Auth.)

  20. Fuel Combustion Laboratory | Transportation Research | NREL

    Science.gov (United States)

    Fuel Combustion Laboratory Fuel Combustion Laboratory NREL's Fuel Combustion Laboratory focuses on designs, using both today's technology and future advanced combustion concepts. This lab supports the combustion chamber platform for fuel ignition kinetics research, was acquired to expand the lab's

  1. Spectroscopy and kinetics of combustion gases at high temperatures

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-12-01

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

  2. Counter radicalization development assistance

    OpenAIRE

    van Hippel, Karin

    2006-01-01

    The paper reviews current research and practice and recommends strategies for development agencies working in the Arab and Muslim world. It builds on the basic assumption that the realization of the Millennium Development Goals will be vital to reduce support for terrorism in the long term. Within this overall framework, emphasis is placed on particular programs that could be specifically applied to counter radicalization.

  3. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali; Khashab, Niveen M.; Fahrenbach, Albert C.; Friedman, Douglas C.; Colvin, Michael T.; Coti, Karla K.; Bení tez, Diego S.; Tkatchouk, Ekaterina; Olsen, John Carl; Belowich, Matthew E.; Carmieli, Raanan; Khatib, Hussam A.; Goddard, William Andrew III; Wasielewski, Michael R.; Stoddart, Fraser Fraser Raser

    2009-01-01

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  4. Sexuality Following Radical Prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Serefoglu, Ege C; Albersen, Maarten

    2017-01-01

    incontinence in relation to sexual activity after surgery. This can present at the time of orgasm (ie, climacturia) or arise during arousal. In general, the problem subsides with time and pelvic floor training and tension penile loops can be used as treatments. Orgasmic disturbances after radical prostatectomy...

  5. Radically enhanced molecular recognition

    KAUST Repository

    Trabolsi, Ali

    2009-12-17

    The tendency for viologen radical cations to dimerize has been harnessed to establish a recognition motif based on their ability to form extremely strong inclusion complexes with cyclobis(paraquat-p-phenylene) in its diradical dicationic redox state. This previously unreported complex involving three bipyridinium cation radicals increases the versatility of host-guest chemistry, extending its practice beyond the traditional reliance on neutral and charged guests and hosts. In particular, transporting the concept of radical dimerization into the field of mechanically interlocked molecules introduces a higher level of control within molecular switches and machines. Herein, we report that bistable and tristable [2]rotaxanes can be switched by altering electrochemical potentials. In a tristable [2]rotaxane composed of a cyclobis(paraquat-p-phenylene) ring and a dumbbell with tetrathiafulvalene, dioxynaphthalene and bipyridinium recognition sites, the position of the ring can be switched. On oxidation, it moves from the tetrathiafulvalene to the dioxynaphthalene, and on reduction, to the bipyridinium radical cation, provided the ring is also reduced simultaneously to the diradical dication. © 2010 Macmillan Publishers Limited. All rights reserved.

  6. Online Radicalization: Bangladesh Perspective

    Science.gov (United States)

    2017-06-09

    radicalization through cyberspace, Bangladesh mostly implements hard powers such as removing contents and restricting access to the internet. However, freedom...cyberspace, Bangladesh mostly implements hard powers such as removing contents and restricting access to the internet. However, freedom of speech...67 An Organizational Approach to Implement the Measures........................................ 69 Formation of

  7. Cation radicals of xanthophylls.

    Science.gov (United States)

    Galinato, Mary Grace I; Niedzwiedzki, Dariusz; Deal, Cailin; Birge, Robert R; Frank, Harry A

    2007-10-01

    Carotenes and xanthophylls are well known to act as electron donors in redox processes. This ability is thought to be associated with the inhibition of oxidative reactions in reaction centers and light-harvesting pigment-protein complexes of photosystem II (PSII). In this work, cation radicals of neoxanthin, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, beta-carotene, and lycopene were generated in solution using ferric chloride as an oxidant and then studied by absorption spectroscopy. The investigation provides a view toward understanding the molecular features that determine the spectral properties of cation radicals of carotenoids. The absorption spectral data reveal a shift to longer wavelength with increasing pi-chain length. However, zeaxanthin and beta-cryptoxanthin exhibit cation radical spectra blue-shifted compared to that of beta-carotene, despite all of these molecules having 11 conjugated carbon-carbon double bonds. CIS molecular orbital theory quantum computations interpret this effect as due to the hydroxyl groups in the terminal rings selectively stabilizing the highest occupied molecular orbitals of preferentially populated s-trans-isomers. The data are expected to be useful in the analysis of spectral results from PSII pigment-protein complexes seeking to understand the role of carotene and xanthophyll cation radicals in regulating excited state energy flow, in protecting PSII reaction centers against photoinhibition, and in dissipating excess light energy absorbed by photosynthetic organisms but not used for photosynthesis.

  8. Photoactivation of isoflavonoid phytoalexins: involvement of free radicals

    International Nuclear Information System (INIS)

    Bakker, J.; Gommers, F.J.; Smits, L.; Fuchs, A.; Vries, F.W. de

    1983-01-01

    Ultraviolet irradiation of isoflavonoid phytoalexins phaseollin, 3.6a. 9-trihydroxypterocarpan, glyceollin, tuberosin and pisatin, but not medicarpin, brought about inactivation of glucose-6-phosphate dehydrogenase in an in vitro assay system. Photoinactivation of the enzyme by photoactivated pisatin in air-saturated solutions was hardly affected by singlet oxygen quenchers such as NaN 3 , bovine serum albumin, histidine or methionine. Neither addition of the hydroxyl radical scavengers mannitol, Na-benzoate and ethanol nor the presence of catalase or superoxide dismutase protected the enzyme against photoinactivation, suggesting that OHradical, H 2 O 2 and O 2 radical are not the reactive oxygen species involved. However, the free radical scavenger S-(2-amino-ethyl)isothiouronium bromide hydrobromide (AET) protected the enzyme against inactivation by photoactivated pisatin. Direct evidence for the generation of free radicals was obtained by ESR measurements of solutions of phaseollin, pisatin and medicarpin in hexane irradiated with ultraviolet light in the presence or absence of O 2 . Phaseollin produced the most stable free radicals, whereas medicarpin hardly gave rise to free radical formation; pisatin took a somewhat intermediate position by producing a strong ESR signal which, however, decayed rather quickly. These results indicate free radical formation as the cause for photoinactivation of enzymes by photoactivated isoflavonoid phytoalexins. (author)

  9. [Research progress on free radicals in human body].

    Science.gov (United States)

    Wang, Q B; Xu, F P; Wei, C X; Peng, J; Dong, X D

    2016-08-10

    Free radicals are the intermediates of metabolism, widely exist in the human bodies. Under normal circumstances, the free radicals play an important role in the metabolic process on human body, cell signal pathway, gene regulation, induction of cell proliferation and apoptosis, so as to maintain the normal growth and development of human body and to inhibit the growth of bacteria, virus and cancer. However, when organic lesion occurs affected by external factors or when equilibrium of the free radicals is tipped in the human body, the free radicals will respond integratedly with lipids, protein or nucleic acid which may jeopardize the health of human bodies. This paper summarizes the research progress of the free radicals conducted in recent years, in relations to the perspective of the types, origins, test methods of the free radicals and their relationship with human's health. In addition, the possible mechanisms of environmental pollutants (such as polycyclic aromatic hydrocarbons) mediating oxidative stress and free radicals scavenging in the body were also summarized.

  10. Sandia Combustion Research: Technical review

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-07-01

    This report contains reports from research programs conducted at the Sandia Combustion Research Facility. Research is presented under the following topics: laser based diagnostics; combustion chemistry; reacting flow; combustion in engines and commercial burners; coal combustion; and industrial processing. Individual projects were processed separately for entry onto the DOE databases.

  11. Influences of the molecular fuel structure on combustion reactions towards soot precursors in selected alkane and alkene flames.

    Science.gov (United States)

    Ruwe, Lena; Moshammer, Kai; Hansen, Nils; Kohse-Höinghaus, Katharina

    2018-04-25

    In this study, we experimentally investigate the high-temperature oxidation kinetics of n-pentane, 1-pentene and 2-methyl-2-butene (2M2B) in a combustion environment using flame-sampling molecular beam mass spectrometry. The selected C5 fuels are prototypes for linear and branched, saturated and unsaturated fuel components, featuring different C-C and C-H bond structures. It is shown that the formation tendency of species, such as polycyclic aromatic hydrocarbons (PAHs), yielded through mass growth reactions increases drastically in the sequence n-pentane fuel-dependent reaction sequences of the gas-phase combustion mechanism that provide explanations for the observed difference in the PAH formation tendency. First, we investigate the fuel-structure-dependent formation of small hydrocarbon species that are yielded as intermediate species during the fuel decomposition, because these species are at the origin of the subsequent mass growth reaction pathways. Second, we review typical PAH formation reactions inspecting repetitive growth sequences in dependence of the molecular fuel structure. Third, we discuss how differences in the intermediate species pool influence the formation reactions of key aromatic ring species that are important for the PAH growth process underlying soot formation. As a main result it was found that for the fuels featuring a C[double bond, length as m-dash]C double bond, the chemistry of their allylic fuel radicals and their decomposition products strongly influences the combination reactions to the initially formed aromatic ring species and as a consequence, the PAH formation tendency.

  12. Free radical transfer in polymers

    International Nuclear Information System (INIS)

    Sonntag, C. von; Bothe, E.; Ulanski, P.

    1998-01-01

    For the present study of free-radical transfer in polymers pulse radiolysis and product studies have been carried out in aqueous solutions using thus far only the water-soluble polymers polyacrylic acid, polymethacrylic acid and polyvinyl alcohol. When OH radicals, generated in the radiolysis of N 2 O-saturated aqueous solutions, react with polymers the lifetime of the polymer radical thus created very much depends on the number of radicals per polymer chain. When there are a large number of radicals per chain their bimolecular decay may be faster than the corresponding (diffusion controlled) decay of monomeric radicals, but when the macromolecule contains only few or even just one radical their lifetime is considerably prolonged. Highly charged polymers such as polyacrylic acid at high pH attain a rod-like conformation which again favors a long lifetime of the radicals. Under such conditions, radical transfer reactions can occur. For example, in polyacrylic acid OH radicals generate two kinds of radicals side by side. The radical in β-position to the carboxylate group converts into the thermodynamically more stable α-radicals by an H-transfer reaction as can be followed by spectrophotometry. Besides radical transfer reactions β-fragmentation reactions occur causing chain scission. Such reactions can be followed in a pulse radiolysis experiment by conductometry, because counter ions are released upon chain scission. Such a process is especially effective in the case of polymethacrylic acid, where it results in a chain depolymerization. An intramolecular H-abstraction is also observed in the γ-radiolysis of polyacrylic acid with the corresponding peroxyl radicals. This causes a chain reaction to occur. The resulting hydroperoxides are unstable and decarboxylate given rise to acetylacetone-like products. In polyvinyl alcohol the peroxyl radicals in α-position to the alcohol function undergo HO 2 -elimination. This prevents a scission of the polymer chain in the

  13. Shale oil combustion

    International Nuclear Information System (INIS)

    Al-dabbas, M.A.

    1992-05-01

    A 'coutant' carbon steel combustion chamber cooled by water jacket was conslructed to burn diesel fuel and mixlure of shale oil and diesel fuels. During experimental work nir fuel ratio was determined, temperaturces were measured using Chromel/ Almel thermocouple, finally the gasous combustion product analysis was carricd out using gas chromatograph technique. The constructed combustion chamber was operating salisfactory for several hours of continous work. According to the measurements it was found that: the flame temperature of a mixture of diesel and shale oil fuels was greater than the flame temperature of diesel fuel. and the sulfer emissious of a mixture of diesel and shale oil fuels was higher than that of diesel fuel. Calculation indicated that the dry gas energy loss was very high and the incomplete combustion energy loss very small. (author). 23 refs., 35 figs

  14. Shale oil combustion

    Energy Technology Data Exchange (ETDEWEB)

    Al-dabbas, M A

    1992-05-01

    A `coutant` carbon steel combustion chamber cooled by water jacket was conslructed to burn diesel fuel and mixlure of shale oil and diesel fuels. During experimental work nir fuel ratio was determined, temperaturces were measured using Chromel/ Almel thermocouple, finally the gasous combustion product analysis was carricd out using gas chromatograph technique. The constructed combustion chamber was operating salisfactory for several hours of continous work. According to the measurements it was found that: the flame temperature of a mixture of diesel and shale oil fuels was greater than the flame temperature of diesel fuel. and the sulfer emissious of a mixture of diesel and shale oil fuels was higher than that of diesel fuel. Calculation indicated that the dry gas energy loss was very high and the incomplete combustion energy loss very small. (author). 23 refs., 35 figs.

  15. Indoor combustion and asthma.

    Science.gov (United States)

    Belanger, Kathleen; Triche, Elizabeth W

    2008-08-01

    Indoor combustion produces both gases (eg, nitrogen dioxide, carbon monoxide) and particulate matter that may affect the development or exacerbation of asthma. Sources in the home include both heating devices (eg, fireplaces, woodstoves, kerosene heaters, flued [ie, vented] or nonflued gas heaters) and gas stoves for cooking. This article highlights the recent literature examining associations between exposure to indoor combustion and asthma development and severity. Since asthma is a chronic condition affecting both children and adults, both age groups are included in this article. Overall, there is some evidence of an association between exposure to indoor combustion and asthma, particularly asthma symptoms in children. Some sources of combustion such as coal stoves have been more consistently associated with these outcomes than other sources such as woodstoves.

  16. Regeneration of phenolic antioxidants from phenoxyl radicals: An ESR and electrochemical study of antioxidant hierarchy

    DEFF Research Database (Denmark)

    Jørgensen, Lars V.; Madsen, Helle L.; Thomsen, Marianne K.

    1999-01-01

    Radicals from the flavonoids quercetin, (+)-catechin, (+/-)-taxifolin and luteolin, and from all-rac-alpha-tocopherol have been generated electrochemically by one-electron oxidation in deaerated dimethylformamide (DMF), and characterised by electron spin resonance spectroscopy (ESR) after spin......-trapping by 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Simulations of the ESR spectrum based on estimated coupling constants of the spin-trapped quercetin radical, confirmed that this antioxidant radical is oxygen-centered. The complex mixture of radicals, quinoid intermediates and stable two-electron oxidation...

  17. Sandia Combustion Research Program

    Energy Technology Data Exchange (ETDEWEB)

    Johnston, S.C.; Palmer, R.E.; Montana, C.A. (eds.)

    1988-01-01

    During the late 1970s, in response to a national energy crisis, Sandia proposed to the US Department of Energy (DOE) a new, ambitious program in combustion research. Shortly thereafter, the Combustion Research Facility (CRF) was established at Sandia's Livermore location. Designated a ''user facility,'' the charter of the CRF was to develop and maintain special-purpose resources to support a nationwide initiative-involving US inventories, industry, and national laboratories--to improve our understanding and control of combustion. This report includes descriptions several research projects which have been simulated by working groups and involve the on-site participation of industry scientists. DOE's Industry Technology Fellowship program, supported through the Office of Energy Research, has been instrumental in the success of some of these joint efforts. The remainder of this report presents results of calendar year 1988, separated thematically into eleven categories. Referred journal articles appearing in print during 1988 and selected other publications are included at the end of Section 11. Our traditional'' research activities--combustion chemistry, reacting flows, diagnostics, engine and coal combustion--have been supplemented by a new effort aimed at understanding combustion-related issues in the management of toxic and hazardous materials.

  18. Muonium-containing vinyl radicals

    International Nuclear Information System (INIS)

    Rhodes, C.J.; Symons, M.C.R.; Roduner, E.; Heming, M.

    1987-01-01

    Exposure of trimethylsilylacetylene and bis(trimethylsilyl)acetylene to positive muons gave radicals whose muon-electron hyperfine coupling constants establish that the corresponding vinyl radicals were formed. (author)

  19. The Rise of Radicals in Bioinorganic Chemistry.

    Science.gov (United States)

    Gray, Harry B; Winkler, Jay R

    2016-10-01

    Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O 2 are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) and tryptophan (Trp) residues have been found in many O 2 -reactive enzymes, raising the possibility that they play an antioxidant protective role. In blue copper proteins with plastocyanin-like domains, Tyr/Trp clusters are uncommon in the low-potential single-domain electron-transfer proteins and in the two-domain copper nitrite reductases. The two-domain muticopper oxidases, however, exhibit clusters of Tyr and Trp residues near the trinuclear copper active site where O 2 is reduced. These clusters may play a protective role to ensure that reactive oxygen species are not liberated during O 2 reduction.

  20. Advice concerning the advantages of a reference incinerator for low-level and intermediate-level radioactive waste processing

    International Nuclear Information System (INIS)

    Luyten, G.B.

    1985-05-01

    In this report, an inventory is presented of new incinerators and flue gas filters used in low and intermediate-level radioactive waste combustion. It is argued that a 'reference equipment' for the combustion of solid and liquid low- and intermediate-level wastes best meets existing Dutch radiation protection standards. A cost-benefit analysis of such an equipment is given including annual costs of investment, capital and exploration. A separate combustion process of organic liquids and carrions is considered finally. (G.J.P.)

  1. The Intermediate Neutrino Program

    CERN Document Server

    Adams, C.; Ankowski, A.M.; Asaadi, J.A.; Ashenfelter, J.; Axani, S.N.; Babu, K.; Backhouse, C.; Band, H.R.; Barbeau, P.S.; Barros, N.; Bernstein, A.; Betancourt, M.; Bishai, M.; Blucher, E.; Bouffard, J.; Bowden, N.; Brice, S.; Bryan, C.; Camilleri, L.; Cao, J.; Carlson, J.; Carr, R.E.; Chatterjee, A.; Chen, M.; Chen, S.; Chiu, M.; Church, E.D.; Collar, J.I.; Collin, G.; Conrad, J.M.; Convery, M.R.; Cooper, R.L.; Cowen, D.; Davoudiasl, H.; de Gouvea, A.; Dean, D.J.; Deichert, G.; Descamps, F.; DeYoung, T.; Diwan, M.V.; Djurcic, Z.; Dolinski, M.J.; Dolph, J.; Donnelly, B.; Dwyer, D.A.; Dytman, S.; Efremenko, Y.; Everett, L.L.; Fava, A.; Figueroa-Feliciano, E.; Fleming, B.; Friedland, A.; Fujikawa, B.K.; Gaisser, T.K.; Galeazzi, M.; Galehouse, D.C.; Galindo-Uribarri, A.; Garvey, G.T.; Gautam, S.; Gilje, K.E.; Gonzalez-Garcia, M.; Goodman, M.C.; Gordon, H.; Gramellini, E.; Green, M.P.; Guglielmi, A.; Hackenburg, R.W.; Hackenburg, A.; Halzen, F.; Han, K.; Hans, S.; Harris, D.; Heeger, K.M.; Herman, M.; Hill, R.; Holin, A.; Huber, P.; Jaffe, D.E.; Johnson, R.A.; Joshi, J.; Karagiorgi, G.; Kaufman, L.J.; Kayser, B.; Kettell, S.H.; Kirby, B.J.; Klein, J.R.; Kolomensky, Yu. G.; Kriske, R.M.; Lane, C.E.; Langford, T.J.; Lankford, A.; Lau, K.; Learned, J.G.; Ling, J.; Link, J.M.; Lissauer, D.; Littenberg, L.; Littlejohn, B.R.; Lockwitz, S.; Lokajicek, M.; Louis, W.C.; Luk, K.; Lykken, J.; Marciano, W.J.; Maricic, J.; Markoff, D.M.; Martinez Caicedo, D.A.; Mauger, C.; Mavrokoridis, K.; McCluskey, E.; McKeen, D.; McKeown, R.; Mills, G.; Mocioiu, I.; Monreal, B.; Mooney, M.R.; Morfin, J.G.; Mumm, P.; Napolitano, J.; Neilson, R.; Nelson, J.K.; Nessi, M.; Norcini, D.; Nova, F.; Nygren, D.R.; Orebi Gann, G.D.; Palamara, O.; Parsa, Z.; Patterson, R.; Paul, P.; Pocar, A.; Qian, X.; Raaf, J.L.; Rameika, R.; Ranucci, G.; Ray, H.; Reyna, D.; Rich, G.C.; Rodrigues, P.; Romero, E.Romero; Rosero, R.; Rountree, S.D.; Rybolt, B.; Sanchez, M.C.; Santucci, G.; Schmitz, D.; Scholberg, K.; Seckel, D.; Shaevitz, M.; Shrock, R.; Smy, M.B.; Soderberg, M.; Sonzogni, A.; Sousa, A.B.; Spitz, J.; St. John, J.M.; Stewart, J.; Strait, J.B.; Sullivan, G.; Svoboda, R.; Szelc, A.M.; Tayloe, R.; Thomson, M.A.; Toups, M.; Vacheret, A.; Vagins, M.; Van de Water, R.G.; Vogelaar, R.B.; Weber, M.; Weng, W.; Wetstein, M.; White, C.; White, B.R.; Whitehead, L.; Whittington, D.W.; Wilking, M.J.; Wilson, R.J.; Wilson, P.; Winklehner, D.; Winn, D.R.; Worcester, E.; Yang, L.; Yeh, M.; Yokley, Z.W.; Yoo, J.; Yu, B.; Yu, J.; Zhang, C.

    2015-01-01

    The US neutrino community gathered at the Workshop on the Intermediate Neutrino Program (WINP) at Brookhaven National Laboratory February 4-6, 2015 to explore opportunities in neutrino physics over the next five to ten years. Scientists from particle, astroparticle and nuclear physics participated in the workshop. The workshop examined promising opportunities for neutrino physics in the intermediate term, including possible new small to mid-scale experiments, US contributions to large experiments, upgrades to existing experiments, R&D plans and theory. The workshop was organized into two sets of parallel working group sessions, divided by physics topics and technology. Physics working groups covered topics on Sterile Neutrinos, Neutrino Mixing, Neutrino Interactions, Neutrino Properties and Astrophysical Neutrinos. Technology sessions were organized into Theory, Short-Baseline Accelerator Neutrinos, Reactor Neutrinos, Detector R&D and Source, Cyclotron and Meson Decay at Rest sessions.This report summ...

  2. The Intermediate Neutrino Program

    Energy Technology Data Exchange (ETDEWEB)

    Adams, C.; et al.

    2015-03-23

    The US neutrino community gathered at the Workshop on the Intermediate Neutrino Program (WINP) at Brookhaven National Laboratory February 4-6, 2015 to explore opportunities in neutrino physics over the next five to ten years. Scientists from particle, astroparticle and nuclear physics participated in the workshop. The workshop examined promising opportunities for neutrino physics in the intermediate term, including possible new small to mid-scale experiments, US contributions to large experiments, upgrades to existing experiments, R&D plans and theory. The workshop was organized into two sets of parallel working group sessions, divided by physics topics and technology. Physics working groups covered topics on Sterile Neutrinos, Neutrino Mixing, Neutrino Interactions, Neutrino Properties and Astrophysical Neutrinos. Technology sessions were organized into Theory, Short-Baseline Accelerator Neutrinos, Reactor Neutrinos, Detector R&D and Source, Cyclotron and Meson Decay at Rest sessions.This report summarizes discussion and conclusions from the workshop.

  3. The Intermediate Neutrino Program

    Energy Technology Data Exchange (ETDEWEB)

    Adams, C. [Yale Univ., New Haven, CT (United States); Alonso, J. R. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Ankowski, A. M. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Asaadi, J. A. [Syracuse Univ., NY (United States); Ashenfelter, J. [Yale Univ., New Haven, CT (United States); Axani, S. N. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Babu, K [Oklahoma State Univ., Stillwater, OK (United States); Backhouse, C. [California Inst. of Technology (CalTech), Pasadena, CA (United States); Band, H. R. [Yale Univ., New Haven, CT (United States); Barbeau, P. S. [Duke Univ., Durham, NC (United States); Barros, N. [Univ. of Pennsylvania, Philadelphia, PA (United States); Bernstein, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Betancourt, M. [Illinois Inst. of Technology, Chicago, IL (United States); Bishai, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Blucher, E. [Univ. of Chicago, IL (United States); Bouffard, J. [State Univ. of New York (SUNY), Albany, NY (United States); Bowden, N. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Brice, S. [Illinois Inst. of Technology, Chicago, IL (United States); Bryan, C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Camilleri, L. [Columbia Univ., New York, NY (United States); Cao, J. [Inst. of High Energy Physics, Beijing (China); Carlson, J. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Carr, R. E. [Columbia Univ., New York, NY (United States); Chatterjee, A. [Univ. of Texas, Arlington, TX (United States); Chen, M. [Univ. of California, Irvine, CA (United States); Chen, S. [Tsinghua Univ., Beijing (China); Chiu, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Church, E. D. [Illinois Inst. of Technology, Chicago, IL (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Collar, J. I. [Univ. of Chicago, IL (United States); Collin, G. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Conrad, J. M. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Convery, M. R. [SLAC National Accelerator Lab., Menlo Park, CA (United States); Cooper, R. L. [Indiana Univ., Bloomington, IN (United States); Cowen, D. [Pennsylvania State Univ., University Park, PA (United States); Davoudiasl, H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gouvea, A. D. [Northwestern Univ., Evanston, IL (United States); Dean, D. J. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Deichert, G. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Descamps, F. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); DeYoung, T. [Michigan State Univ., East Lansing, MI (United States); Diwan, M. V. [Brookhaven National Lab. (BNL), Upton, NY (United States); Djurcic, Z. [Argonne National Lab. (ANL), Argonne, IL (United States); Dolinski, M. J. [Drexel Univ., Philadelphia, PA (United States); Dolph, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Donnelly, B. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Dwyer, D. A. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Dytman, S. [Univ. of Pittsburgh, PA (United States); Efremenko, Y. [Univ. of Tennessee, Knoxville, TN (United States); Everett, L. L. [Univ. of Wisconsin, Madison, WI (United States); Fava, A. [University of Padua, Padova (Italy); Figueroa-Feliciano, E. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Fleming, B. [Yale Univ., New Haven, CT (United States); Friedland, A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Fujikawa, B. K. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Gaisser, T. K. [Univ. of Delaware, Newark, DE (United States); Galeazzi, M. [Univ. of Miami, FL (United States); Galehouse, DC [Univ. of Akron, OH (United States); Galindo-Uribarri, A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Garvey, G. T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Gautam, S. [Tribhuvan Univ., Kirtipur (Nepal); Gilje, K. E. [Illinois Inst. of Technology, Chicago, IL (United States); Gonzalez-Garcia, M. [Stony Brook Univ., NY (United States); Goodman, M. C. [Argonne National Lab. (ANL), Argonne, IL (United States); Gordon, H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Gramellini, E. [Yale Univ., New Haven, CT (United States); Green, M. P. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Guglielmi, A. [University of Padua, Padova (Italy); Hackenburg, R. W. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hackenburg, A. [Yale Univ., New Haven, CT (United States); Halzen, F. [Univ. of Wisconsin, Madison, WI (United States); Han, K. [Yale Univ., New Haven, CT (United States); Hans, S. [Brookhaven National Lab. (BNL), Upton, NY (United States); Harris, D. [Illinois Inst. of Technology, Chicago, IL (United States); Heeger, K. M. [Yale Univ., New Haven, CT (United States); Herman, M. [Brookhaven National Lab. (BNL), Upton, NY (United States); Hill, R. [Univ. of Chicago, IL (United States); Holin, A. [Univ. College London, Bloomsbury (United Kingdom); Huber, P. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Jaffe, D. E. [Brookhaven National Lab. (BNL), Upton, NY (United States); Johnson, R. A. [Univ. of Cincinnati, OH (United States); Joshi, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Karagiorgi, G. [Univ. of Manchester (United Kingdom); Kaufman, L. J. [Indiana Univ., Bloomington, IN (United States); Kayser, B. [Illinois Inst. of Technology, Chicago, IL (United States); Kettell, S. H. [Brookhaven National Lab. (BNL), Upton, NY (United States); Kirby, B. J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Klein, J. R. [Univ. of Texas, Arlington, TX (United States); Kolomensky, Y. G. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Kriske, R. M. [Univ. of Minnesota, Minneapolis, MN (United States); Lane, C. E. [Drexel Univ., Philadelphia, PA (United States); Langford, T. J. [Yale Univ., New Haven, CT (United States); Lankford, A. [Univ. of California, Irvine, CA (United States); Lau, K. [Univ. of Houston, TX (United States); Learned, J. G. [Univ. of Hawaii, Honolulu, HI (United States); Ling, J. [Univ. of Illinois, Urbana-Champaign, IL (United States); Link, J. M. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Lissauer, D. [Brookhaven National Lab. (BNL), Upton, NY (United States); Littenberg, L. [Brookhaven National Lab. (BNL), Upton, NY (United States); Littlejohn, B. R. [Illinois Inst. of Technology, Chicago, IL (United States); Lockwitz, S. [Illinois Inst. of Technology, Chicago, IL (United States); Lokajicek, M. [Inst. of Physics of the Academy of Sciences of Czech Republic, Prague (Czech Republic); Louis, W. C. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Luk, K. [Univ. of California, Berkeley, CA (United States); Lykken, J. [Illinois Inst. of Technology, Chicago, IL (United States); Marciano, W. J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Maricic, J. [Univ. of Hawaii, Honolulu, HI (United States); Markoff, D. M. [North Carolina Central Univ., Durham, NC (United States); Caicedo, D. A. M. [Illinois Inst. of Technology, Chicago, IL (United States); Mauger, C. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Mavrokoridis, K. [Univ. of Liverpool (United Kingdom); McCluskey, E. [Illinois Inst. of Technology, Chicago, IL (United States); McKeen, D. [Univ. of Washington, Seattle, WA (United States); McKeown, R. [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States); Mills, G. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Mocioiu, I. [Pennsylvania State Univ., University Park, PA (United States); Monreal, B. [Univ. of California, Santa Barbara, CA (United States); Mooney, M. R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Morfin, J. G. [Illinois Inst. of Technology, Chicago, IL (United States); Mumm, P. [National Inst. of Standards and Technology (NIST), Boulder, CO (United States); Napolitano, J. [Temple Univ., Philadelphia, PA (United States); Neilson, R. [Drexel Univ., Philadelphia, PA (United States); Nelson, J. K. [College of William and Mary, Williamsburg, VA (United States); Nessi, M. [European Organization for Nuclear Research (CERN), Geneva (Switzerland); Norcini, D. [Yale Univ., New Haven, CT (United States); Nova, F. [Univ. of Texas, Austin, TX (United States); Nygren, D. R. [Univ. of Texas, Arlington, TX (United States); Gann, GDO [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Palamara, O. [Illinois Inst. of Technology, Chicago, IL (United States); Parsa, Z. [Brookhaven National Lab. (BNL), Upton, NY (United States); Patterson, R. [California Inst. of Technology (CalTech), Pasadena, CA (United States); Paul, P. [Stony Brook Univ., NY (United States); Pocar, A. [Univ. of Massachusetts, Amherst, MA (United States); Qian, X. [Brookhaven National Lab. (BNL), Upton, NY (United States); Raaf, J. L. [Illinois Inst. of Technology, Chicago, IL (United States); Rameika, R. [Illinois Inst. of Technology, Chicago, IL (United States); Ranucci, G. [National Inst. of Nuclear Physics, Milano (Italy); Ray, H. [Univ. of Florida, Gainesville, FL (United States); Reyna, D. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Rich, G. C. [Triangle Universities Nuclear Lab., Durham, NC (United States); Rodrigues, P. [Univ. of Rochester, NY (United States); Romero, E. R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States); Rosero, R. [Brookhaven National Lab. (BNL), Upton, NY (United States); Rountree, S. D. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Rybolt, B. [Univ. of Tennessee, Knoxville, TN (United States); Sanchez, M. C. [Iowa State Univ., Ames, IA (United States); Santucci, G. [Stony Brook Univ., NY (United States); Schmitz, D. [Univ. of Chicago, IL (United States); Scholberg, K. [Duke Univ., Durham, NC (United States); Seckel, D. [Univ. of Delaware, Newark, DE (United States); Shaevitz, M. [Columbia Univ., New York, NY (United States); Shrock, R. [Stony Brook Univ., NY (United States); Smy, M. B. [Univ. of California, Irvine, CA (United States); Soderberg, M. [Syracuse Univ., NY (United States); Sonzogni, A. [Brookhaven National Lab. (BNL), Upton, NY (United States); Sousa, A. B. [Univ. of Cincinnati, OH (United States); Spitz, J. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); John, J. M. S. [Univ. of Cincinnati, OH (United States); Stewart, J. [Brookhaven National Lab. (BNL), Upton, NY (United States); Strait, J. B. [Illinois Inst. of Technology, Chicago, IL (United States); Sullivan, G. [Univ. of Maryland, College Park, MD (United States); Svoboda, R. [Univ. of California, Davis, CA (United States); Szelc, A. M. [Yale Univ., New Haven, CT (United States); Tayloe, R. [Indiana Univ., Bloomington, IN (United States); Thomson, M. A. [Univ. of Cambridge (United Kingdom); Toups, M. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Vacheret, A. [Univ. of Oxford (United Kingdom); Vagins, M. [Univ. of California, Irvine, CA (United States); Water, R. G. V. D. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Vogelaar, R. B. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Weber, M. [Bern (Switzerland); Weng, W. [Brookhaven National Lab. (BNL), Upton, NY (United States); Wetstein, M. [Univ. of Chicago, IL (United States); White, C. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); White, B. R. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Whitehead, L. [Univ. of Houston, TX (United States); Whittington, D. W. [Indiana Univ., Bloomington, IN (United States); Wilking, M. J. [Stony Brook Univ., NY (United States); Wilson, R. J. [Colorado State Univ., Fort Collins, CO (United States); Wilson, P. [Illinois Inst. of Technology, Chicago, IL (United States); Winklehner, D. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Winn, D. R. [Fairfield Univ., CT (United States); Worcester, E. [Brookhaven National Lab. (BNL), Upton, NY (United States); Yang, L. [Univ. of Illinois, Urbana-Champaign, IL (United States); Yeh, M [Brookhaven National Lab. (BNL), Upton, NY (United States); Yokley, Z. W. [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Yoo, J. [Illinois Inst. of Technology, Chicago, IL (United States); Yu, B. [Brookhaven National Lab. (BNL), Upton, NY (United States); Yu, J. [Univ. of Texas, Arlington, TX (United States); Zhang, C. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2017-04-03

    The US neutrino community gathered at the Workshop on the Intermediate Neutrino Program (WINP) at Brookhaven National Laboratory February 4-6, 2015 to explore opportunities in neutrino physics over the next five to ten years. Scientists from particle, astroparticle and nuclear physics participated in the workshop. The workshop examined promising opportunities for neutrino physics in the intermediate term, including possible new small to mid-scale experiments, US contributions to large experiments, upgrades to existing experiments, R&D plans and theory. The workshop was organized into two sets of parallel working group sessions, divided by physics topics and technology. Physics working groups covered topics on Sterile Neutrinos, Neutrino Mixing, Neutrino Interactions, Neutrino Properties and Astrophysical Neutrinos. Technology sessions were organized into Theory, Short-Baseline Accelerator Neutrinos, Reactor Neutrinos, Detector R&D and Source, Cyclotron and Meson Decay at Rest sessions.This report summarizes discussion and conclusions from the workshop.

  4. Reactive intermediates in the gas phase generation and monitoring

    CERN Document Server

    Setser, D W

    2013-01-01

    Reactive Intermediates in the Gas Phase: Generation and Monitoring covers methods for reactive intermediates in the gas phase. The book discusses the generation and measurement of atom and radical concentrations in flow systems; the high temperature flow tubes, generation and measurement of refractory species; and the electronically excited long-lived states of atoms and diatomic molecules in flow systems. The text also describes the production and detection of reactive species with lasers in static systems; the production of small positive ions in a mass spectrometer; and the discharge-excite

  5. Intermediate energy data

    International Nuclear Information System (INIS)

    Koning, A.J.; Fukahori, T.; Hasegawa, A.

    1998-01-01

    Subgroup 13 (SG13) on Intermediate Energy Nuclear data was formed by NEA Nuclear Science Committee to solve common problems of these types of data for nuclear applications. An overview is presented in this final report of the present activities of SG13, including data needs, high-priority nuclear data request list (nuclides), compilation of experimental data, specialists meetings and benchmarks, data formats and data libraries. Some important accomplishments are summarized, and recommendations are presented. (R.P.)

  6. Types of organic materials present in BNFL intermediate level waste streams

    International Nuclear Information System (INIS)

    Barlow, P.

    1988-01-01

    This presentation lists the constituents present in BNFL intermediate-level radioactive wastes. The inorganic and organic components are listed and there is a detailed analysis of the plutonium contaminated materials in terms of proportion of combustible and non-combustible content, up to the year 2000. A description of the Waste Treatment Complex at Sellafield is presented. The research programme for leach testing, sorption and solubility testing and decomposition of organic matter was outlined. (U.K.)

  7. Time-resolved FTIR emission studies of laser photofragmentation and radical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Leone, S.R. [Univ. of Colorado, Boulder (United States)

    1993-12-01

    Recent studies have focused specifically on collision processes, such as single collision energy transfer, reaction dynamics, and radical reactions. The authors employ novel FTIR techniques in the study of single collision energy transfer processes using translationally fast H atom, as well as radical-radical reactions, e.g. CH{sub 3} + O, CF{sub 3} + H(D), and Cl + C{sub 2}H{sub 5}. The fast atoms permit unique high energy regions of certain transition states of combustion species to be probed for the first time.

  8. Free radical explosive composition

    Science.gov (United States)

    Walker, Franklin E.; Wasley, Richard J.

    1979-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a getter additive comprising a compound or mixture of compounds capable of capturing or deactivating free radicals or ions under mechanical or electrical shock conditions and which is not an explosive. Exemplary getter additives are isocyanates, olefins and iodine.

  9. Trends in radical prostatectomy.

    Science.gov (United States)

    Eastham, James; Tokuda, Yuji; Scardino, Peter

    2009-02-01

    The surgical treatment of prostate cancer ideally removes the entire cancer, avoids excessive blood loss or serious perioperative complications, and results in complete recovery of continence and potency. To achieve this, the surgeon must excise sufficient periprostatic tissue to cure the cancer while preserving the cavernosal nerves required for erectile function and the neuromusculature required for normal urinary and bowel function. Here we will examine recent trends in radical prostatectomy, focusing on surgical technique.

  10. Deciphering free-radical code of radiation effects

    International Nuclear Information System (INIS)

    Volovyk, S.; Bazyka, D.; Loganovsky, K.; Bebeshko, V.

    2007-01-01

    Complete text of publication follows. Objective: Ionizing radiation is fundamental environmental factor for life origin and evolution. Free radicals, primordial 'sea' for life conceiving and existence, induced by cosmic and terrestrial background radiation, are evolutionally archetypal, ubiquitous, and omnipotent in physiological- pathophysiological dichotomy. Classical free-radical paradigm in radiation biology and medicine, focused in essence on oxidative damage, needs new conceptualization and generalization. Methods: Suggested novel insights into free radicals dual immanent nature and functions in organism systems are based on original concepts of radicals dynamic charge transfer (CT) - redox ambivalence (interactional nucleo-, electro-, and ambiphilicity spectrum); pertinent chemical reactivity and selectivity delocalization model; physiological functional ambivalence and complementarity, and dynamic free-radical homeostasis. Results: Subtle perturbations in radicals CT spatiotemporal homeodynamics, in responsive signaling / controlling networks, concomitant alterations in genes expression, transcription, and apoptosis, redox control of mitochondrial ET chain, telomere/telomerase balance, DNA CT, circadian clock, hemispheric biochemical dominance/accentuation, including alteration of nitric oxide-superoxide complementarity, membranes permeability, neurotransmission pattern, synaptic circuitry, etc under radiation exposure have more fundamental impact on organism systems (especially CNS and CVS) deterioration than simple radicals inflicted oxidative (nitrosative) damage of cellular constituents. Conclusions: This novel conceptualization of free-radical paradigm constitutes new dimension in deciphering molecular mechanisms of radiation effects on subtle borderline norm-pathology and continuity-discontinuity dichotomy in organisms systems disorders - CT(redox)omics, which involves investigation of CT, redox, and spin states of free radicals, DNA bases

  11. Reactions of linoleic acid peroxyl radicals with phenolic antioxidants: a pulse radiolysis study

    International Nuclear Information System (INIS)

    Erben-Russ, Michael; Bors, Wolf; Saran, Manfred

    1987-01-01

    Linoleic acid peroxyl radicals (LOO) can be viewed as model intermediates occurring during lipid peroxidation processes. Formation and reactions of these species were investigated in aqueous alkaline solution using pulse radiolysis combined with kinetic spectroscopy. Irradiation of linoleic acid in N 2 O/O 2 -saturated solutions leads to a mixture of peroxyl radical isomers; reaction of 13-hydroperoxylinoleic acid (13-LOOH) with azide radicals in N 2 O-saturated solution produces 13-LOO radicals specifically. These peroxyl radicals cannot be observed directly, but their reactions with kaempferol and quercetin, acting as radical-scavenging antioxidants, produced strongly absorbing aroxyl radicals (ArO). The same aroxyl radicals were generated by OH and N 3 with rate constants exceeding 10 9 dm 3 mol -1 s -1 . Applying a reaction scheme that includes competing generation and decay reactions of both LOO and ArO radicals, individual rate constants were derived for LOO reactions with the phenols (> 10 7 dm 3 mol -1 s-? 1 ), with aroxyl radicals to form covalent adducts (> 10 8 dm 3 mol -1 s -1 ), as well as for their bimilecular decay (3.0 x 10 8 dm 3 mol -1 s -1 ). These results demonstrate high reactivity of fatty acid peroxyl radicals and flavone antioxidants in aqueous solution. (author)

  12. Reactions of linoleic acid peroxyl radicals with phenolic antioxidants: a pulse radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Erben-Russ, M.; Bors, W.; Saran, M.

    1987-09-01

    Linoleic acid peroxyl radicals (LOO) can be viewed as model intermediates occurring during lipid peroxidation processes. Formation and reactions of these species were investigated in aqueous alkaline solution using pulse radiolysis combined with kinetic spectroscopy. Irradiation of linoleic acid in N/sub 2/O/O/sub 2/-saturated solutions leads to a mixture of peroxyl radical isomers; reaction of 13-hydroperoxylinoleic acid (13-LOOH) with azide radicals in N/sub 2/O-saturated solution produces 13-LOO radicals specifically. These peroxyl radicals cannot be observed directly, but their reactions with kaempferol and quercetin, acting as radical-scavenging antioxidants, produced strongly absorbing aroxyl radicals (ArO). The same aroxyl radicals were generated by OH and N/sub 3/ with rate constants exceeding 10/sup 9/ dm/sup 3/ mol/sup -1/ s/sup -1/. Applying a reaction scheme that includes competing generation and decay reactions of both LOO and ArO radicals, individual rate constants were derived for LOO reactions with the phenols (> 10/sup 7/ dm/sup 3/ mol/sup -1/ s-./sup 1/), with aroxyl radicals to form covalent adducts (> 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/), as well as for their bimilecular decay (3.0 x 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/). These results demonstrate high reactivity of fatty acid peroxyl radicals and flavone antioxidants in aqueous solution.

  13. Transient flow combustion

    Science.gov (United States)

    Tacina, R. R.

    1984-01-01

    Non-steady combustion problems can result from engine sources such as accelerations, decelerations, nozzle adjustments, augmentor ignition, and air perturbations into and out of the compressor. Also non-steady combustion can be generated internally from combustion instability or self-induced oscillations. A premixed-prevaporized combustor would be particularly sensitive to flow transients because of its susceptability to flashback-autoignition and blowout. An experimental program, the Transient Flow Combustion Study is in progress to study the effects of air and fuel flow transients on a premixed-prevaporized combustor. Preliminary tests performed at an inlet air temperature of 600 K, a reference velocity of 30 m/s, and a pressure of 700 kPa. The airflow was reduced to 1/3 of its original value in a 40 ms ramp before flashback occurred. Ramping the airflow up has shown that blowout is more sensitive than flashback to flow transients. Blowout occurred with a 25 percent increase in airflow (at a constant fuel-air ratio) in a 20 ms ramp. Combustion resonance was found at some conditions and may be important in determining the effects of flow transients.

  14. Nitrate radicals and biogenic volatile organic compounds ...

    Science.gov (United States)

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in

  15. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  16. Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

    Energy Technology Data Exchange (ETDEWEB)

    Wink, D A [National Cancer Inst., Frederick, MD (United States); Desrosiers, M F [National Inst. of Standards and Technology, Gaithersburg, MD (United States)

    1991-01-01

    The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3.5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant (BR{sub 2}{sup -}). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive inter-mediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented. (author).

  17. Unusual spin-trap chemistry for the reaction of hydroxyl radical with the carcinogen N-nitrosodimethylamine

    International Nuclear Information System (INIS)

    Wink, D.A.; Desrosiers, M.F.

    1991-01-01

    The reaction of the potent carcinogen N-nitrosodimethylamine (NDMA) with hydroxyl radical generated via radiolysis was studied using EPR techniques. Attempts to spin trap NDMA radical intermediates with 3.5-dibromo-4-nitrosobenzene sulfonate (DBNBS) produced only unusual DBNBS radicals. One of these radicals was shown to be generated by both reaction of DBNBS with nitric oxide, and direct oxidation of DBNBS with an inorganic oxidant (BR 2 - ). Another DBNBS radical was identified as a sulfite spin adduct resulting from the degradation of DBNBS by a NDMA reactive inter-mediate. In the absence of DBNBS, hydroxyl radical reaction with NDMA gave the dimethylnitroxide produced an EPR spectrum nearly identical to that of NDMA solutions with DBNBS added before radiolysis. A proposed mechanism accounting for these observations is presented. (author)

  18. Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

    Science.gov (United States)

    Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 d...

  19. Combustion and regulation; Combustion et reglementation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    This conference was organized after the publication of the French by-law no 2010 relative to combustion installations and to the abatement of atmospheric pollution. Five topics were discussed during the conference: the new regulations, their content, innovations and modalities of application; the means of energy suppliers to face the new provisions and their schedule; the manufacturers proposals for existing installations and the new equipments; the administration control; and the impact of the new measures on exploitation and engineering. Twenty papers and 2 journal articles are reported in these proceedings. (J.S.)

  20. The intermediate state in Patd

    African Journals Online (AJOL)

    ) Jesus had assumed. (concerning the 'intermediate state') as existing, anything which does not exist. Three basic things about the intermediate state emerge from the parable: (a) Jesus recognizes that at the moment of death, in ipso articulo.

  1. Synthesis and Free Radical Scavenging Activity of New Hydroxybenzylidene Hydrazines

    Directory of Open Access Journals (Sweden)

    Frantisek Sersen

    2017-05-01

    Full Text Available Hydroxybenzylidene hydrazines exhibit a wide spectrum of biological activities. Here, we report synthesis and free radical scavenging activity of nine new N-(hydroxybenzylidene-N′-[2,6-dinitro-4-(trifluoromethyl]phenylhydrazines. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR, 19F-NMR, IR spectroscopy, LC-MS, and elemental analysis. The prepared compounds were tested for their activity to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH, galvinoxyl radical (GOR, and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS radicals. The free radical scavenging activity expressed as SC50 values of these compounds varied in a wide range, from a strong to no radical scavenging effect. The most effective radical scavengers were hydroxybenzylidene hydrazines containing three hydroxyl groups in the benzylidene part of their molecules. The prepared compounds were also tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts. IC50 values of these compounds varied in wide range, from an intermediate to no inhibitory effect.

  2. Synthesis and Free Radical Scavenging Activity of New Hydroxybenzylidene Hydrazines.

    Science.gov (United States)

    Sersen, Frantisek; Gregan, Fridrich; Kotora, Peter; Kmetova, Jarmila; Filo, Juraj; Loos, Dusan; Gregan, Juraj

    2017-05-29

    Hydroxybenzylidene hydrazines exhibit a wide spectrum of biological activities. Here, we report synthesis and free radical scavenging activity of nine new N-(hydroxybenzylidene)-N'-[2,6-dinitro-4-(trifluoromethyl)]phenylhydrazines. The chemical structures of these compounds were confirmed by 1H-NMR, 13C-NMR, 19F-NMR, IR spectroscopy, LC-MS, and elemental analysis. The prepared compounds were tested for their activity to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH), galvinoxyl radical (GOR), and 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulphonic acid (ABTS) radicals. The free radical scavenging activity expressed as SC50 values of these compounds varied in a wide range, from a strong to no radical scavenging effect. The most effective radical scavengers were hydroxybenzylidene hydrazines containing three hydroxyl groups in the benzylidene part of their molecules. The prepared compounds were also tested for their activity to inhibit photosynthetic electron transport in spinach chloroplasts. IC50 values of these compounds varied in wide range, from an intermediate to no inhibitory effect.

  3. [Intermediate energy nuclear physics

    International Nuclear Information System (INIS)

    1989-01-01

    This report summarizes work in experimental Intermediate Energy Nuclear Physics carried out between October 1, 1988 and October 1, 1989 at the Nuclear Physics Laboratory of the University of Colorado, Boulder, under grant DE-FG02-86ER-40269 with the United States Department of Energy. The experimental program is very broadly based, including pion-nucleon studies at TRIUMF, inelastic pion scattering and charge exchange reactions at LAMPF, and nucleon charge exchange at LAMPF/WNR. In addition, a number of other topics related to accelerator physics are described in this report

  4. Combustible structural composites and methods of forming combustible structural composites

    Science.gov (United States)

    Daniels, Michael A.; Heaps, Ronald J.; Steffler, Eric D.; Swank, W. David

    2013-04-02

    Combustible structural composites and methods of forming same are disclosed. In an embodiment, a combustible structural composite includes combustible material comprising a fuel metal and a metal oxide. The fuel metal is present in the combustible material at a weight ratio from 1:9 to 1:1 of the fuel metal to the metal oxide. The fuel metal and the metal oxide are capable of exothermically reacting upon application of energy at or above a threshold value to support self-sustaining combustion of the combustible material within the combustible structural composite. Structural-reinforcing fibers are present in the composite at a weight ratio from 1:20 to 10:1 of the structural-reinforcing fibers to the combustible material. Other embodiments and aspects are disclosed.

  5. Free Radical Imaging Using In Vivo Dynamic Nuclear Polarization-MRI.

    Science.gov (United States)

    Utsumi, Hideo; Hyodo, Fuminori

    2015-01-01

    Redox reactions that generate free radical intermediates are essential to metabolic processes, and their intermediates can produce reactive oxygen species, which may promote diseases related to oxidative stress. The development of an in vivo electron spin resonance (ESR) spectrometer and its imaging enables us noninvasive and direct measurement of in vivo free radical reactions in living organisms. The dynamic nuclear polarization magnetic resonance imaging (DNP-MRI), also called PEDRI or OMRI, is also a new imaging method for observing free radical species in vivo. The spatiotemporal resolution of free radical imaging with DNP-MRI is comparable with that in MRI, and each of the radical species can be distinguished in the spectroscopic images by changing the frequency or magnetic field of ESR irradiation. Several kinds of stable nitroxyl radicals were used as spin probes to detect in vivo redox reactions. The signal decay of nitroxyl probes, which is determined with in vivo DNP-MRI, reflects the redox status under oxidative stress, and the signal decay is suppressed by prior administration of antioxidants. In addition, DNP-MRI can also visualize various intermediate free radicals from the intrinsic redox molecules. This noninvasive method, in vivo DNP-MRI, could become a useful tool for investigating the mechanism of oxidative injuries in animal disease models and the in vivo effects of antioxidant drugs. © 2015 Elsevier Inc. All rights reserved.

  6. Optical Tomography in Combustion

    DEFF Research Database (Denmark)

    Evseev, Vadim

    spectral measurements at several line-of-sights with a view to applications for tomographic measurements on full-scale industrial combustion systems. The system was successfully applied on industrial scale for simultaneous fast exhaust gas temperature measurements in the three optical ports of the exhaust......D project, it was also important to investigate the spectral properties of major combustion species such as carbon dioxide and carbon monoxide in the infrared range at high temperatures to provide the theoretical background for the development of the optical tomography methods. The new software....... JQSRT 113 (2012) 2222, 10.1016/j.jqsrt.2012.07.015] included in the PhD thesis as an attachment. The knowledge and experience gained in the PhD project is the first important step towards introducing the advanced optical tomography methods of combustion diagnostics developed in the project to future...

  7. Internal combustion engine

    Science.gov (United States)

    Baker, Quentin A.; Mecredy, Henry E.; O'Neal, Glenn B.

    1991-01-01

    An improved engine is provided that more efficiently consumes difficult fuels such as coal slurries or powdered coal. The engine includes a precombustion chamber having a portion thereof formed by an ignition plug. The precombustion chamber is arranged so that when the piston is proximate the head, the precombustion chamber is sealed from the main cylinder or the main combustion chamber and when the piston is remote from the head, the precombustion chamber and main combustion chamber are in communication. The time for burning of fuel in the precombustion chamber can be regulated by the distance required to move the piston from the top dead center position to the position wherein the precombustion chamber and main combustion chamber are in communication.

  8. Fuel and combustion stratification study of Partially Premixed Combustion

    OpenAIRE

    Izadi Najafabadi, M.; Dam, N.; Somers, B.; Johansson, B.

    2016-01-01

    Relatively high levels of stratification is one of the main advantages of Partially Premixed Combustion (PPC) over the Homogeneous Charge Compression Ignition (HCCI) concept. Fuel stratification smoothens heat release and improves controllability of this kind of combustion. However, the lack of a clear definition of “fuel and combustion stratifications” is obvious in literature. Hence, it is difficult to compare stratification levels of different PPC strategies or other combustion concepts. T...

  9. Aerosols from biomass combustion

    Energy Technology Data Exchange (ETDEWEB)

    Nussbaumer, T

    2001-07-01

    This report is the proceedings of a seminar on biomass combustion and aerosol production organised jointly by the International Energy Agency's (IEA) Task 32 on bio energy and the Swiss Federal Office of Energy (SFOE). This collection of 16 papers discusses the production of aerosols and fine particles by the burning of biomass and their effects. Expert knowledge on the environmental impact of aerosols, formation mechanisms, measurement technologies, methods of analysis and measures to be taken to reduce such emissions is presented. The seminar, visited by 50 participants from 11 countries, shows, according to the authors, that the reduction of aerosol emissions resulting from biomass combustion will remain a challenge for the future.

  10. High Gravity (g) Combustion

    Science.gov (United States)

    2006-02-01

    UNICORN (Unsteady Ignition and Combustion with Reactions) code10. Flame propagation in a tube that is 50-mm wide and 1000-mm long (similar to that...turbine engine manufacturers, estimating the primary zone space heating rate. Both combustion systems, from Company A and Company B, required a much...MBTU/atm-hr-ft3) Te m pe ra tu re R is e (K ) dP/P = 2% dP/P = 2.5% dP/P = 3% dP/P = 3.5% dP/P = 4% Company A Company B Figure 13: Heat Release Rate

  11. Alcohol combustion chemistry

    KAUST Repository

    Sarathy, Mani

    2014-10-01

    Alternative transportation fuels, preferably from renewable sources, include alcohols with up to five or even more carbon atoms. They are considered promising because they can be derived from biological matter via established and new processes. In addition, many of their physical-chemical properties are compatible with the requirements of modern engines, which make them attractive either as replacements for fossil fuels or as fuel additives. Indeed, alcohol fuels have been used since the early years of automobile production, particularly in Brazil, where ethanol has a long history of use as an automobile fuel. Recently, increasing attention has been paid to the use of non-petroleum-based fuels made from biological sources, including alcohols (predominantly ethanol), as important liquid biofuels. Today, the ethanol fuel that is offered in the market is mainly made from sugar cane or corn. Its production as a first-generation biofuel, especially in North America, has been associated with publicly discussed drawbacks, such as reduction in the food supply, need for fertilization, extensive water usage, and other ecological concerns. More environmentally friendly processes are being considered to produce alcohols from inedible plants or plant parts on wasteland. While biofuel production and its use (especially ethanol and biodiesel) in internal combustion engines have been the focus of several recent reviews, a dedicated overview and summary of research on alcohol combustion chemistry is still lacking. Besides ethanol, many linear and branched members of the alcohol family, from methanol to hexanols, have been studied, with a particular emphasis on butanols. These fuels and their combustion properties, including their ignition, flame propagation, and extinction characteristics, their pyrolysis and oxidation reactions, and their potential to produce pollutant emissions have been intensively investigated in dedicated experiments on the laboratory and the engine scale

  12. Combustibility of tetraphenylborate solids

    International Nuclear Information System (INIS)

    Walker, D.D.

    1989-01-01

    Liquid slurries expected under normal in-tank processing (ITP) operations are not ignitible because of their high water content. However, deposits of dry solids from the slurries are combustible and produce dense, black smoke when burned. The dry solids burn similarly to Styrofoam and more easily than sawdust. It is the opinion of fire hazard experts that a benzene vapor deflagration could ignite the dry solids. A tetraphenylborate solids fire will rapidly plug the waste tank HEPA ventilation filters due to the nature of the smoke produced. To prevent ignition and combustion of these solids, the waste tanks have been equipped with a nitrogen inerting system

  13. Studies in combustion dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Koszykowski, M.L. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    The goal of this program is to develop a fundamental understanding and a quantitative predictive capability in combustion modeling. A large part of the understanding of the chemistry of combustion processes comes from {open_quotes}chemical kinetic modeling.{close_quotes} However, successful modeling is not an isolated activity. It necessarily involves the integration of methods and results from several diverse disciplines and activities including theoretical chemistry, elementary reaction kinetics, fluid mechanics and computational science. Recently the authors have developed and utilized new tools for parallel processing to implement the first numerical model of a turbulent diffusion flame including a {open_quotes}full{close_quotes} chemical mechanism.

  14. Some aspects of radiation-induced free-radical chemistry of biologically important molecules

    International Nuclear Information System (INIS)

    Sonntag, C. von

    1992-01-01

    Biologically relevant material is usually associated with considerable amounts of water. When ionizing radiation interacts with such material one must consider two modes of energy deposition: the direct effect (ionizing radiation is absorbed by the biomolecules) and the indirect effect (ionizing radiation is absorbed by the surrounding water). In the direct effect, radical cations plus electrons, and excited states of the biomolecules are formed. In the indirect effect the water is decomposed resulting in the formation of the water radicals OH,H and e aq - . These reactive intermediates then interact with the biomolecules. When such systems are irradiated oxygen is often present. As a result of this, the radicals formed in the biomolecules by the various routes are converted into the corresponding peroxyl radicals. In certain cases, e.g. with the nucleobases of DNA, radical cations can be produced in dilute aqueous solutions by radiation-generated SO 4 - radicals, and the fate of these nucleobase radical cations studied by pulse radiolysis and product analysis. Attention will be drawn to the fact that frequently some of the reaction products of the radical cations with water are identical to those formed by OH radical attack, but that there are also marked differences. Similarly, protonation of radical anions (formed by the reaction of solvated electrons with the biomolecules) and the reaction of H-atoms with these molecules can lead to radical intermediates with considerably differing characteristics. Our present knowledge of the variety of reactions of the peroxyl radicals occurring in aqueous solutions will be briefly discussed, emphasizing the large variety of HO 2 /O 2 - elimination reactions and pointing to the reversibility of the oxygen addition (RO 2 →R + O 2 ) in some systems recently studied. (author)

  15. Combustion stratification for naphtha from CI combustion to PPC

    NARCIS (Netherlands)

    Vallinayagam, R.; Vedharaj, S.; An, Y.; Dawood, A.; Izadi Najafabadi, M.; Somers, L.M.T.; Johansson, B.H.

    2017-01-01

    This study demonstrated the change in combustion homogeneity from conventional diesel combustion via partially premixed combustion towards HCCI. Experiments are performed in an optical diesel engine at a speed of 1200 rpm with diesel fuel. Single injection strategy is employed and the fuel is

  16. Computational Study of Stratified Combustion in an Optical Diesel Engine

    KAUST Repository

    Jaasim, Mohammed

    2017-03-28

    Full cycle simulations of KAUST optical diesel engine were conducted in order to provide insights into the details of fuel spray, mixing, and combustion characteristics at different start of injection (SOI) conditions. Although optical diagnostics provide valuable information, the high fidelity simulations with matched parametric conditions improve fundamental understanding of relevant physical and chemical processes by accessing additional observables such as the local mixture distribution, intermediate species concentrations, and detailed chemical reaction rates. Commercial software, CONVERGE™, was used as the main simulation tool, with the Reynolds averaged Navier-Stokes (RANS) turbulence model and the multi-zone (SAGE) combustion model to compute the chemical reaction terms. SOI is varied from late compression ignition (CI) to early partially premixed combustion (PPC) conditions. The simulation results revealed a stronger correlation between fuel injection timing and combustion phasing for late SOI conditions, whereas the combustion phasing starts to decouple from SOI for early SOI cases. The predictions are consistent with the experimental observations, in terms of the overall trends in combustion and emission characteristics, while the high fidelity simulations provided further insights into the effects of mixture stratifications resulting from different SOI conditions.

  17. Manipulating radicals: Using cobalt to steer radical reactions

    OpenAIRE

    Chirilă, A.

    2017-01-01

    This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

  18. Toxicology of Biodiesel Combustion products

    Science.gov (United States)

    1. Introduction The toxicology of combusted biodiesel is an emerging field. Much of the current knowledge about biological responses and health effects stems from studies of exposures to other fuel sources (typically petroleum diesel, gasoline, and wood) incompletely combusted. ...

  19. Airborne measurement of peroxy radicals in the lower troposphere

    Science.gov (United States)

    Andrés Hernández, Maria Dolores; Horstjann, Markus; Kartal, Deniz; Krebsbach, Marc; Linke, Christian; Lichtenstern, Michael; Andrey, Javier; Burrows, John P.

    2013-04-01

    The importance of peroxy radicals in the tropospheric chemistry is well recognized in the scientific literature. Hydroxy- and organic peroxy radicals (HO2 and RO2, R being an organic chain) are key intermediates in the OH radical initiated oxidation of CO and SO2, of volatile organic compounds (VOC), in the ozonolysis of alkenes and photo-oxidation of carbonyl species. Peroxy radicals are responsible for the ozone production in the troposphere, the formation of peroxides and other oxidants. Although radical chemistry in the troposphere has been subject of intensive research in the past three decades, it is still very few known about the vertical distribution of peroxy radicals. Airborne observations are scarce in spite of their particular importance to improve the understanding of the tropospheric chemistry and the oxidising capacity of the atmosphere at different altitudes. In situ trace gas measurements were carried out in summer 2010 on board of the INTA (Instituto Nacional de Técnicas Aeroespaciales) C212 aircraft over Spain in the frame of the EUFAR project VERDRILLT (VERtical Distribution of Radicals In the Lower Layers of the Troposphere), and in cooperation with the DLR (Deutsches Zentrum für Luft- und Raumfahrt), the University of Wuppertal, the CEAM (Centro de Estudios Ambientales del Mediterráneo) and the UPV-EHU University in Bilbao. VERDRILLT aimed at getting a deeper understanding of the vertical distribution of peroxy radicals in the lower layers of the troposphere. Measurements were taken over urban areas and extensions of different vegetation under meteorological conditions favouring active photochemistry and convection from the ground into close atmospheric layers. Results and main findings will be presented and discussed.

  20. Underground treatment of combustible minerals

    Energy Technology Data Exchange (ETDEWEB)

    Sarapuu, E

    1954-10-14

    A process is described for treating oil underground, consisting in introducing several electrodes spaced one from the other in a bed of combustibles underground so that they come in electric contact with this bed of combustibles remaining insulated from the ground, and applying to the electrodes a voltage sufficient to produce an electric current across the bed of combustibles, so as to heat it and create an electric connection between the electrodes on traversing the bed of combustibles.

  1. Atmospheric Oxidation Mechanism of Furfural Initiated by Hydroxyl Radicals.

    Science.gov (United States)

    Zhao, Xiaocan; Wang, Liming

    2017-05-04

    Furfural is emitted into the atmosphere because of its potential applications as an intermediate to alkane fuels from biomass, industrial usages, and biomass burning. The kinetic and mechanistic information on the furfural chemistry is necessary to assess the fate of furfural in the atmosphere and its impact on the air quality. Here we studied the atmospheric oxidation mechanisms of furfural initiated by the OH radicals using quantum chemistry and kinetic calculations. The reaction of OH and furfural was initiated mainly by OH additions to C 2 and C 5 positions, forming R2 and R5 adducts, which could undergo rapid ring-breakage to form R2B and R5B, respectively. Our calculations showed that these intermediate radicals reacted rather slowly with O 2 under the atmospheric conditions because the additions of O 2 to these radicals are only slightly exothermic and highly reversible. Alternatively, these radicals would react directly with O 3 , NO 2 , HO 2 /RO 2 , etc. Namely, the atmospheric oxidation of furfural would unlikely result in ozone formation. Under typical atmospheric conditions, the main products in OH-initiated furfural oxidation include 2-oxo-3-pentene-1,5-dialdehyde, 5-hydroxy-2(5H)-furanone, 4-oxo-2- butenoic acid, and 2,5-furandione. These compounds will likely stay in the gas phase and are subject to further photo-oxidation.

  2. Supersonic Combustion Ramjet Research

    Science.gov (United States)

    2012-08-01

    was in collaboration with Prof. R. Bowersox (Texas A&M University) and Dr. K. Kobayashi ( Japanese Aerospace Exploration Agency, JAXA). 4.2 Ignition... cinema stereoscopic PIV system for the measurement of micro- and meso-scale turbulent premixed flame dynamics,” Paper B13, 5th US Combustion

  3. Infrared monitoring of combustion

    International Nuclear Information System (INIS)

    Bates, S.C.; Morrison, P.W. Jr.; Solomon, P.R.

    1991-01-01

    In this paper, the use of Fourier Transform Infrared (FT-IR) spectroscopy for combustion monitoring is described. A combination of emission, transmission, and reflection FT-IR spectroscopy yields data on the temperature and composition of the gases, surfaces and suspended particles in the combustion environment. Detection sensitivity of such trace exhaust gases as CO, CO 2 , SO 2 , NO x , and unburned hydrocarbons is at the ppm level. Tomographic reconstruction converts line-of-sight measurements into spatially resolved temperature and concentration data. Examples from various combustion processes are used to demonstrate the capabilities of the technique. Industrial measurements are described that have been performed directly in the combustion zone and in the exhaust duct of a large chemical recovery boiler. Other measurements of hot slag show how FT-IR spectroscopy can determine the temperature and optical properties of surfaces. In addition, experiments with water droplets show that transmission FT-IR data yield spectra that characterize particle size and number density

  4. Combustible dust tests

    Science.gov (United States)

    The sugar dust explosion in Georgia on February 7, 2008 killed 14 workers and injured many others (OSHA, 2009). As a consequence of this explosion, OSHA revised its Combustible Dust National Emphasis (NEP) program. The NEP targets 64 industries with more than 1,000 inspections and has found more tha...

  5. Properties of the radicals formed by one-electron oxidation of acetaminophen - a pulse radiolysis study

    International Nuclear Information System (INIS)

    Bisby, R.H.; Tabassum, N.

    1988-01-01

    The semi-iminoquinone radical of acetaminophen, which has previously been proposed as a possible hepatotoxic intermediate in the cytochrome P-450 catalysed oxidation of acetaminophen, has been generated and studied by pulse radiolysis. In the absence of other reactive solutes, the radical decays rapidly by second order kinetics with a rate constant (2k 2 ) of (2.2 ± 0.4) x 10 9 M -1 sec -1 . In alkaline solutions the radical deprotonates with a pK of 11.1 ± 0.1 to form a radical-anion. The acetaminophen radical-anion reacts with resorcinol at high pH values, leading to the formation of a transient equilibrium from which the one-electron reduction potential of the semi-iminoquinone radical of acetaminophen is estimated to be + 0.707 ± 0.01 V at pH 7. This value predicts that acetaminophen should be oxidised by thiyl radicals. This was confirmed by pulse radiolysis experiments for reaction of the cysteinyl radical, for which rate constants of 7 x 10 6 M -1 sec -1 at pH7 and 2.7 x 10 8 M -1 sec -1 at pH 11.3 were obtained. The reaction of O 2 with the acetaminophen semi-iminoquinone radical could not be detected by pulse radiolysis, and alternative mechanisms for superoxide radical formation are discussed. (author)

  6. Investigation of the role of bicyclic peroxy radicals in the oxidation mechanism of toluene.

    Science.gov (United States)

    Birdsall, Adam W; Andreoni, John F; Elrod, Matthew J

    2010-10-07

    The products of the primary OH-initiated oxidation of toluene were investigated using the turbulent flow chemical ionization mass spectrometry technique under different oxygen, NO, and initial OH radical concentrations as well as a range of total pressures. The bicyclic peroxy radical intermediate, a key proposed intermediate species in the Master Chemical Mechanism (MCM) for the atmospheric oxidation of toluene, was detected for the first time. The toluene oxidation mechanism was shown to have a strong oxygen concentration dependence, presumably due to the central role of the bicyclic peroxy radical in determining the stable product distribution at atmospheric oxygen concentrations. The results also suggest a potential role for bicyclic peroxy radical + HO(2) reactions at high HO(2)/NO ratios. These reactions are postulated to be a source of the inconsistencies between environmental chamber results and predictions from the MCM.

  7. Device to lower NOx in a gas turbine engine combustion system

    Science.gov (United States)

    Laster, Walter R; Schilp, Reinhard; Wiebe, David J

    2015-02-24

    An emissions control system for a gas turbine engine including a flow-directing structure (24) that delivers combustion gases (22) from a burner (32) to a turbine. The emissions control system includes: a conduit (48) configured to establish fluid communication between compressed air (22) and the combustion gases within the flow-directing structure (24). The compressed air (22) is disposed at a location upstream of a combustor head-end and exhibits an intermediate static pressure less than a static pressure of the combustion gases within the combustor (14). During operation of the gas turbine engine a pressure difference between the intermediate static pressure and a static pressure of the combustion gases within the flow-directing structure (24) is effective to generate a fluid flow through the conduit (48).

  8. A spectroscopy study of gasoline partially premixed compression ignition spark assisted combustion

    International Nuclear Information System (INIS)

    Pastor, J.V.; García-Oliver, J.M.; García, A.; Micó, C.; Durrett, R.

    2013-01-01

    Highlights: ► PPC combustion combined with spark assistance and gasoline fuel on a CI engine. ► Chemiluminescence of different chemical species describes the progress of combustion reaction. ► Spectra of a novel combustion mode under SACI conditions is described. ► UV–Visible spectrometry, high speed imaging and pressure diagnostic were employed for analysis. - Abstract: Nowadays many research efforts are focused on the study and development of new combustion modes, mainly based on the use of locally lean air–fuel mixtures. This characteristic, combined with exhaust gas recirculation, provides low combustion temperatures that reduces pollutant formation and increases efficiency. However these combustion concepts have some drawbacks, related to combustion phasing control, which must be overcome. In this way, the use of a spark plug has shown to be a good solution to improve phasing control in combination with lean low temperature combustion. Its performance is well reported on bibliography, however phenomena involving the combustion process are not completely described. The aim of the present work is to develop a detailed description of the spark assisted compression ignition mode by means of application of UV–Visible spectrometry, in order to improve insight on the combustion process. Tests have been performed in an optical engine by means of broadband radiation imaging and emission spectrometry. The engine hardware is typical of a compression ignition passenger car application. Gasoline was used as the fuel due to its low reactivity. Combining broadband luminosity images with pressure-derived heat-release rate and UV–Visible spectra, it was possible to identify different stages of the combustion reaction. After the spark discharge, a first flame kernel appears and starts growing as a premixed flame front, characterized by a low and constant heat-release rate in combination with the presence of remarkable OH radical radiation. Heat release increases

  9. Emission behavior of OH radical in internal EGR using a 2-cycle engine; 2 cycle engine wo mochiita naibu EGR no OH radical no hakko kyodo

    Energy Technology Data Exchange (ETDEWEB)

    Hashimoto, S; Amino, Y; Yoshida, K; Shoji, H; Saima, A [Nihon University, Tokyo (Japan)

    1997-10-01

    The purpose of this study was to examine and consider the influence, which the remained gas exercised on combustion. 2-cycle engine was Used as the test engine. Internal EGR was run. The means was that the test engine was fitted the back pressure control plate on the exhaust port. The conditions, which were run with internal EGR and without internal EGR, were compared. The OH radical, which plays important role in combustion of hydrocarbon fuels, was measured with emission spectroscopy. In internal EGR, the unburned end gas on exhaust port side was susceptible to the remained gas. 6 refs., 8 figs., 1 tab.

  10. Low emission internal combustion engine

    Science.gov (United States)

    Karaba, Albert M.

    1979-01-01

    A low emission, internal combustion compression ignition engine having a cylinder, a piston movable in the cylinder and a pre-combustion chamber communicating with the cylinder near the top thereof and in which low emissions of NO.sub.x are achieved by constructing the pre-combustion chamber to have a volume of between 70% and 85% of the combined pre-chamber and main combustion chamber volume when the piston is at top dead center and by variably controlling the initiation of fuel injection into the pre-combustion chamber.

  11. Utilization of ash from municipal solid waste combustion

    Energy Technology Data Exchange (ETDEWEB)

    Jones, C.; Hahn, J.; Magee, B.; Yuen, N.; Sandefur, K.; Tom, J.; Yap, C.

    1999-09-01

    This ash study investigated the beneficial use of municipal waste combustion combined ash from the H-POWER facility in Oahu. These uses were grouped into intermediate cover for final closure of the Waipahu landfill, daily cover at the Waimanalo Gulch Landfill, and partial replacement for aggregate in asphalt for road paving. All proposed uses examine combined fly and bottom ash from a modern waste-to-energy facility that meets requirements of the Clean Air Act Amendments for Maximum Achievable Control Technology.

  12. Plasma assisted combustion : Interaction of a flat flame with a nanosecond dielectric barrier discharge plasma

    NARCIS (Netherlands)

    Elkholy, A.H.E.; van Oijen, J.A.; de Goey, L.P.H.

    2016-01-01

    Using of non-equilibrium Plasma-assisted for ignition, combustion and high speed flow applications are rapidly developing in the last decades due to its ability to produce a large amount of radicals and excited species. Which has a great potential in flame stabilization and emission control.

  13. Hydrogen assisted diesel combustion

    Energy Technology Data Exchange (ETDEWEB)

    Lilik, Gregory K.; Boehman, Andre L. [The EMS Energy Institute, The Pennsylvania State University, University Park, PA 16802 (United States); Zhang, Hedan; Haworth, Daniel C. [Department of Mechanical and Nuclear Engineering, The Pennsylvania State University, University Park, PA 16802 (United States); Herreros, Jose Martin [Escuela Tecnica Superior de Ingenieros Industriales, Universidad de Castilla La-Mancha, Avda. Camilo Jose Cela s/n, 13071 Ciudad Real (Spain)

    2010-05-15

    Hydrogen assisted diesel combustion was investigated on a DDC/VM Motori 2.5L, 4-cylinder, turbocharged, common rail, direct injection light-duty diesel engine, with a focus on exhaust emissions. Hydrogen was substituted for diesel fuel on an energy basis of 0%, 2.5%, 5%, 7.5%, 10% and 15% by aspiration of hydrogen into the engine's intake air. Four speed and load conditions were investigated (1800 rpm at 25% and 75% of maximum output and 3600 rpm at 25% and 75% of maximum output). A significant retarding of injection timing by the engine's electronic control unit (ECU) was observed during the increased aspiration of hydrogen. The retarding of injection timing resulted in significant NO{sub X} emission reductions, however, the same emission reductions were achieved without aspirated hydrogen by manually retarding the injection timing. Subsequently, hydrogen assisted diesel combustion was examined, with the pilot and main injection timings locked, to study the effects caused directly by hydrogen addition. Hydrogen assisted diesel combustion resulted in a modest increase of NO{sub X} emissions and a shift in NO/NO{sub 2} ratio in which NO emissions decreased and NO{sub 2} emissions increased, with NO{sub 2} becoming the dominant NO{sub X} component in some combustion modes. Computational fluid dynamics analysis (CFD) of the hydrogen assisted diesel combustion process captured this trend and reproduced the experimentally observed trends of hydrogen's effect on the composition of NO{sub X} for some operating conditions. A model that explicitly accounts for turbulence-chemistry interactions using a transported probability density function (PDF) method was better able to reproduce the experimental trends, compared to a model that ignores the influence of turbulent fluctuations on mean chemical production rates, although the importance of the fluctuations is not as strong as has been reported in some other recent modeling studies. The CFD results confirm

  14. Chemical Kinetics of Hydrocarbon Ignition in Practical Combustion Systems

    International Nuclear Information System (INIS)

    Westbrook, C.K.

    2000-01-01

    Chemical kinetic factors of hydrocarbon oxidation are examined in a variety of ignition problems. Ignition is related to the presence of a dominant chain branching reaction mechanism that can drive a chemical system to completion in a very short period of time. Ignition in laboratory environments is studied for problems including shock tubes and rapid compression machines. Modeling of the laboratory systems are used to develop kinetic models that can be used to analyze ignition in practical systems. Two major chain branching regimes are identified, one consisting of high temperature ignition with a chain branching reaction mechanism based on the reaction between atomic hydrogen with molecular oxygen, and the second based on an intermediate temperature thermal decomposition of hydrogen peroxide. Kinetic models are then used to describe ignition in practical combustion environments, including detonations and pulse combustors for high temperature ignition, and engine knock and diesel ignition for intermediate temperature ignition. The final example of ignition in a practical environment is homogeneous charge, compression ignition (HCCI) which is shown to be a problem dominated by the kinetics intermediate temperature hydrocarbon ignition. Model results show why high hydrocarbon and CO emissions are inevitable in HCCI combustion. The conclusion of this study is that the kinetics of hydrocarbon ignition are actually quite simple, since only one or two elementary reactions are dominant. However, there are many combustion factors that can influence these two major reactions, and these are the features that vary from one practical system to another

  15. Free radicals in dicarboxylic acids: an e.s.r. study of radical conversions in γ-irradiated single crystals of glutaric acid and glutaric-2,2,4,4-d4 acid

    International Nuclear Information System (INIS)

    Bergene, R.; Minegishi, A.; Riesz, P.

    1980-01-01

    The γ-radiation-induced free radicals in single crystals of glutaric acid and glutaric-2,2,4,4-d 4 acid were studied in the temperature range 77-300 K by e.s.r. techniques. At 77 K the decarboxylation radical and the anion are stabilized. At higher temperatures the decarboxylation radical is found to be converted into a hydrogen abstraction radical with an activation energy of 6.3 +- 0.5 kcal/mole for the non-deuterated crystal. This radical is stable at room temperature. The anion seems to be converted to a unidentified intermediate radical which in turn is converted to the σ-acyl radical. An analysis of the g-value anisotropy and of the 13 C hyperfine splitting variation for this radical in the deuterated crystal is consistent with the assigned radical structure. By heat treatment the σ-acyl radical is converted to another form of the hydrogen abstraction radical with an activation energy of 9.6 +- 0.6 kcal/mole in the deuterated crystal. U.V.-light (lambda= 254 nm) transforms one of the room temperature radicals into the other. (author)

  16. Discourses and Models of Intermediality

    OpenAIRE

    Schröter, Jens

    2011-01-01

    In his article "Discourses and Models of Intermediality" Jens Schröter discusses the question as to what relations do different discourses pose between different "media." Schröter identifies four models of discourse: 1) synthetic intermediality: a "fusion" of different media to super-media, a model with roots in the Wagnerian concept of Gesamtkunstwerk with political connotations, 2) formal (or transmedial) intermediality: a concept based on formal structures not "specific" to one medium but ...

  17. Information acquisition and financial intermediation

    OpenAIRE

    Boyarchenko, Nina

    2012-01-01

    This paper considers the problem of information acquisition in an intermediated market, where the specialists have access to superior technology for acquiring information. These informational advantages of specialists relative to households lead to disagreement between the two groups, changing the shape of the intermediation-constrained region of the economy and increasing the frequency of periods when the intermediation constraint binds. Acquiring the additional information is, however, cost...

  18. Hydroxyl radical reactivity with diethylhydroxylamine

    International Nuclear Information System (INIS)

    Gorse, R.A. Jr.; Lii, R.R.; Saunders, B.B.

    1977-01-01

    Diethylhydroxylamine (DEHA) reacts with gas-phase hydroxyl radicals on every third collision, whereas the corresponding reaction in aqueous solution is considerably slower. The high gas-phase reactivity explains the predicted inhibitory effect of DEHA in atmospheric smog processes. Results from the studies in the aqueous phase are helpful in predicting the mechanism of the reaction of DEHA with hydroxyl radicals

  19. Muoniated acyl and thioacyl radicals

    International Nuclear Information System (INIS)

    McKenzie, Iain; Brodovitch, Jean-Claude; Ghandi, Khashayar; Percival, Paul W.

    2006-01-01

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and 14 N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and 14 N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy

  20. Muoniated acyl and thioacyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    McKenzie, Iain [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Brodovitch, Jean-Claude [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Ghandi, Khashayar [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada); Percival, Paul W. [TRIUMF and Department of Chemistry, 8888 University Drive, Simon Fraser University, Burnaby B.C., V5A 1S6 (Canada)]. E-mail: percival@sfu.ca

    2006-03-31

    The product of the reaction of muonium with tert-butylisocyanate was previously assigned as the muoniated tert-butylaminyl radical (I. McKenzie, J.-C. Brodovitch, K. Ghandi, S. Kecman, P. W. Percival, Physica B 326 (2003) 76). This assignment is incorrect since the muon and {sup 14}N hyperfine-coupling constants (hfcc) of this radical would have the opposite sign, which is in conflict with the experimental results. The radical is now reassigned as the muoniated N-tert-butylcarbamoyl radical, based on the similarities between the experimental muon and {sup 14}N hfcc and hfcc calculated at the UB3LYP/6-311G(d,p)//UB3LYP/EPR-III level. The large zero-point energy in the N-Mu bond results in the dissociation barrier of the muoniated N-tert-butylcarbamoyl radical being above the combined energy of the reactants, in contrast to the N-tert-butylcarbamoyl radical where the dissociation barrier lies below the combined energy of the reactants. The reaction of muonium with tert-butylisothiocyanate produced both conformers of the muoniated N-tert-butylthiocarbamoyl radical and their assignment was based on the similarities between the experimental and calculated muon hfcc. These are the first acyl and thioacyl radicals to be directly detected by muon spin spectroscopy.

  1. Combustion Characteristics of C5 Alcohols and a Skeletal Mechanism for Homogeneous Charge Compression Ignition Combustion Simulation

    KAUST Repository

    Park, Sungwoo

    2015-10-27

    C5 alcohols are considered alternative fuels because they emit less greenhouse gases and fewer harmful pollutants. In this study, the combustion characteristics of 2-methylbutanol (2-methyl-1-butanol) and isopentanol (3-methyl-1-butanol) and their mixtures with primary reference fuels (PRFs) were studied using a detailed chemical kinetic model obtained from merging previously published mechanisms. Ignition delay times of the C5 alcohol/air mixtures were compared to PRFs at 20 and 40 atm. Reaction path analyses were conducted at intermediate and high temperatures to identify the most influential reactions controlling ignition of C5 alcohols. The direct relation graph with expert knowledge methodology was used to eliminate unimportant species and reactions in the detailed mechanism, and the resulting skeletal mechanism was tested at various homogeneous charge compression ignition (HCCI) engine combustion conditions. These simulations were used to investigate the heat release characteristics of the methyl-substituted C5 alcohols, and the results show relatively strong reactions at intermediate temperatures prior to hot ignition. C5 alcohol blending in PRF75 in HCCI combustion leads to a significant decrease of low-temperature heat release (LTHR) and a delay of the main combustion. The heat release features demonstrated by C5 alcohols can be used to improve the design and operation of advanced engine technologies.

  2. Combustion strategy : United Kingdom

    Energy Technology Data Exchange (ETDEWEB)

    Greenhalgh, D. [Heriot-Watt Univ., Edingburgh, Scotland (United Kingdom). School of Engineering and Physical Sciences

    2009-07-01

    The United Kingdom's combustion strategy was briefly presented. Government funding sources for universities were listed. The United Kingdom Research Councils that were listed included the Arts and Humanities Research Council (AHRC) and the Biotechnology and Biological Sciences Research Council (BBSRC); the Engineering and Physical Sciences Research Council (EPSRC); the Economic and Social Research Council; the Medical Research Council; the Natural Environment Research Council; and the Science and Technology Facilities Council. The EPSRC supported 65 grants worth 30.5 million pounds. The combustion industry was noted to be dominated by three main players of which one was by far the largest. The 3 key players were Rolls-Royce; Jaguar Land Rover; and Doosan Babcock. Industry and government involvement was also discussed for the BIS Technology Strategy Board, strategy technology areas, and strategy application areas.

  3. Aerosols from biomass combustion

    Energy Technology Data Exchange (ETDEWEB)

    Nussbaumer, T.

    2001-07-01

    This report is the proceedings of a seminar on biomass combustion and aerosol production organised jointly by the International Energy Agency's (IEA) Task 32 on bio energy and the Swiss Federal Office of Energy (SFOE). This collection of 16 papers discusses the production of aerosols and fine particles by the burning of biomass and their effects. Expert knowledge on the environmental impact of aerosols, formation mechanisms, measurement technologies, methods of analysis and measures to be taken to reduce such emissions is presented. The seminar, visited by 50 participants from 11 countries, shows, according to the authors, that the reduction of aerosol emissions resulting from biomass combustion will remain a challenge for the future.

  4. Plasma Assisted Combustion

    Science.gov (United States)

    2007-02-28

    Tracking an individual streamer branch among others in a pulsed induced discharge J. Phys. D: Appl. Phys. 35 2823--9 [29] van Veldhuizen E M and Rutgers...2005) AIAA–2005–0405. [99] E.M. Van Veldhuizen (ed) Electrical Discharges for Environmental Purposes: Fun- damentals and Applications (New York: Nova...Vandooren J, Van Tiggelen P J 1977 Reaction Mechanism and Rate Constants in Lean Hydrogen–Nitrous Oxide Flames Combust. Flame 28 165 [201] Dean A M, Steiner

  5. Fluid-bed combustion

    Energy Technology Data Exchange (ETDEWEB)

    Hunt, G.; Schoebotham, N.

    1981-02-01

    In Energy Equipment Company's two-stage fluidized bed system, partial combustion in a fluidized bed is followed by burn-off of the generated gases above the bed. The system can be retrofitted to existing boilers, and can burn small, high ash coal efficiently. It has advantages when used as a hot gas generator for process drying. Tests on a boiler at a Cadbury Schweppes plant are reported.

  6. Combustion science and engineering

    CERN Document Server

    Annamalai, Kalyan

    2006-01-01

    Introduction and Review of Thermodynamics Introduction Combustion Terminology Matter and Its Properties Microscopic Overview of Thermodynamics Conservation of Mass and Energy and the First Law of Thermodynamics The Second Law of Thermodynamics Summary Stoichiometry and Thermochemistry of Reacting Systems Introduction Overall Reactions Gas Analyses Global Conservation Equations for Reacting Systems Thermochemistry Summary Appendix Reaction Direction and Equilibrium Introduction Reaction Direction and Chemical Equilibrium Chemical Equilibrium Relations Vant Hoff Equation Adi

  7. Missing Peroxy Radical Sources Within a Rural Forest Canopy

    Science.gov (United States)

    Wolfe, G. M.; Cantrell, C.; Kim, S.; Mauldin, R. L., III; Karl, T.; Harley, P.; Turnipseed, A.; Zheng, W.; Flocke, F.; Apel, E. C.; hide

    2013-01-01

    Organic peroxy (RO2) and hydroperoxy (HO2) radicals are key intermediates in the photochemical processes that generate ozone, secondary organic aerosol and reactive nitrogen reservoirs throughout the troposphere. In regions with ample biogenic hydrocarbons, the richness and complexity of peroxy radical chemistry presents a significant challenge to current-generation models, especially given the scarcity of measurements in such environments. We present peroxy radical observations acquired within a Ponderosa pine forest during the summer 2010 Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Organic Carbon Study (BEACHON-ROCS). Total peroxy radical mixing ratios reach as high as 180 pptv and are among the highest yet recorded. Using the comprehensive measurement suite to constrain a near-explicit 0-D box model, we investigate the sources, sinks and distribution of peroxy radicals below the forest canopy. The base chemical mechanism underestimates total peroxy radicals by as much as a factor of 3. Since primary reaction partners for peroxy radicals are either measured (NO) or under-predicted (HO2 and RO2, i.e. self-reaction), missing sources are the most likely explanation for this result. A close comparison of model output with observations reveals at least two distinct source signatures. The first missing source, characterized by a sharp midday maximum and a strong dependence on solar radiation, is consistent with photolytic production of HO2. The diel profile of the second missing source peaks in the afternoon and suggests a process that generates RO2 independently of sun-driven photochemistry, such as ozonolysis of reactive hydrocarbons. The maximum magnitudes of these missing sources (approximately 120 and 50 pptv min-1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within forests. We conclude that a similar mechanism may underlie many such observations.

  8. ESR investigation of the reactions of glutathione, cysteine and penicillamine thiyl radicals: competitive formation of RSOcenter dot, Rcenter dot, RSSRcenter dot-. , and RSScenter dot

    Energy Technology Data Exchange (ETDEWEB)

    Becker, David; Swarts, Steven; Champagne, Mark; Sevilla, M D

    1988-05-01

    The reactions of cysteine, glutathione and penicillamine thiyl radicals with oxygen and their parent thiols in frozen solutions have been elucidated with e.s.r. The major sulfur radicals observed are: (1) thiyl radicals, RS center dot; (2) disulfide radical anions, RSSR anion radicals; (3) perthiyl radicals, RSS center dot and upon introduction of oxygen; (4) sulfinyl radicals, RSO center dot, where R represents the remainder of the cysteine, glutathione or penicillamine moiety. The radical product observed depends on pH, concentration of thiol, and presence or absence of molecular oxygen. The sulfinyl radical is a ubiquitous intermediate, peroxyl radical attack on thiols may lead to sulfinyl radicals. The authors elaborate the observed reaction sequences that lead to sulfinyl radicals and, using /sup 17/O isotopic substitution studies, demonstrate the oxygen atom in sulfinyl radicals originates from dissolved molecular oxygen. The glutathione radical is found to abstract hydrogen from the ..cap alpha..-carbon position on the cysteine residue of glutathione to form a carbon-centred radical.

  9. Issues in waste combustion

    Energy Technology Data Exchange (ETDEWEB)

    Gustavsson, Lennart; Robertson, Kerstin; Tullin, Claes [Swedish National Testing and Research Inst., Boraas (Sweden); Sundquist, Lena; Wrangensten, Lars [AaF-Energikonsult AB, Stockholm (Sweden); Blom, Elisabet [AaF-Processdesign AB, Stockholm (Sweden)

    2003-05-01

    The main purpose of this review is to provide an overview of the state-of-the-art on research and development issues related to waste combustion with relevance for Swedish conditions. The review focuses on co-combustion in grate and fluidised bed furnaces. It is primarily literature searches in relevant databases of scientific publications with to material published after 1995. As a complement, findings published in different report series, have also been included. Since the area covered by this report is very wide, we do not claim to cover the issues included completely and it has not been possitile to evaluate the referred studies in depth. Basic knowledge about combustion issues is not included since such information can be found elsewhere in the literature. Rather, this review should be viewed as an overview of research and development in the waste-to-energy area and as such we hope that it will inspire scientists and others to further work in relevant areas.

  10. The MHD intermediate shock interaction with an intermediate wave: Are intermediate shocks physical?

    International Nuclear Information System (INIS)

    Wu, C.C.

    1988-01-01

    Contrary to the usual belief that MHD intermediate shocks are extraneous, the authors have recently shown by numerical solutions of dissipative MHD equations that intermediate shocks are admissible and can be formed through nonlinear steepening from a continuous wave. In this paper, he clarifies the differences between the conventional view and the results by studying the interaction of an MHD intermediate shock with an intermediate wave. The study reaffirms his results. In addition, the study shows that there exists a larger class of shocklike solutions in the time-dependent dissiaptive MHD equations than are given by the MHD Rankine-Hugoniot relations. it also suggests a mechanism for forming rotational discontinuities through the interaction of an intermediate shock with an intermediate wave. The results are of importance not only to the MHD shock theory but also to studies such as magnetic field reconnection models

  11. Addressing Emerging Risks: Scientific and Regulatory Challenges Associated with Environmentally Persistent Free Radicals

    Directory of Open Access Journals (Sweden)

    Tammy R. Dugas

    2016-06-01

    Full Text Available Airborne fine and ultrafine particulate matter (PM are often generated through widely-used thermal processes such as the combustion of fuels or the thermal decomposition of waste. Residents near Superfund sites are exposed to PM through the inhalation of windblown dust, ingestion of soil and sediments, and inhalation of emissions from the on-site thermal treatment of contaminated soils. Epidemiological evidence supports a link between exposure to airborne PM and an increased risk of cardiovascular and pulmonary diseases. It is well-known that during combustion processes, incomplete combustion can lead to the production of organic pollutants that can adsorb to the surface of PM. Recent studies have demonstrated that their interaction with metal centers can lead to the generation of a surface stabilized metal-radical complex capable of redox cycling to produce ROS. Moreover, these free radicals can persist in the environment, hence their designation as Environmentally Persistent Free Radicals (EPFR. EPFR has been demonstrated in both ambient air PM2.5 (diameter < 2.5 µm and in PM from a variety of combustion sources. Thus, low-temperature, thermal treatment of soils can potentially increase the concentration of EPFR in areas in and around Superfund sites. In this review, we will outline the evidence to date supporting EPFR formation and its environmental significance. Furthermore, we will address the lack of methodologies for specifically addressing its risk assessment and challenges associated with regulating this new, emerging contaminant.

  12. Fluidized bed combustion of low-grade coal and wastes: Research and development

    Energy Technology Data Exchange (ETDEWEB)

    Borodulya, V.A.; Dikalenko, V.I.; Palchonok, G.I.; Vinogradov, L.M. [Academy of Sciences of Belarus, Minsk (Belarus). A.V. Luikov Heat and Mass Transfer Inst.; Dobkin, S.M.; Telegin, E.M. [Special Design Office, Brest (Belarus)

    1994-12-31

    Experimental studies were carried out to investigate devolatilization of fuel as single spherical particles of wood, hydrolytic lignin, leather sewage sludge and Belarussian brown coals in a fluidized bed of sand. It is found that the devolatilization process depends on moisture and ash contents in fuel and on the external heat and mass transfer rate. The char combustion occurs largely in the intermediate region. Kinetic parameters of the devolatilization and char combustion are obtained. A low-capacity fluidized bed boiler suitable for combustion of coal and different wastes is described.

  13. Radical-mediated reduction of the dithiocarbamate group under tin-free conditions.

    Science.gov (United States)

    McMaster, Claire; Bream, Robert N; Grainger, Richard S

    2012-06-28

    Reductive desulfurisation of dithiocarbamates is conveniently achieved using H(3)PO(2)-Et(3)N-ACCN in refluxing dioxane. Fused and spirocyclic β-lactams, prepared through 4-exo trig carbamoyl radical cyclisation-dithiocarbamate group transfer reactions, are reduced without fragmentation of the strained 4-membered ring. Diethyl tetraacetyl-d-glucopyranosyl dithiocarbamate is selectively reduced with or without acyloxy group migration depending on reaction conditions and choice of reductant. Deuterium incorporation from D(3)PO(2)-Et(3)N is observed for a system involving a nucleophilic radical intermediate, but not in the case of the electrophilic radical obtained through acyloxy group migration on a glucose derivative.

  14. Methyl Radicals in Oxidative Coupling of Methane Directly Confirmed by Synchrotron VUV Photoionization Mass Spectroscopy

    Science.gov (United States)

    Luo, Liangfeng; Tang, Xiaofeng; Wang, Wendong; Wang, Yu; Sun, Shaobo; Qi, Fei; Huang, Weixin

    2013-01-01

    Gas-phase methyl radicals have been long proposed as the key intermediate in catalytic oxidative coupling of methane, but the direct experimental evidence still lacks. Here, employing synchrotron VUV photoionization mass spectroscopy, we have directly observed the formation of gas-phase methyl radicals during oxidative coupling of methane catalyzed by Li/MgO catalysts. The concentration of gas-phase methyl radicals correlates well with the yield of ethylene and ethane products. These results lead to an enhanced fundamental understanding of oxidative coupling of methane that will facilitate the exploration of new catalysts with improved performance. PMID:23567985

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-12-15

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

  16. Technology for Transient Simulation of Vibration during Combustion Process in Rocket Thruster

    Science.gov (United States)

    Zubanov, V. M.; Stepanov, D. V.; Shabliy, L. S.

    2018-01-01

    The article describes the technology for simulation of transient combustion processes in the rocket thruster for determination of vibration frequency occurs during combustion. The engine operates on gaseous propellant: oxygen and hydrogen. Combustion simulation was performed using the ANSYS CFX software. Three reaction mechanisms for the stationary mode were considered and described in detail. The way for obtaining quick CFD-results with intermediate combustion components using an EDM model was found. The way to generate the Flamelet library with CFX-RIF was described. A technique for modeling transient combustion processes in the rocket thruster was proposed based on the Flamelet library. A cyclic irregularity of the temperature field like vortex core precession was detected in the chamber. Frequency of flame precession was obtained with the proposed simulation technique.

  17. The Diesel Combustion Collaboratory: Combustion Researchers Collaborating over the Internet

    Energy Technology Data Exchange (ETDEWEB)

    C. M. Pancerella; L. A. Rahn; C. Yang

    2000-02-01

    The Diesel Combustion Collaborator (DCC) is a pilot project to develop and deploy collaborative technologies to combustion researchers distributed throughout the DOE national laboratories, academia, and industry. The result is a problem-solving environment for combustion research. Researchers collaborate over the Internet using DCC tools, which include: a distributed execution management system for running combustion models on widely distributed computers, including supercomputers; web-accessible data archiving capabilities for sharing graphical experimental or modeling data; electronic notebooks and shared workspaces for facilitating collaboration; visualization of combustion data; and video-conferencing and data-conferencing among researchers at remote sites. Security is a key aspect of the collaborative tools. In many cases, the authors have integrated these tools to allow data, including large combustion data sets, to flow seamlessly, for example, from modeling tools to data archives. In this paper the authors describe the work of a larger collaborative effort to design, implement and deploy the DCC.

  18. Internal combustion engine using premixed combustion of stratified charges

    Science.gov (United States)

    Marriott, Craig D [Rochester Hills, MI; Reitz, Rolf D [Madison, WI

    2003-12-30

    During a combustion cycle, a first stoichiometrically lean fuel charge is injected well prior to top dead center, preferably during the intake stroke. This first fuel charge is substantially mixed with the combustion chamber air during subsequent motion of the piston towards top dead center. A subsequent fuel charge is then injected prior to top dead center to create a stratified, locally richer mixture (but still leaner than stoichiometric) within the combustion chamber. The locally rich region within the combustion chamber has sufficient fuel density to autoignite, and its self-ignition serves to activate ignition for the lean mixture existing within the remainder of the combustion chamber. Because the mixture within the combustion chamber is overall premixed and relatively lean, NO.sub.x and soot production are significantly diminished.

  19. Intermediate valence spectroscopy

    International Nuclear Information System (INIS)

    Gunnarsson, O.; Schoenhammer, K.

    1987-01-01

    Spectroscopic properties of intermediate valence compounds are studied using the Anderson model. Due to the large orbital and spin degeneracy N/sub f/ of the 4f-level, 1/N/sub f/ can be treated as a small parameter. This approach provides exact T = 0 results for the Anderson impurity model in the limit N/sub f/ → ∞, and by adding 1/N/sub f/ corrections some properties can be calculated accurately even for N/sub f/ = 1 or 2. In particular valence photoemission and resonance photoemission spectroscopies are studied. A comparison of theoretical and experimental spectra provides an estimate of the parameters in the model. Core level photoemission spectra provide estimates of the coupling between the f-level and the conduction states and of the f-level occupancy. With these parameters the model gives a fair description of other electron spectroscopies. For typical parameters the model predicts two structures in the f-spectrum, namely one structure at the f-level and one at the Fermi energy. The resonance photoemission calculation gives a photon energy dependence for these two peaks in fair agreement with experiment. The peak at the Fermi energy is partly due to a narrow Kondo resonance, resulting from many-body effects and the presence of a continuous, partly filled conduction band. This resonance is related to a large density of low-lying excitations, which explains the large susceptibility and specific heat observed for these systems at low temperatures. 38 references, 11 figures, 2 tables

  20. Free radical generation induced by ultrasound in red wine and model wine: An EPR spin-trapping study

    OpenAIRE

    Zhang, Quing An; Shen, Yuan; Fan, Xue-Hui; García-Martín, Juan Francisco; Wang, Xi; Song, Yun

    2015-01-01

    © 2015 Published by Elsevier B.V. Direct evidence for the formation of 1-hydroxylethyl radicals by ultrasound in red wine and air-saturated model wine is presented in this paper. Free radicals are thought to be the key intermediates in the ultrasound processing of wine, but their nature has not been established yet. Electron paramagnetic resonance (EPR) spin trapping with 5,5-dimethyl-l-pyrrolin N-oxide (DMPO) was used for the detection of hydroxyl free radicals and 1-hydroxylethyl free radic...

  1. Valence isomerization of hexamethyl(dewar benzene) radical cation. Pulse radiolytic investigation

    International Nuclear Information System (INIS)

    Gebicki, J.; Marcinek, A.; Mayer, J.

    1989-01-01

    Organic radical ions are important intermediates in a wide variety of electron-transfer reactions. Both the steady-state and time-resolved techniques have been extensively applied to probe various aspects of their chemistry. We have recently established that low-temperature pulse radiolysis can be successfully applied to the kinetic study of radical ion transformations with very low activation barriers. The target of the present investigation is the hexamethyl(Dewar benzene) (HMDB)-hexamethylbenzene (HMDB) system. Studies by the CIDNP technique indicated the presence of two distinguishable radical cations in the system HMDB-HMB. This view has not been supported by a nanosecond spectroscopic observation which failed to reveal any evidence for a radical cation other than HMB sm-bullet+ . The aim of this work is to present spectroscopic evidence for two different radical cations HMDB sm-bullet+ -HMB sm-bullet+ and the activation barrier for their interconversion

  2. Development of flameless combustion; Desarrollo de la combustion sin flama

    Energy Technology Data Exchange (ETDEWEB)

    Flores Sauceda, M. Leonardo; Cervantes de Gortari, Jaime Gonzalo [Universidad Nacional Autonoma de Mexico, Mexico, D.F. (Mexico)]. E-mail: 8344afc@prodigy.net.mx; jgonzalo@servidor.unam.mx

    2010-11-15

    The paper intends contribute to global warming mitigation joint effort that develops technologies to capture the CO{sub 2} produced by fossil fuels combustion and to reduce emission of other greenhouse gases like the NO{sub x}. After reviewing existing combustion bibliography is pointed out that (a) touches only partial aspects of the collective system composed by Combustion-Heat transfer process-Environment, whose interactions are our primary interest and (b) most specialists think there is not yet a clearly winning technology for CO{sub 2} capture and storage. In this paper the study of combustion is focused as integrated in the aforementioned collective system where application of flameless combustion, using oxidant preheated in heat regenerators and fluent gas recirculation into combustion chamber plus appropriated heat and mass balances, simultaneously results in energy saving and environmental impact reduction. [Spanish] El trabajo pretende contribuir al esfuerzo conjunto de mitigacion del calentamiento global que aporta tecnologias para capturar el CO{sub 2} producido por la combustion de combustibles fosiles y para disminuir la emision de otros gases invernadero como NOx. De revision bibliografica sobre combustion se concluye que (a) trata aspectos parciales del sistema compuesto por combustion-proceso de trasferencia de calor-ambiente, cuyas interacciones son nuestro principal interes (b) la mayoria de especialistas considera no hay todavia una tecnologia claramente superior a las demas para captura y almacenaje de CO{sub 2}. Se estudia la combustion como parte integrante del mencionado sistema conjunto, donde la aplicacion de combustion sin flama, empleando oxidante precalentado mediante regeneradores de calor y recirculacion de gases efluentes ademas de los balances de masa y energia adecuados, permite tener simultaneamente ahorros energeticos e impacto ambiental reducido.

  3. Microjet burners for molecular-beam sources and combustion studies

    Science.gov (United States)

    Groeger, Wolfgang; Fenn, John B.

    1988-09-01

    A novel microjet burner is described in which combustion is stabilized by a hot wall. The scale is so small that the entire burner flow can be passed through a nozzle only 0.2 mm or less in diameter into an evacuated chamber to form a supersonic free jet with expansion so rapid that all collisional processes in the jet gas are frozen in a microsecond or less. This burner can be used to provide high-temperature source gas for free jet expansion to produce intense beams of internally hot molecules. A more immediate use would seem to be in the analysis of combustion products and perhaps intermediates by various kinds of spectroscopies without some of the perturbation effects encountered in probe sampling of flames and other types of combustion devices. As an example of the latter application of this new tool, we present infrared emission spectra for jet gas obtained from the combustion of oxygen-hydrocarbon mixtures both fuel-rich and fuel-lean operation. In addition, we show results obtained by mass spectrometric analysis of the combustion products.

  4. Mechanism of influence water vapor on combustion characteristics of propane-air mixture

    Science.gov (United States)

    Larionov, V. M.; Mitrofanov, G. A.; Sachovskii, A. V.; Kozar, N. K.

    2016-01-01

    The article discusses the results of an experimental study of the effect of water vapor at the flame temperature. Propane-butane mixture with air is burning on a modified Bunsen burner. Steam temperature was varied from 180 to 260 degrees. Combustion parameters changed by steam temperature and its proportion in the mixture with the fuel. The fuel-air mixture is burned in the excess air ratio of 0.1. It has been established that the injection of steam changes the characteristics of combustion fuel-air mixture and increase the combustion temperature. The concentration of CO in the combustion products is substantially reduced. Raising the temperature in the combustion zone is associated with increased enthalpy of the fuel by the added steam enthalpy. Reducing the concentration of CO is caused by decrease in the average temperature in the combustion zone by applying steam. Concentration of active hydrogen radicals and oxygen increases in the combustion zone. That has a positive effect on the process of combustion.

  5. Welding. Performance Objectives. Intermediate Course.

    Science.gov (United States)

    Vincent, Kenneth

    Several intermediate performance objectives and corresponding criterion measures are listed for each of nine terminal objectives for an intermediate welding course. The materials were developed for a 36-week (3 hours daily) course designed to prepare the student for employment in the field of welding. Electric welding and specialized (TIG & MIG)…

  6. Intermediate structure and threshold phenomena

    International Nuclear Information System (INIS)

    Hategan, Cornel

    2004-01-01

    The Intermediate Structure, evidenced through microstructures of the neutron strength function, is reflected in open reaction channels as fluctuations in excitation function of nuclear threshold effects. The intermediate state supporting both neutron strength function and nuclear threshold effect is a micro-giant neutron threshold state. (author)

  7. Insignificant disease among men with intermediate-risk prostate cancer.

    Science.gov (United States)

    Hong, Sung Kyu; Vertosick, Emily; Sjoberg, Daniel D; Scardino, Peter T; Eastham, James A

    2014-12-01

    A paucity of data exists on the insignificant disease potentially suitable for active surveillance (AS) among men with intermediate-risk prostate cancer (PCa). We tried to identify pathologically insignificant disease and its preoperative predictors in men who underwent radical prostatectomy (RP) for intermediate-risk PCa. We analyzed data of 1,630 men who underwent RP for intermediate-risk disease. Total tumor volume (TTV) data were available in 332 men. We examined factors associated with classically defined pathologically insignificant cancer (organ-confined disease with TTV ≤0.5 ml with no Gleason pattern 4 or 5) and pathologically favorable cancer (organ-confined disease with no Gleason pattern 4 or 5) potentially suitable for AS. Decision curve analysis was used to assess clinical utility of a multivariable model including preoperative variables for predicting pathologically unfavorable cancer. In the entire cohort, 221 of 1,630 (13.6 %) total patients had pathologically favorable cancer. Among 332 patients with TTV data available, 26 (7.8 %) had classically defined pathologically insignificant cancer. Between threshold probabilities of 20 and 40 %, decision curve analysis demonstrated that using multivariable model to identify AS candidates would not provide any benefit over simply treating all men who have intermediate-risk disease with RP. Although a minority of patients with intermediate-risk disease may harbor pathologically favorable or insignificant cancer, currently available conventional tools are not sufficiently able to identify those patients.

  8. Environmentally persistent free radicals amplify ultrafine particle mediated cellular oxidative stress and cytotoxicity

    Directory of Open Access Journals (Sweden)

    Balakrishna Shrilatha

    2009-04-01

    Full Text Available Abstract Background Combustion generated particulate matter is deposited in the respiratory tract and pose a hazard to the lungs through their potential to cause oxidative stress and inflammation. We have previously shown that combustion of fuels and chlorinated hydrocarbons produce semiquinone-type radicals that are stabilized on particle surfaces (i.e. environmentally persistent free radicals; EPFRs. Because the composition and properties of actual combustion-generated particles are complex, heterogeneous in origin, and vary from day-to-day, we have chosen to use surrogate particle systems. In particular, we have chosen to use the radical of 2-monochlorophenol (MCP230 as the EPFR because we have previously shown that it forms a EPFR on Cu(IIO surfaces and catalyzes formation of PCDD/F. To understand the physicochemical properties responsible for the adverse pulmonary effects of combustion by-products, we have exposed human bronchial epithelial cells (BEAS-2B to MCP230 or the CuO/silica substrate. Our general hypothesis was that the EPFR-containing particle would have greater toxicity than the substrate species. Results Exposure of BEAS-2B cells to our combustion generated particle systems significantly increased reactive oxygen species (ROS generation and decreased cellular antioxidants resulting in cell death. Resveratrol treatment reversed the decline in cellular glutathione (GSH, glutathione peroxidase (GPx, and superoxide dismutase (SOD levels for both types of combustion-generated particle systems. Conclusion The enhanced cytotoxicity upon exposure to MCP230 correlated with its ability to generate more cellular oxidative stress and concurrently reduce the antioxidant defenses of the epithelial cells (i.e. reduced GSH, SOD activity, and GPx. The EPFRs in MCP230 also seem to be of greater biological concern due to their ability to induce lipid peroxidation. These results are consistent with the oxidizing nature of the CuO/silica ultrafine

  9. Radical production in biological systems

    International Nuclear Information System (INIS)

    Johnson, J.R.; Akabani, G.

    1994-10-01

    This paper describes our effort to develop a metric for radiation exposure that is more fundamental than adsorbed dose and upon which a metric for exposure to chemicals could be based. This metric is based on the production of radicals by the two agents. Radicals produced by radiation in biological systems commonly assumed to be the same as those produced in water despite the presence of a variety of complex molecules. This may explain why the extensive efforts to describe the relationship between energy deposition (track structure) and molecular damage to DNA, based on the spectrum of radicals produced, have not been successful in explaining simple biological effects such as cell killing. Current models assume that DNA and its basic elements are immersed in water-like media and only model the production and diffusion of water-based radicals and their interaction with DNA structures; these models lack the cross sections associated with each macro-component of DNA and only treat water-based radicals. It has been found that such models are not realistic because DNA is not immersed in pure water. A computer code capable of simulating electron tracks, low-energy electrons, energy deposition in small molecules, and radical production and diffusion in water like media has been developed. This code is still in at a primitive stage and development is continuing. It is being used to study radical production by radiation, and radical diffusion and interactions in simple molecular systems following their production. We are extending the code to radical production by chemicals to complement our PBPK modeling efforts. It therefore has been developed primarily for use with radionuclides that are in biological materials, and not for radiation fields

  10. Guest Editorial: Processes of Radicalization and De-Radicalization

    Directory of Open Access Journals (Sweden)

    Donatella Della Porta

    2012-05-01

    Full Text Available The study of radicalization and de-radicalization, understood as processes leading towards the increased or decreased use of political violence, is central to the question of how political violence emerges, how it can be prevented, and how it can be contained. The focus section of this issue of the International Journal of Conflict and Violence addresses radicalization and de-radicalization, seeking to develop a more comprehensive understanding of the processes, dynamics, and mechanisms involved and taking an interdisciplinary approach to overcome the fragmentation into separate disciplines and focus areas. Contributions by Pénélope Larzillière, Felix Heiduk, Bill Kissane, Hank Johnston, Christian Davenport and Cyanne Loyle, Veronique Dudouet, and Lasse Lindekilde address repressive settings, legitimacy, institutional aspects, organizational outcomes, and dynamics in Europe, Asia, Africa, and North and South America.

  11. Intermediate neutron spectrum problems and the intermediate neutron spectrum experiment

    International Nuclear Information System (INIS)

    Jaegers, P.J.; Sanchez, R.G.

    1996-01-01

    Criticality benchmark data for intermediate energy spectrum systems does not exist. These systems are dominated by scattering and fission events induced by neutrons with energies between 1 eV and 1 MeV. Nuclear data uncertainties have been reported for such systems which can not be resolved without benchmark critical experiments. Intermediate energy spectrum systems have been proposed for the geological disposition of surplus fissile materials. Without the proper benchmarking of the nuclear data in the intermediate energy spectrum, adequate criticality safety margins can not be guaranteed. The Zeus critical experiment now under construction will provide this necessary benchmark data

  12. Sulfur Chemistry in Combustion I

    DEFF Research Database (Denmark)

    Johnsson, Jan Erik; Glarborg, Peter

    2000-01-01

    of the sulphur compounds in fossil fuels and the possibilities to remove them will be given. Then the combustion of sulphur species and their influence on the combustion chemistry and especially on the CO oxidation and the NOx formation will be described. Finally the in-situ removal of sulphur in the combustion...... process by reaction between SO2 and calcium containing sorbents and the influence on the NOx chemistry will be treated....

  13. Redox properties of free radicals

    International Nuclear Information System (INIS)

    Neta, P.

    1981-01-01

    Results of electron transfer reactions observed and monitored by pulse radiolysis are reported. This technique allows determination of the first one-electron reduction or oxidation of a compound rather than the overall two-electron transfer usually reported. Pulse radiolysis allows the determination of absolute rate constants for reactions of free radicals and helps elucidate the mechanisms involved. Studies using this technique to study radicals derived from quinones, nitro compounds, pyridines, phenols, and anilines are reported. Radicals of biochemical interest arising from riboflavin, ascorbic acid, vitamin K 3 , vitamin E, MAD + , porphyrins, etc. have also been studied

  14. Hot wire radicals and reactions

    International Nuclear Information System (INIS)

    Zheng Wengang; Gallagher, Alan

    2006-01-01

    Threshold ionization mass spectroscopy is used to measure radical (and stable gas) densities at the substrate of a tungsten hot wire (HW) reactor. We report measurements of the silane reaction probability on the HW and the probability of Si and H release from the HW. We describe a model for the atomic H release, based on the H 2 dissociation model. We note major variations in silicon-release, with dependence on prior silane exposure. Measured radical densities versus silane pressure yield silicon-silane and H-silane reaction rate coefficients, and the dominant radical fluxes to the substrate

  15. Pulsating combustion - Combustion characteristics and reduction of emissions

    Energy Technology Data Exchange (ETDEWEB)

    Lindholm, Annika

    1999-11-01

    In the search for high efficiency combustion systems pulsating combustion has been identified as one of the technologies that potentially can meet the objectives of clean combustion and good fuel economy. Pulsating combustion offers low emissions of pollutants, high heat transfer and efficient combustion. Although it is an old technology, the interest in pulsating combustion has been renewed in recent years, due to its unique features. Various applications of pulsating combustion can be found, mainly as drying and heating devices, of which the latter also have had commercial success. It is, however, in the design process of a pulse combustor, difficult to predict the operating frequency, the heat release etc., due to the lack of a well founded theory of the phenomenon. Research concerning control over the combustion process is essential for developing high efficiency pulse combustors with low emissions. Natural gas fired Helmholtz type pulse combustors have been the experimental objects of this study. In order to investigate the interaction between the fluid dynamics and the chemistry in pulse combustors, laser based measuring techniques as well as other conventional measuring techniques have been used. The experimental results shows the possibilities to control the combustion characteristics of pulsating combustion. It is shown that the time scales in the large vortices created at the inlet to the combustion chamber are very important for the operation of the pulse combustor. By increasing/decreasing the time scale for the large scale mixing the timing of the heat release is changed and the operating characteristics of the pulse combustor changes. Three different means for NO{sub x} reduction in Helmholtz type pulse combustors have been investigated. These include exhaust gas recirculation, alteration of air/fuel ratio and changed inlet geometry in the combustion chamber. All used methods achieved less than 10 ppm NO{sub x} emitted (referred to stoichiometric

  16. Reaction between peroxynitrite and boronates: EPR spin-trapping, HPLC analyses, and quantum mechanical study of the free radical pathway

    Science.gov (United States)

    Sikora, Adam; Zielonka, Jacek; Lopez, Marcos; Dybala-Defratyka, Agnieszka; Joseph, Joy; Marcinek, Andrzej; Kalyanaraman, Balaraman

    2013-01-01

    Recently we showed that peroxynitrite (ONOO−) reacts directly and rapidly with aromatic and aliphatic boronic acids (k ≈ 106 M−1s−1). Product analyses and substrate consumption data indicated that ONOO− reacts stoichiometrically with boronates, yielding the corresponding phenols as the major product (~85–90%), and the remaining products (10–15%) were proposed to originate from free radical intermediates (phenyl and phenoxyl radicals). Here we investigated in detail the minor, free radical pathway of boronate reaction with ONOO−. The electron paramagnetic resonance (EPR) spin-trapping technique was used to characterize the free radical intermediates formed from the reaction between boronates and ONOO−. Using 2-methyl-2-nitrosopropane (MNP) and 5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide (DEPMPO) spin traps, phenyl radicals were trapped and detected. Although phenoxyl radicals were not detected, the positive effects of molecular oxygen, and inhibitory effects of hydrogen atom donors (acetonitrile, and 2-propanol) and general radical scavengers (GSH, NADH, ascorbic acid and tyrosine) on the formation of phenoxyl radical-derived nitrated product, suggest that phenoxyl radical was formed as the secondary species. We propose that the initial step of the reaction involves the addition of ONOO− to the boron atom in boronates. The anionic intermediate undergoes both heterolytic (major pathway) and homolytic (minor pathway) cleavage of the peroxy (O-O) bond to form phenol and nitrite as a major product (via a non-radical mechanism), or a radical pair PhB(OH)2O•−…•NO2 as a minor product. It is conceivable that phenyl radicals are formed by the fragmentation of PhB(OH)2O•− radical anion. According to the DFT quantum mechanical calculations, the energy barrier for the dissociation of PhB(OH)2O•− radical anion to form phenyl radicals is only a few kcal/mol, suggesting rapid and spontaneous fragmentation of PhB(OH)2O•− radical anion

  17. Advanced modeling of oxy-fuel combustion of natural gas

    Energy Technology Data Exchange (ETDEWEB)

    Chungen Yin

    2011-01-15

    The main goal of this small-scale project is to investigate oxy-combustion of natural gas (NG) through advanced modeling, in which radiation, chemistry and mixing will be reasonably resolved. 1) A state-of-the-art review was given regarding the latest R and D achievements and status of oxy-fuel technology. The modeling and simulation status and achievements in the field of oxy-fuel combustion were also summarized; 2) A computer code in standard c++, using the exponential wide band model (EWBM) to evaluate the emissivity and absorptivity of any gas mixture at any condition, was developed and validated in detail against data in literature. A new, complete, and accurate WSGGM, applicable to both air-fuel and oxy-fuel combustion modeling and applicable to both gray and non-gray calculation, was successfully derived, by using the validated EWBM code as the reference mode. The new WSGGM was implemented in CFD modeling of two different oxy-fuel furnaces, through which its great, unique advantages over the currently most widely used WSGGM were demonstrated. 3) Chemical equilibrium calculations were performed for oxy-NG flame and air-NG flame, in which dissociation effects were considered to different degrees. Remarkable differences in oxy-fuel and air-fuel combustion were revealed, and main intermediate species that play key roles in oxy-fuel flames were identified. Different combustion mechanisms are compared, e.g., the most widely used 2-step global mechanism, refined 4-step global mechanism, a global mechanism developed for oxy-fuel using detailed chemical kinetic modeling (CHEMKIN) as reference. 4) Over 15 CFD simulations were done for oxy-NG combustion, in which radiation, chemistry, mixing, turbulence-chemistry interactions, and so on were thoroughly investigated. Among all the simulations, RANS combined with 2-step and refined 4-step mechanism, RANS combined with CHEMKIN-based new global mechanism for oxy-fuel modeling, and LES combined with different combustion

  18. Combustion from basics to applications

    CERN Document Server

    Lackner, Maximilian; Winter, Franz

    2013-01-01

    Combustion, the process of burning, is defined as a chemical reaction between a combustible reactant (the fuel) and an oxidizing agent (such as air) in order to produce heat and in most cases light while new chemical species (e.g., flue gas components) are formed. This book covers a gap on the market by providing a concise introduction to combustion. Most of the other books currently available are targeted towards the experienced users and contain too many details and/or contain knowledge at a fairly high level. This book provides a brief and clear overview of the combustion basics, suitable f

  19. Mathematical Modeling in Combustion Science

    CERN Document Server

    Takeno, Tadao

    1988-01-01

    An important new area of current research in combustion science is reviewed in the contributions to this volume. The complicated phenomena of combustion, such as chemical reactions, heat and mass transfer, and gaseous flows, have so far been studied predominantly by experiment and by phenomenological approaches. But asymptotic analysis and other recent developments are rapidly changing this situation. The contributions in this volume are devoted to mathematical modeling in three areas: high Mach number combustion, complex chemistry and physics, and flame modeling in small scale turbulent flow combustion.

  20. Combustion Byproducts Recycling Consortium

    Energy Technology Data Exchange (ETDEWEB)

    Ziemkiewicz, Paul; Vandivort, Tamara; Pflughoeft-Hassett, Debra; Chugh, Y Paul; Hower, James

    2008-08-31

    Each year, over 100 million tons of solid byproducts are produced by coal-burning electric utilities in the United States. Annual production of flue gas desulfurization (FGD) byproducts continues to increase as the result of more stringent sulfur emission restrictions. In addition, stricter limits on NOx emissions mandated by the 1990 Clean Air Act have resulted in utility burner/boiler modifications that frequently yield higher carbon concentrations in fly ash, which restricts the use of the ash as a cement replacement. Controlling ammonia in ash is also of concern. If newer, “clean coal” combustion and gasification technologies are adopted, their byproducts may also present a management challenge. The objective of the Combustion Byproducts Recycling Consortium (CBRC) is to develop and demonstrate technologies to address issues related to the recycling of byproducts associated with coal combustion processes. A goal of CBRC is that these technologies, by the year 2010, will lead to an overall ash utilization rate from the current 34% to 50% by such measures as increasing the current rate of FGD byproduct use and increasing in the number of uses considered “allowable” under state regulations. Another issue of interest to the CBRC would be to examine the environmental impact of both byproduct utilization and disposal. No byproduct utilization technology is likely to be adopted by industry unless it is more cost-effective than landfilling. Therefore, it is extremely important that the utility industry provide guidance to the R&D program. Government agencies and privatesector organizations that may be able to utilize these materials in the conduct of their missions should also provide input. The CBRC will serve as an effective vehicle for acquiring and maintaining guidance from these diverse organizations so that the proper balance in the R&D program is achieved.

  1. Hydroxyl radical induced transformation of phenylurea herbicides: A theoretical study

    International Nuclear Information System (INIS)

    Mile, Viktória; Harsányi, Ildikó; Kovács, Krisztina; Földes, Tamás; Takács, Erzsébet; Wojnárovits, László

    2017-01-01

    Aromatic ring hydroxylation reactions occurring during radiolysis of aqueous solutions are studied on the example of phenylurea herbicides by Density Functional Theory calculations. The effect of the aqueous media is taken into account by using the Solvation Model Based on Density model. Hydroxyl radical adds to the ring because the activation free energies (0.4–47.2 kJ mol −1 ) are low and also the Gibbs free energies have high negative values ((−27.4) to (−5.9) kJ mol −1 ). According to the calculations in most of cases the ortho- and para-addition is preferred in agreement with the experimental results. In these reactions hydroxycyclohexadienyl type radicals form. In a second type reaction, when loss of chlorine atom takes place, OH/Cl substitution occurs without cyclohexadienyl type intermediate. - Highlights: • Attack of • OH to aniline, phenol, fenuron, monuron, diuron was studied by DFT. • Ortho-para directing is suggested with –NH 2 , –OH and –NHCON(CH 3 ) 2 groups. • • OH addition to the ring gives hydroxycyclohexadienyl radical. • Attack at C-Cl leads to • OH/Cl substitution without cyclohexadienyl intermediate.

  2. CONTINENT RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    Yu. P. Sernyak

    2013-01-01

    Full Text Available Objective: to evaluate the impact of dissection of the dorsal venous complex without pre-ligation, suturing, or coagulation during radical prostatectomy (RPE in patients with localized prostate cancer (PC on the quality of surgery and the function of urinary retention.Subjects and methods. The data of 42 patients who had undergone posterior and anterior anatomical repair and vesicourethral anastomosis using a V-lock suture after prostatectomy were analyzed. All the patients were divided into 2 groups. Group 1 consisted of 22 patients in whom the dorsal venous complex was closed using a 3-0 vicryl suture before urethral dissection. Group 2 included 20 patients in whom the urethra was dissected without suturing the venous complex.Results. In group 1, complete urinary retention after catheter removal was noted in 9 (40.9 % and 15 (68 % patients within 24 hours and after 3 months, respectively. Following 12 months, two (9 % patients were observed to have partial mild urinary incontinence (as many as 2 pads per day. Group 2 patients showed complete urinary retention in 17 (85 % cases on the first day after catheter removal; all the patients retained urine 3 months later.Conclusion. In patients with localized PC, dissection of the dorsal venous complex without presuturing during laparoscopic RPE exerts a considerable impact on the preservation of urinary retention, namely 45% more of the patients reported complete urinary retention in early periods and 10 % more did this in later periods. At the same time, there was no statistically significant increase in intraoperative blood loss (p > 0.05, the number of positive edges, or biochemical recurrences.

  3. CONTINENT RADICAL PROSTATECTOMY

    Directory of Open Access Journals (Sweden)

    Yu. P. Sernyak

    2014-07-01

    Full Text Available Objective: to evaluate the impact of dissection of the dorsal venous complex without pre-ligation, suturing, or coagulation during radical prostatectomy (RPE in patients with localized prostate cancer (PC on the quality of surgery and the function of urinary retention.Subjects and methods. The data of 42 patients who had undergone posterior and anterior anatomical repair and vesicourethral anastomosis using a V-lock suture after prostatectomy were analyzed. All the patients were divided into 2 groups. Group 1 consisted of 22 patients in whom the dorsal venous complex was closed using a 3-0 vicryl suture before urethral dissection. Group 2 included 20 patients in whom the urethra was dissected without suturing the venous complex.Results. In group 1, complete urinary retention after catheter removal was noted in 9 (40.9 % and 15 (68 % patients within 24 hours and after 3 months, respectively. Following 12 months, two (9 % patients were observed to have partial mild urinary incontinence (as many as 2 pads per day. Group 2 patients showed complete urinary retention in 17 (85 % cases on the first day after catheter removal; all the patients retained urine 3 months later.Conclusion. In patients with localized PC, dissection of the dorsal venous complex without presuturing during laparoscopic RPE exerts a considerable impact on the preservation of urinary retention, namely 45% more of the patients reported complete urinary retention in early periods and 10 % more did this in later periods. At the same time, there was no statistically significant increase in intraoperative blood loss (p > 0.05, the number of positive edges, or biochemical recurrences.

  4. The combustion of sodium

    International Nuclear Information System (INIS)

    Newman, R.N.

    1978-01-01

    The burning rates of sodium in the form of vapour jets, droplets, sprays and unconfined and confined pools have been reviewed. Attention has been paid to assessing the value of models in the various combustion modes. Additional models have been constructed for the descriptions of laminar and turbulent vapour jets, stationary droplets, forced convection over ambient pool fires together with correlations for peak pressures in confined pool environments. Where appropriate experiments with sodium have not been conducted, the likely behaviour is predicted by comparison with the burning of other fuels, particularly in the field of large free ambient fires. Some areas where further knowledge is required are highlighted. (author)

  5. Alternate fuels; Combustibles alternos

    Energy Technology Data Exchange (ETDEWEB)

    Romero Paredes R, Hernando; Ambriz G, Juan Jose [Universidad Autonoma Metropolitana. Iztapalapa (Mexico)

    2003-07-01

    In the definition and description of alternate fuels we must center ourselves in those technological alternatives that allow to obtain compounds that differ from the traditional ones, in their forms to be obtained. In this article it is tried to give an overview of alternate fuels to the conventional derivatives of petroleum and that allow to have a clear idea on the tendencies of modern investigation and the technological developments that can be implemented in the short term. It is not pretended to include all the tendencies and developments of the present world, but those that can hit in a relatively short term, in accordance with agreed with the average life of conventional fuels. Nevertheless, most of the conversion principles are applicable to the spectrum of carbonaceous or cellulosic materials which are in nature, are cultivated or wastes of organic origin. Thus one will approach them in a successive way, the physical, chemical and biological conversions that can take place in a production process of an alternate fuel or the same direct use of the fuel such as burning the sweepings derived from the forests. [Spanish] En la definicion y descripcion de combustibles alternos nos debemos centrar en aquellas alternativas tecnologicas que permitan obtener compuestos que difieren de los tradicionales, al menos en sus formas de ser obtenidos. En este articulo se pretende dar un panorama de los combustibles alternos a los convencionales derivados del petroleo y que permita tener una idea clara sobre las tendencias de la investigacion moderna y los desarrollos tecnologicos que puedan ser implementados en el corto plazo. No se pretende abarcar todas las tendencias y desarrollos del mundo actual, sino aquellas que pueden impactar en un plazo relativamente corto, acordes con la vida media de los combustibles convencionales. Sin embargo, la mayor parte de los principios de conversion son aplicables al espectro de materiales carbonaceos o celulosicos los cuales se

  6. Fluidised bed combustion system

    International Nuclear Information System (INIS)

    McKenzie, E.C.

    1976-01-01

    Fluidized bed combustion systems that facilitates the maintenance of the depth of the bed are described. A discharge pipe projects upwardly into the bed so that bed material can flow into its upper end and escape downwardly. The end of the pipe is surrounded by an enclosure and air is discharged into the enclosure so that material will enter the pipe from within the enclosure and have been cooled in the enclosure by the air discharged into it. The walls of the enclosure may themselves be cooled

  7. Radical Change by Entrepreneurial Design

    National Research Council Canada - National Science Library

    Roberts, Nancy C

    1998-01-01

    .... Radical change by entrepreneurial design then becomes the focal point, in order to acquaint the reader with the strategies and tactics of well-known entrepreneurs who have been successful in molding...

  8. Penile rehabilitation after radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Ohl, Dana A; Ralph, David

    2013-01-01

    The pathophysiology of erectile dysfunction after radical prostatectomy (RP) is believed to include neuropraxia, which leads to temporarily reduced oxygenation and subsequent structural changes in penile tissue. This results in veno-occlusive dysfunction, therefore, penile rehabilitation programmes...

  9. Fuel and combustion stratification study of Partially Premixed Combustion

    NARCIS (Netherlands)

    Izadi Najafabadi, M.; Dam, N.; Somers, B.; Johansson, B.

    2016-01-01

    Relatively high levels of stratification is one of the main advantages of Partially Premixed Combustion (PPC) over the Homogeneous Charge Compression Ignition (HCCI) concept. Fuel stratification smoothens heat release and improves controllability of this kind of combustion. However, the lack of a

  10. Basic study on the generation of RF plasmas in premixed oxy-combustion with methane

    International Nuclear Information System (INIS)

    Osaka, Yugo; Razzak, M.A.; Kobayashi, Noriyuki; Ohno, Noriyasu; Takamura, Shuichi; Uesugi, Yoshihiko

    2010-01-01

    Oxy-combustion generates a high temperature field (above 3000 K), which is applied to next generation power plants and high temperature industrial technologies because of N 2 free processes. However, the combustion temperature is so high that the furnace wall may be fatally damaged. In addition, it is very difficult to control the heat flux and chemical species' concentrations because of rapid chemical reactions. We have developed a new method for controlling the flame by electromagnetic force on this field. In this paper, we experimentally investigated the power coupling between the premixed oxy-combustion with methane and radio frequency (RF) power through the induction coil. By optimizing the power coupling, we observed that the flame can absorb RF power up to 1.5 kW. Spectroscopic measurements also showed an increase in the emission intensity from OH radicals in the flame, indicating improved combustibility. (author)

  11. Radical prostatectomy. Results and indications

    International Nuclear Information System (INIS)

    Jacqmin, D.

    1997-01-01

    Radical prostatectomy is the surgical curative treatment of localized prostate cancer. The survival is good in young patients (<70) with T2 N0M0 tumors and more than 10 year's life expectancy. Side-effects are urinary incontinence, impotence and anastomosis stricture. Quality of life should be considered as an important factor for the choice of the patient between radical prostatectomy, radiotherapy and follow-up. (author)

  12. Radical Islamism and Failed Developmentalism

    OpenAIRE

    Rahnema, Saeed

    2008-01-01

    The rise of radical Islamism in recent years does not limit the applicability of the concept of cultural nationalism. Rather the two are intertwined in ways which this article will attempt to highlight. Islam took specific national forms as modern nation-states arose and the contemporary resurgence of radical Islamism also follows that modern pattern. I examine the emergence of the three most important movements in the Islamic world, namely, the Muslim Brotherhood in Egypt, Jama'at-e Islami i...

  13. Combustion Stratification for Naphtha from CI Combustion to PPC

    KAUST Repository

    Vallinayagam, R.

    2017-03-28

    This study demonstrates the combustion stratification from conventional compression ignition (CI) combustion to partially premixed combustion (PPC). Experiments are performed in an optical CI engine at a speed of 1200 rpm for diesel and naphtha (RON = 46). The motored pressure at TDC is maintained at 35 bar and fuelMEP is kept constant at 5.1 bar to account for the difference in fuel properties between naphtha and diesel. Single injection strategy is employed and the fuel is injected at a pressure of 800 bar. Photron FASTCAM SA4 that captures in-cylinder combustion at the rate of 10000 frames per second is employed. The captured high speed video is processed to study the combustion homogeneity based on an algorithm reported in previous studies. Starting from late fuel injection timings, combustion stratification is investigated by advancing the fuel injection timings. For late start of injection (SOI), a direct link between SOI and combustion phasing is noticed. At early SOI, combustion phasing depends on both intake air temperature and SOI. In order to match the combustion phasing (CA50) of diesel, the intake air temperature is increased to 90°C for naphtha. The combustion stratification from CI to PPC is also investigated for various level of dilution by displacing oxygen with nitrogen in the intake. The start of combustion (SOC) was delayed with the increase in dilution and to compensate for this, the intake air temperature is increased. The mixture homogeneity is enhanced for higher dilution due to longer ignition delay. The results show that high speed image is initially blue and then turned yellow, indicating soot formation and oxidation. The luminosity of combustion images decreases with early SOI and increased dilution. The images are processed to generate the level of stratification based on the image intensity. The level of stratification is same for diesel and naphtha at various SOI. When O concentration in the intake is decreased to 17.7% and 14

  14. Mass spectrometric characterization of a pyrolytic radical source using femtosecond ionization

    Energy Technology Data Exchange (ETDEWEB)

    Frey, H M; Beaud, P; Mischler, B; Radi, P P; Tzannis, A P; Gerber, T [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Radicals play, as reactive species, an important role in the chemistry of combustion. In contrast to atmospheric flames where spectra are congested due to high vibrational and rotational excitation, experiments in the cold environment of a molecular beam (MB) yield clean spectra that can be easily attributed to one species by Resonantly Enhanced Multi Photon Ionization (REMP). A pyrolytic radical source has been set up. To characterize the efficiency of the source `soft` ionization with femto second pulses is applied which results in less fragmentation, simplifying the interpretation of the mass spectrum. (author) figs., tabs., refs.

  15. Some Factors Affecting Combustion in an Internal-Combustion Engine

    Science.gov (United States)

    Rothrock, A M; Cohn, Mildred

    1936-01-01

    An investigation of the combustion of gasoline, safety, and diesel fuels was made in the NACA combustion apparatus under conditions of temperature that permitted ignition by spark with direct fuel injection, in spite of the compression ratio of 12.7 employed. The influence of such variables as injection advance angle, jacket temperature, engine speed, and spark position was studied. The most pronounced effect was that an increase in the injection advance angle (beyond a certain minimum value) caused a decrease in the extent and rate of combustion. In almost all cases combustion improved with increased temperature. The results show that at low air temperatures the rates of combustion vary with the volatility of the fuel, but that at high temperatures this relationship does not exist and the rates depend to a greater extent on the chemical nature of the fuel.

  16. Preliminary assessment of combustion modes for internal combustion wave rotors

    Science.gov (United States)

    Nalim, M. Razi

    1995-01-01

    Combustion within the channels of a wave rotor is examined as a means of obtaining pressure gain during heat addition in a gas turbine engine. Several modes of combustion are considered and the factors that determine the applicability of three modes are evaluated in detail; premixed autoignition/detonation, premixed deflagration, and non-premixed compression ignition. The last two will require strong turbulence for completion of combustion in a reasonable time in the wave rotor. The compression/autoignition modes will require inlet temperatures in excess of 1500 R for reliable ignition with most hydrocarbon fuels; otherwise, a supplementary ignition method must be provided. Examples of combustion mode selection are presented for two core engine applications that had been previously designed with equivalent 4-port wave rotor topping cycles using external combustion.

  17. Laparoscopic radical cystectomy: key points

    Directory of Open Access Journals (Sweden)

    D. V. Perlin

    2018-01-01

    Full Text Available Background. Radical cystectomy remains the golden standard for treatment of muscle invasive bladder cancer. Objective: to duplicate with highest accuracy the open radical cystectomy procedure, which we successfully utilized earlier in our clinic, in the of laparoscopic conditions in order to preserve the advantages of minimally invasive procedures and retain the reliability of the tried and tested open surgery.Materials and methods. In the report were included 35 patients (27 men and 8 women with bladder cancer, who underwent laparoscopic radical cystectomy in Volgograd Regional Center of Urology and Nephrology between April 2013 and March 2016. Only the patients who had been submitted to full intracorporal ileal conduits were included.Results. The mean operative time was 378 minutes, the mean blood loss was 285 millilitres, the mean length of hospital stay was 12.4 days, only 20 % of patients required the narcotic anesthetics. The postoperative complication rate was 11.4 %. However, the majority of the patients were successfully treated with minimally invasive procedures. Generally, our results were similar to other reported studies.Conclusion. Laparoscopic radical cystectomy is a safe and efficient modality of treatment of bladder cancer. However, it needs more procedures and longer observation period to establish laparoscopic radical cystectomy as an alternative to open radical cystectomy.

  18. Production of free radical by magnetized sheet plasma with vertical gas-flow

    International Nuclear Information System (INIS)

    Tonegawa, Akira; Takatori, Masahiko; Kawamura, Kazutaka

    1995-01-01

    Free radicals play an important role in plasma processing, environment problem, and space plasma and so on because of their outstanding physical properties. Although much work has been done on the free radicals in the reactive plasma, very little is known about the production mechanism of the free radicals against various plasma parameters. To overcome this problem, we have proposed to do a new system of a magnetized sheet plasma with vertical gas-flow. The sheet plasma is a special type of strongly magnetized highly ionized slab plasma. This system is controlled to the parameters of radicals and plasma independently. Therefore, it is possible to make a quantitative analysis of free radicals as the simple one. In this paper, we describe the magnetized sheet plasma with vertical gas-flow system and report the preliminary results of production of the free radical. In particular, we show to produce and control the OH free radical which has been the most commonly studied combustion species

  19. Path planning during combustion mode switch

    Science.gov (United States)

    Jiang, Li; Ravi, Nikhil

    2015-12-29

    Systems and methods are provided for transitioning between a first combustion mode and a second combustion mode in an internal combustion engine. A current operating point of the engine is identified and a target operating point for the internal combustion engine in the second combustion mode is also determined. A predefined optimized transition operating point is selected from memory. While operating in the first combustion mode, one or more engine actuator settings are adjusted to cause the operating point of the internal combustion engine to approach the selected optimized transition operating point. When the engine is operating at the selected optimized transition operating point, the combustion mode is switched from the first combustion mode to the second combustion mode. While operating in the second combustion mode, one or more engine actuator settings are adjusted to cause the operating point of the internal combustion to approach the target operating point.

  20. AIR EMISSIONS FROM SCRAP TIRE COMBUSTION

    Science.gov (United States)

    The report discusses air emissions from two types of scrap tire combustion: uncontrolled and controlled. Uncontrolled sources are open tire fires, which produce many unhealthful products of incomplete combustion and release them directly into the atmosphere. Controlled combustion...

  1. Plasma igniter for internal-combustion engines

    Science.gov (United States)

    Breshears, R. R.; Fitzgerald, D. J.

    1978-01-01

    Hot ionized gas (plasma) ignites air/fuel mixture in internal combustion engines more effectively than spark. Electromagnetic forces propel plasma into combustion zone. Combustion rate is not limited by flame-front speed.

  2. Application of enantioselective radical reactions: synthesis of (+)-ricciocarpins A and B.

    Science.gov (United States)

    Sibi, Mukund P; He, Liwen

    2004-05-27

    Enantioselective synthesis of (+)-ricciocarpins A and B has been achieved in 41 and 45% overall yields, respectively, starting from a beta-substituted oxazolidinone. The key steps in the strategy are an enantioselective conjugate radical addition and the addition of a furyl organometallic to a key aldehyde intermediate. [reaction--see text

  3. Guanosine radical reactivity explored by pulse radiolysis coupled with transient electrochemistry.

    Science.gov (United States)

    Latus, A; Alam, M S; Mostafavi, M; Marignier, J-L; Maisonhaute, E

    2015-06-04

    We follow the reactivity of a guanosine radical created by a radiolytic electron pulse both by spectroscopic and electrochemical methods. This original approach allows us to demonstrate that there is a competition between oxidation and reduction of these intermediates, an important result to further analyse the degradation or repair pathways of DNA bases.

  4. Intermediate Levels of Visual Processing

    National Research Council Canada - National Science Library

    Nakayama, Ken

    1998-01-01

    ...) surface representation, here we have shown that there is an intermediate level of visual processing, between the analysis of the image and higher order representations related to specific objects; (2...

  5. Gaseous emissions during concurrent combustion of biomass and non-recyclable municipal solid waste

    Directory of Open Access Journals (Sweden)

    Oakey John

    2011-02-01

    Full Text Available Abstract Background Biomass and municipal solid waste offer sustainable sources of energy; for example to meet heat and electricity demand in the form of combined cooling, heat and power. Combustion of biomass has a lesser impact than solid fossil fuels (e.g. coal upon gas pollutant emissions, whilst energy recovery from municipal solid waste is a beneficial component of an integrated, sustainable waste management programme. Concurrent combustion of these fuels using a fluidised bed combustor may be a successful method of overcoming some of the disadvantages of biomass (high fuel supply and distribution costs, combustion characteristics and characteristics of municipal solid waste (heterogeneous content, conflict with materials recycling. It should be considered that combustion of municipal solid waste may be a financially attractive disposal route if a 'gate fee' value exists for accepting waste for combustion, which will reduce the net cost of utilising relatively more expensive biomass fuels. Results Emissions of nitrogen monoxide and sulphur dioxide for combustion of biomass are suppressed after substitution of biomass for municipal solid waste materials as the input fuel mixture. Interactions between these and other pollutants such as hydrogen chloride, nitrous oxide and carbon monoxide indicate complex, competing reactions occur between intermediates of these compounds to determine final resultant emissions. Conclusions Fluidised bed concurrent combustion is an appropriate technique to exploit biomass and municipal solid waste resources, without the use of fossil fuels. The addition of municipal solid waste to biomass combustion has the effect of reducing emissions of some gaseous pollutants.

  6. Gaseous emissions during concurrent combustion of biomass and non-recyclable municipal solid waste.

    Science.gov (United States)

    Laryea-Goldsmith, René; Oakey, John; Simms, Nigel J

    2011-02-01

    Biomass and municipal solid waste offer sustainable sources of energy; for example to meet heat and electricity demand in the form of combined cooling, heat and power. Combustion of biomass has a lesser impact than solid fossil fuels (e.g. coal) upon gas pollutant emissions, whilst energy recovery from municipal solid waste is a beneficial component of an integrated, sustainable waste management programme. Concurrent combustion of these fuels using a fluidised bed combustor may be a successful method of overcoming some of the disadvantages of biomass (high fuel supply and distribution costs, combustion characteristics) and characteristics of municipal solid waste (heterogeneous content, conflict with materials recycling). It should be considered that combustion of municipal solid waste may be a financially attractive disposal route if a 'gate fee' value exists for accepting waste for combustion, which will reduce the net cost of utilising relatively more expensive biomass fuels. Emissions of nitrogen monoxide and sulphur dioxide for combustion of biomass are suppressed after substitution of biomass for municipal solid waste materials as the input fuel mixture. Interactions between these and other pollutants such as hydrogen chloride, nitrous oxide and carbon monoxide indicate complex, competing reactions occur between intermediates of these compounds to determine final resultant emissions. Fluidised bed concurrent combustion is an appropriate technique to exploit biomass and municipal solid waste resources, without the use of fossil fuels. The addition of municipal solid waste to biomass combustion has the effect of reducing emissions of some gaseous pollutants.

  7. Effect of reagents and medium nature on direction of cation-radical transformations in the reaction of diarylamines with nitrosonium borofluoride

    International Nuclear Information System (INIS)

    Koshechko, V.G.; Inozemtsev, A.N.; Pokhodenko, V.O.

    1983-01-01

    Diphenylamine and 4, 4'-dimethoxydiphenylamine in acetonitrile are oxidized monoelectronically by NOBF 4 . On the 4, 4'-dimethoxydiphenylamine example a maximum current concentration of intermediate cation-radicals formed in this reaction is measured. Cation-radicals in acetonitrile get dimeric transforming into products of oxidizing condensation of amines, with no respective nitrozamines being observed. Nitrosamines production on through cation-radical-NO recombination is realized but in the presence of protonoacceptor solvents, in particular pyridine

  8. Reactions of carbon radicals generated by 1,5-transposition of reactive centers

    Directory of Open Access Journals (Sweden)

    ZIVORAD CEKOVIC

    2005-03-01

    Full Text Available Radical intermediates can undergo specific reactions, such as intramolecular rearrangements, i.e., the transpositions of radical centers, which are not known in classical ionic organic reactions. 1,5-Transposition of a radical center to a non-activated carbon atom are of great synthetic importance. It can be successfully applied for the introduction of different functional groups (oxygen, nitrogen, sulfur, halogens onto a carbon atom remote from the present functional group. In addition to functionalization of a remote non-activated carbon atom, the formation of new C-C bonds on the d-carbon atom have also been achieved. 1,5-Transposition of the radical centers takes place from alkoxyl, aminyl and carbon radicals to a remote carbon atom. Relocation of the radical centers preferentially involves 1,5-transfer of a hydrogen atom, although migrations of some other groups are known. The reactions of the carbon radical generated by 1,5-relocation of the radical center are presented and their synthetic applications are reviewed.

  9. Simple model of inhibition of chain-branching combustion processes

    Science.gov (United States)

    Babushok, Valeri I.; Gubernov, Vladimir V.; Minaev, Sergei S.; Miroshnichenko, Taisia P.

    2017-11-01

    A simple kinetic model has been suggested to describe the inhibition and extinction of flame propagation in reaction systems with chain-branching reactions typical for hydrocarbon systems. The model is based on the generalised model of the combustion process with chain-branching reaction combined with the one-stage reaction describing the thermal mode of flame propagation with the addition of inhibition reaction steps. Inhibitor addition suppresses the radical overshoot in flame and leads to the change of reaction mode from the chain-branching reaction to a thermal mode of flame propagation. With the increase of inhibitor the transition of chain-branching mode of reaction to the reaction with straight-chains (non-branching chain reaction) is observed. The inhibition part of the model includes a block of three reactions to describe the influence of the inhibitor. The heat losses are incorporated into the model via Newton cooling. The flame extinction is the result of the decreased heat release of inhibited reaction processes and the suppression of radical overshoot with the further decrease of the reaction rate due to the temperature decrease and mixture dilution. A comparison of the results of modelling laminar premixed methane/air flames inhibited by potassium bicarbonate (gas phase model, detailed kinetic model) with the results obtained using the suggested simple model is presented. The calculations with the detailed kinetic model demonstrate the following modes of combustion process: (1) flame propagation with chain-branching reaction (with radical overshoot, inhibitor addition decreases the radical overshoot down to the equilibrium level); (2) saturation of chemical influence of inhibitor, and (3) transition to thermal mode of flame propagation (non-branching chain mode of reaction). The suggested simple kinetic model qualitatively reproduces the modes of flame propagation with the addition of the inhibitor observed using detailed kinetic models.

  10. The games radicals play : special issue on free radicals and radical ions

    OpenAIRE

    Walton, J.C.; Williams, F.

    2015-01-01

    Chemistry and Physics have aptly been described as “most excellent children of Intellect and Art” [1]. Both these “children” engage with many playthings, and molecules rank as one of their first favorites, especially radicals, which are amongst the most lively and exciting. Checking out radicals dancing to the music of entropy round their potential energy ballrooms is surely both entertaining and enlightening. Radicals’ old favorite convolutions are noteworthy, but the new styles, modes and a...

  11. In-cylinder Combustion and Soot Evolution in the Transition from Conventional CI mode to PPC

    KAUST Repository

    An, Yanzhao

    2018-01-09

    The present study intends to explore the in-cylinder combustion and evolution of soot emission during the transition from conventional compression ignition (CI) combustion to partially premixed combustion (PPC) at low load conditions. In-cylinder combustion images and engine-out emissions were measured in an optical engine fueled with low octane heavy naphtha fuel (RON = 50). Full cycle engine simulations were performed using a three-dimensional computational fluid dynamics code CONVERGETM, coupled with gas phase chemical kinetics, turbulence, and particulate size mimic soot model. The simulations were performed under low load conditions (IMEP ~ 2 to 3 bar) at an engine speed of 1200 rpm. The start of injection (SOI) was advanced from late (-10 CAD aTDC) to early fuel injection timings (-40 CAD aTDC) to realize the combustion transition from CI combustion to PPC. The simulation results of combustion and emission are compared with the experimental results at both CI and PPC combustion modes. The results of the study show a typical low-temperature stratified lean combustion at PPC mode, while high-temperature spray-driven combustion is evident at CI mode. The in-cylinder small intermediates species such as acetylene (C2H2), propargyl (C3H3), cyclopentadienyl (C5H5) and polycyclic aromatic hydrocarbons (PAHs) were significantly suppressed at PPC mode. Nucleation reaction of PAHs collision contributed to main soot mass production. The distribution of soot mass and particle number density was consistent with the distribution of high-temperature zones at CI and PPC combustion modes.

  12. Radical Addition to Iminium Ions and Cationic Heterocycles

    Directory of Open Access Journals (Sweden)

    Johannes Tauber

    2014-10-01

    Full Text Available Carbon-centered radicals represent highly useful reactive intermediates in organic synthesis. Their nucleophilic character is reflected by fast additions to electron deficient C=X double bonds as present in iminium ions or cationic heterocycles. This review covers diverse reactions of preformed or in situ-generated cationic substrates with various types of C-radicals, including alkyl, alkoxyalkyl, trifluoromethyl, aryl, acyl, carbamoyl, and alkoxycarbonyl species. Despite its high reactivity, the strong interaction of the radical’s SOMO with the LUMO of the cation frequently results in a high regioselectivity. Intra- and intermolecular processes such as the Minisci reaction, the Porta reaction, and the Knabe rearrangement will be discussed along with transition metal and photoredox catalysis or electrochemical methods to generate the odd-electron species.

  13. Site-specific management of miscanthus genotypes for combustion and anaerobic digestion

    NARCIS (Netherlands)

    Kiesel, Andreas; Nunn, Christopher; Iqbal, Yasir; Weijde, Van der Tim; Wagner, Moritz; Özgüven, Mensure; Tarakanov, Ivan; Kalinina, Olena; Trindade, Luisa M.; Clifton-Brown, John; Lewandowski, Iris

    2017-01-01

    In Europe, the perennial C4 grass miscanthus is currently mainly cultivated for energy generation via combustion. In recent years, anaerobic digestion has been identified as a promising alternative utilization pathway. Anaerobic digestion produces a higher-value intermediate (biogas), which can be

  14. A thermodynamic analysis of the environmental indicators of natural gas combustion processes

    Science.gov (United States)

    Elsukov, V. K.

    2010-07-01

    Environmental indicators of the natural gas combustion process are studied using the model of extreme intermediate states developed at the Melent’ev Institute of Power Engineering Systems. Technological factors responsible for generation of polycyclic aromatic hydrocarbons and hydrogen cyanide are revealed. Measures for reducing the amounts of polycyclic aromatic hydrocarbons, hydrogen cyanide, nitrogen oxide, and other pollutants emitted from boilers are developed.

  15. Combustion & Laser Diagnostics Research Complex (CLDRC)

    Data.gov (United States)

    Federal Laboratory Consortium — Description: The Combustion and Laser Diagnostics Research Complex (CLRDC) supports the experimental and computational study of fundamental combustion phenomena to...

  16. Modelling of plume chemistry of high flying aircraft with H2 combustion engines

    International Nuclear Information System (INIS)

    Weibring, G.; Zellner, R.

    1993-01-01

    Emissions from hydrogen fueled aircraft engines include large concentrations of radicals such as NO, OH, O and H. We describe the result of modelling studies in which the evolution of the radical chemistry in an expanding and cooling plume for three different mixing velocities is evaluated. The simulations were made for hydrogen combustion engines at an altitude of 26 km. For the fastest mixing conditions, the radical concentrations decrease only because of dilution with the ambient air, since the time for chemical reaction is too short. With lower mixing velocities, however, larger chemical conversions were determined. For the slowest mixing conditions the unburned hydrogen is converted into water. As a consequence the radicals O and OH increase considerably around 1400 K. The only exception being NO, for which no chemical change during the expansion is found. The concentrations of the reservoir molecules like H 2 O 2 , N 2 O 5 or HNO 3 have been calculated to remain relatively small. (orig.)

  17. Large Eddy simulation of turbulent hydrogen-fuelled supersonic combustion in an air cross-flow

    Science.gov (United States)

    Ingenito, A.; Cecere, D.; Giacomazzi, E.

    2013-09-01

    The main aim of this article is to provide a theoretical understanding of the physics of supersonic mixing and combustion. Research in advanced air-breathing propulsion systems able to push vehicles well beyond is of interest around the world. In a scramjet, the air stream flow captured by the inlet is decelerated but still maintains supersonic conditions. As the residence time is very short , the study of an efficient mixing and combustion is a key issue in the ongoing research on compressible flows. Due to experimental difficulties in measuring complex high-speed unsteady flowfields, the most convenient way to understand unsteady features of supersonic mixing and combustion is to use computational fluid dynamics. This work investigates supersonic combustion physics in the Hyshot II combustion chamber within the Large Eddy simulation framework. The resolution of this turbulent compressible reacting flow requires: (1) highly accurate non-dissipative numerical schemes to properly simulate strong gradients near shock waves and turbulent structures away from these discontinuities; (2) proper modelling of the small subgrid scales for supersonic combustion, including effects from compressibility on mixing and combustion; (3) highly detailed kinetic mechanisms (the Warnatz scheme including 9 species and 38 reactions is adopted) accounting for the formation and recombination of radicals to properly predict flame anchoring. Numerical results reveal the complex topology of the flow under investigation. The importance of baroclinic and dilatational effects on mixing and flame anchoring is evidenced. Moreover, their effects on turbulence-scale generation and the scaling law are analysed.

  18. Scavenging of free-radical metabolites of aniline xenobiotics and drugs by amino acid derivatives: toxicological implications of radical-transfer reactions.

    Science.gov (United States)

    Michail, Karim; Baghdasarian, Argishti; Narwaley, Malyaj; Aljuhani, Naif; Siraki, Arno G

    2013-12-16

    We investigated a novel scavenging mechanism of arylamine free radicals by poly- and monoaminocarboxylates. Free radicals of arylamine xenobiotics and drugs did not react with oxygen in peroxidase-catalyzed reactions; however, they showed marked oxygen uptake in the presence of an aminocarboxylate. These free-radical intermediates were identified using the spin trap 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and electron paramagnetic resonance (EPR) spectrometry. Diethylenetriaminepentaacetic acid (DTPA), a polyaminocarboxylate, caused a concentration-dependent attenuation of N-centered radicals produced by the peroxidative metabolism of arylamines with the subsequent formation of secondary aliphatic carbon-centered radicals stemming from the cosubstrate molecule. Analogously, N,N-dimethylglycine (DMG) and N-methyliminodiacetate (MIDA), but not iminodiacetic acid (IDA), demonstrated a similar scavenging effect of arylamine-derived free radicals in a horseradish peroxidase/H2O2 system. Using human promyelocytic leukemia (HL-60) cell lysate as a model of human neutrophils, DTPA, MIDA, and DMG readily reduced anilinium cation radicals derived from the arylamines and gave rise to the corresponding carbon radicals. The rate of peroxidase-triggered polymerization of aniline was studied as a measure of nitrogen-radical scavenging. Although, IDA had no effect on the rate of aniline polymerization, this was almost nullified in the presence of DTPA and MIDA at half of the molar concentration of the aniline substrate, whereas a 20 molar excess of DMPO caused only a partial inhibition. Furthermore, the yield of formaldehyde, a specific reaction endproduct of the oxidation of aminocarboxylates by aniline free-radical metabolites, was quantitatively determined. Azobenzene, a specific reaction product of peroxidase-catalyzed free-radical dimerization of aniline, was fully abrogated in the presence of DTPA, as confirmed by GC/MS. Under aerobic conditions, a radical-transfer reaction

  19. Combustion instability control in the model of combustion chamber

    International Nuclear Information System (INIS)

    Akhmadullin, A N; Ahmethanov, E N; Iovleva, O V; Mitrofanov, G A

    2013-01-01

    An experimental study of the influence of external periodic perturbations on the instability of the combustion chamber in a pulsating combustion. As an external periodic disturbances were used sound waves emitted by the electrodynamics. The purpose of the study was to determine the possibility of using the method of external periodic perturbation to control the combustion instability. The study was conducted on a specially created model of the combustion chamber with a swirl burner in the frequency range from 100 to 1400 Hz. The study found that the method of external periodic perturbations may be used to control combustion instability. Depending on the frequency of the external periodic perturbation is observed as an increase and decrease in the amplitude of the oscillations in the combustion chamber. These effects are due to the mechanisms of synchronous and asynchronous action. External periodic disturbance generated in the path feeding the gaseous fuel, showing the high efficiency of the method of management in terms of energy costs. Power required to initiate periodic disturbances (50 W) is significantly smaller than the thermal capacity of the combustion chamber (100 kW)

  20. Export Intermediation and the Internet

    DEFF Research Database (Denmark)

    Andersen, Poul Houman

    2005-01-01

    It is claimed that the remarkable growth in numbers of connected firms to the Internet marks a radical shift in current organisation of international business channels. For export intermediaries these new possibilities pose a threat to their current market position. However, virtual market presence...

  1. Reversible formation of high-valent-iron-oxo-porphyrin intermediate in heme-based catalysis: revisiting the kinetic model for horseradish peroxidase.

    NARCIS (Netherlands)

    Haandel, van M.J.H.; Primus, J.L.; Teunis, C.; Boersma, M.G.; Osman, A.M.; Veeger, C.; Rietjens, I.M.C.M.

    1998-01-01

    Many heme-containing biocatalysts exert their catalytic action through the initial formation of so-called high-valent-iron-oxo porphyrin intermediates. For horseradish peroxidase the initial intermediate formed has been identified as a high-valent-iron-oxo porphyrin π-radical cation, called compound

  2. Conversion of alkyl radicals to allyl radicals in irradiated single crystal mats of polyethylene

    International Nuclear Information System (INIS)

    Fujimura, T.; Hayakawa, N.; Kuriyama, I.

    1978-01-01

    The decay of alkyl radicals, the conversion of alkyl radicals to allyl radicals and the trapping of allyl radicals in irradiated single crystal mats of polyethylene have been studied by electron spin resonance (e.s.r.). It has been suggested that in the crystal core alkyl radicals react with trans-vinylene double bonds and are converted into trans-vinylene allyl radicals; at the crystal surface, alkyl radicals react with vinyl end groups and are converted into allyl radicals with vinyl end groups. The decay of radical pairs and the formation of trans-vinylene double bonds are discussed. (author)

  3. 17.9.3 Radical cations of diazo compounds

    Science.gov (United States)

    Davies, A. G.

    This document is part of Subvolume E2 `Phosphorus-Centered Radicals, Radicals Centered on Other Heteroatoms, Organic Radical Ions' of Volume 26 `Magnetic Properties of Free Radicals' of Landolt-Börnstein Group II `Molecules and Radicals'.

  4. Space Station Freedom combustion research

    Science.gov (United States)

    Faeth, G. M.

    1992-01-01

    Extended operations in microgravity, on board spacecraft like Space Station Freedom, provide both unusual opportunities and unusual challenges for combustion science. On the one hand, eliminating the intrusion of buoyancy provides a valuable new perspective for fundamental studies of combustion phenomena. On the other hand, however, the absence of buoyancy creates new hazards of fires and explosions that must be understood to assure safe manned space activities. These considerations - and the relevance of combustion science to problems of pollutants, energy utilization, waste incineration, power and propulsion systems, and fire and explosion hazards, among others - provide strong motivation for microgravity combustion research. The intrusion of buoyancy is a greater impediment to fundamental combustion studies than to most other areas of science. Combustion intrinsically heats gases with the resulting buoyant motion at normal gravity either preventing or vastly complicating measurements. Perversely, this limitation is most evident for fundamental laboratory experiments; few practical combustion phenomena are significantly affected by buoyancy. Thus, we have never observed the most fundamental combustion phenomena - laminar premixed and diffusion flames, heterogeneous flames of particles and surfaces, low-speed turbulent flames, etc. - without substantial buoyant disturbances. This precludes rational merging of theory, where buoyancy is of little interest, and experiments, that always are contaminated by buoyancy, which is the traditional path for developing most areas of science. The current microgravity combustion program seeks to rectify this deficiency using both ground-based and space-based facilities, with experiments involving space-based facilities including: laminar premixed flames, soot processes in laminar jet diffusion flames, structure of laminar and turbulent jet diffusion flames, solid surface combustion, one-dimensional smoldering, ignition and flame

  5. Iodine-catalyzed diazo activation to access radical reactivity.

    Science.gov (United States)

    Li, Pan; Zhao, Jingjing; Shi, Lijun; Wang, Jin; Shi, Xiaodong; Li, Fuwei

    2018-05-17

    Transition-metal-catalyzed diazo activation is a classical way to generate metal carbene, which are valuable intermediates in synthetic organic chemistry. An alternative iodine-catalyzed diazo activation is disclosed herein under either photo-initiated or thermal-initiated conditions, which represents an approach to enable carbene radical reactivity. This metal-free diazo activation strategy were successfully applied into olefin cyclopropanation and epoxidation, and applying this method to pyrrole synthesis under thermal-initiated conditions further demonstrates the unique reactivity using this method over typical metal-catalyzed conditions.

  6. Free radical generation induced by ultrasound in red wine and model wine: An EPR spin-trapping study.

    Science.gov (United States)

    Zhang, Qing-An; Shen, Yuan; Fan, Xue-Hui; Martín, Juan Francisco García; Wang, Xi; Song, Yun

    2015-11-01

    Direct evidence for the formation of 1-hydroxylethyl radicals by ultrasound in red wine and air-saturated model wine is presented in this paper. Free radicals are thought to be the key intermediates in the ultrasound processing of wine, but their nature has not been established yet. Electron paramagnetic resonance (EPR) spin trapping with 5,5-dimethyl-l-pyrrolin N-oxide (DMPO) was used for the detection of hydroxyl free radicals and 1-hydroxylethyl free radicals. Spin adducts of hydroxyl free radicals were detected in DMPO aqueous solution after sonication while 1-hydroxylethyl free radical adducts were observed in ultrasound-processed red wine and model wine. The latter radical arose from ethanol oxidation via the hydroxyl radical generated by ultrasound in water, thus providing the first direct evidence of the formation of 1-hydroxylethyl free radical in red wine exposed to ultrasound. Finally, the effects of ultrasound frequency, ultrasound power, temperature and ultrasound exposure time were assessed on the intensity of 1-hydroxylethyl radical spin adducts in model wine. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Reactions of stabilized Criegee Intermediates

    Science.gov (United States)

    Vereecken, Luc; Harder, Hartwig; Novelli, Anna

    2014-05-01

    Carbonyl oxides (Criegee intermediates) were proposed as key intermediates in the gas phase ozonolysis of alkenes in 1975 by Rudolf Criegee. Despite the importance of ozonolysis in atmospheric chemistry, direct observation of these intermediates remained elusive, with only indirect experimental evidence for their role in the oxidation of hydrocarbons, e.g. through scavenging experiments. Direct experimental observation of stabilized CI has only been achieved since 2008. Since then, a concerted effort using experimental and theoretical means is in motion to characterize the chemistry and kinetics of these reactive intermediates. We present the results of theoretical investigations of the chemistry of Criegee intermediates with a series of coreactants which may be of importance in the atmosphere, in experimental setups, or both. This includes the CI+CI cross-reaction, which proceeds with a rate coefficient near the collision limit and can be important in experimental conditions. The CI + alkene reactions show strong dependence of the rate coefficient depending on the coreactants, but is generally found to be rather slow. The CI + ozone reaction is sufficiently fast to occur both in experiment and the free troposphere, and acts as a sink for CI. The reaction of CI with hydroperoxides, ROOH, is complex, and leads both to the formation of oligomers, as to the formation of reactive etheroxides, with a moderately fast rate coefficient. The importance of these reactions is placed in the context of the reaction conditions in different atmospheric environments ranging from unpolluted to highly polluted.

  8. Addressing Emerging Risks: Scientific and Regulatory Challenges Associated with Environmentally Persistent Free Radicals.

    Science.gov (United States)

    Dugas, Tammy R; Lomnicki, Slawomir; Cormier, Stephania A; Dellinger, Barry; Reams, Margaret

    2016-06-08

    Airborne fine and ultrafine particulate matter (PM) are often generated through widely-used thermal processes such as the combustion of fuels or the thermal decomposition of waste. Residents near Superfund sites are exposed to PM through the inhalation of windblown dust, ingestion of soil and sediments, and inhalation of emissions from the on-site thermal treatment of contaminated soils. Epidemiological evidence supports a link between exposure to airborne PM and an increased risk of cardiovascular and pulmonary diseases. It is well-known that during combustion processes, incomplete combustion can lead to the production of organic pollutants that can adsorb to the surface of PM. Recent studies have demonstrated that their interaction with metal centers can lead to the generation of a surface stabilized metal-radical complex capable of redox cycling to produce ROS. Moreover, these free radicals can persist in the environment, hence their designation as Environmentally Persistent Free Radicals (EPFR). EPFR has been demonstrated in both ambient air PM2.5 (diameter challenges associated with regulating this new, emerging contaminant.

  9. Fundamental limitations of non-thermal plasma processing for internal combustion engine NOx control

    International Nuclear Information System (INIS)

    Penetrante, B.M.

    1993-01-01

    This paper discusses the physics and chemistry of non-thermal plasma processing for post-combustion NO x control in internal combustion engines. A comparison of electron beam and electrical discharge processing is made regarding their power consumption, radical production, NO x removal mechanisms, and by product formation. Can non-thermal deNO x operate efficiently without additives or catalysts? How much electrical power does it cost to operate? What are the by-products of the process? This paper addresses these fundamental issues based on an analysis of the electron-molecule processes and chemical kinetics

  10. High resolution spectroscopy of jet cooled phenyl radical: The ν{sub 1} and ν{sub 2} a{sub 1} symmetry C–H stretching modes

    Energy Technology Data Exchange (ETDEWEB)

    Chang, Chih-Hsuan; Nesbitt, David J. [JILA, National Institute of Standards and Technology, University of Colorado, Boulder, Colorado 80309, USA and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309 (United States)

    2016-07-28

    A series of CH stretch modes in phenyl radical (C{sub 6}H{sub 5}) has been investigated via high resolution infrared spectroscopy at sub-Doppler resolution (∼60 MHz) in a supersonic discharge slit jet expansion. Two fundamental vibrations of a{sub 1} symmetry, ν{sub 1} and ν{sub 2}, are observed and rotationally analyzed for the first time, corresponding to in-phase and out-of-phase symmetric CH stretch excitation at the ortho/meta/para and ortho/para C atoms with respect to the radical center. The ν{sub 1} and ν{sub 2} band origins are determined to be 3073.968 50(8) cm{sup −1} and 3062.264 80(7) cm{sup −1}, respectively, which both agree within 5 cm{sup −1} with theoretical anharmonic scaling predictions based on density functional B3LYP/6-311g++(3df,3dp) calculations. Integrated band strengths for each of the CH stretch bands are analyzed, with the relative intensities agreeing remarkably well with theoretical predictions. Frequency comparison with previous low resolution Ar-matrix spectroscopy [A. V. Friderichsen et al., J. Am. Chem. Soc. 123, 1977 (2001)] reveals a nearly uniform Δν ≈ + 10-12 cm{sup −1} blue shift between gas phase and Ar matrix values for ν{sub 1} and ν{sub 2}. This differs substantially from the much smaller red shift (Δν ≈ − 1 cm{sup −1}) reported for the ν{sub 19} mode, and suggests a simple physical model in terms of vibrational mode symmetry and crowding due to the matrix environment. Finally, the infrared phenyl spectra are well described by a simple asymmetric rigid rotor Hamiltonian and show no evidence for spectral congestion due to intramolecular vibrational coupling, which bodes well for high resolution studies of other ring radicals and polycyclic aromatic hydrocarbons. In summary, the combination of slit jet discharge methods with high resolution infrared lasers enables spectroscopic investigation of even highly reactive combustion and interstellar radical intermediates under gas phase, jet

  11. Radical-Mediated Enzymatic Polymerizations

    Science.gov (United States)

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  12. Catalytic Combustion of Gasified Waste

    Energy Technology Data Exchange (ETDEWEB)

    Kusar, Henrik

    2003-09-01

    This thesis concerns catalytic combustion for gas turbine application using a low heating-value (LHV) gas, derived from gasified waste. The main research in catalytic combustion focuses on methane as fuel, but an increasing interest is directed towards catalytic combustion of LHV fuels. This thesis shows that it is possible to catalytically combust a LHV gas and to oxidize fuel-bound nitrogen (NH{sub 3}) directly into N{sub 2} without forming NO{sub x} The first part of the thesis gives a background to the system. It defines waste, shortly describes gasification and more thoroughly catalytic combustion. The second part of the present thesis, paper I, concerns the development and testing of potential catalysts for catalytic combustion of LHV gases. The objective of this work was to investigate the possibility to use a stable metal oxide instead of noble metals as ignition catalyst and at the same time reduce the formation of NO{sub x} In paper II pilot-scale tests were carried out to prove the potential of catalytic combustion using real gasified waste and to compare with the results obtained in laboratory scale using a synthetic gas simulating gasified waste. In paper III, selective catalytic oxidation for decreasing the NO{sub x} formation from fuel-bound nitrogen was examined using two different approaches: fuel-lean and fuel-rich conditions. Finally, the last part of the thesis deals with deactivation of catalysts. The various deactivation processes which may affect high-temperature catalytic combustion are reviewed in paper IV. In paper V the poisoning effect of low amounts of sulfur was studied; various metal oxides as well as supported palladium and platinum catalysts were used as catalysts for combustion of a synthetic gas. In conclusion, with the results obtained in this thesis it would be possible to compose a working catalytic system for gas turbine application using a LHV gas.

  13. Producer for vegetal combustibles for internal-combustion motors

    Energy Technology Data Exchange (ETDEWEB)

    1943-12-28

    A producer is described for internal-combustion motors fed with wood or agricultural byproducts characterized by the fact that its full operation is independent of the degree of wetness of the material used.

  14. Reducing emissions from diesel combustion

    International Nuclear Information System (INIS)

    Anon.

    1992-01-01

    This paper contains information dealing with engine design to reduce emissions and improve or maintain fuel economy. Topics include: Observation of High Pressure Fuel Spray with Laser Light Sheet Method; Determination of Engine Cylinder Pressures from Crankshaft Speed Fluctuations; Combustion Similarity for Different Size Diesel Engines: Theoretical Prediction and Experimental Results; Prediction of Diesel Engine Particulate Emission During Transient Cycles; Characteristics and Combustibility of Particulate Matter; Dual-Fuel Diesel Engine Using Butane; Measurement of Flame Temperature Distribution in D.I. Diesel Engine with High Pressure Fuel Injection: and Combustion in a Small DI Diesel Engine at Starting

  15. Search for intermediate vector bosons

    International Nuclear Information System (INIS)

    Cline, D.B.; Rubbia, C.; van der Meer, S.

    1982-01-01

    Over the past 15 years a new class of unified theories has been developed to describe the forces acting between elementary particles. The most successful of the new theories establishes a link between electromagnetism and the weak force. A crucial prediction of this unified electroweak theory is the existence of three massive particles called intermediate vector bosons. If these intermediate vector bosons exist and if they have properties attributed to them by electroweak theory, they should soon be detected, as the world's first particle accelerator with enough energy to create such particles has recently been completed at the European Organization for Nuclear Research (CERN) in Geneva. The accelerator has been converted to a colliding beam machine in which protons and antiprotons collide head on. According to electroweak theory, intermediate vector bosons can be created in proton-antiproton collisions. (SC)

  16. Search for intermediate vector bosons

    International Nuclear Information System (INIS)

    Klajn, D.B.; Rubbia, K.; Meer, S.

    1983-01-01

    Problem of registration and search for intermediate vector bosons is discussed. According to weak-current theory there are three intermediate vector bosons with +1(W + )-1(W - ) and zero (Z 0 ) electric charges. It was suggested to conduct the investigation into particles in 1976 by cline, Rubbia and Makintair using proton-antiproton beams. Major difficulties of the experiment are related to the necessity of formation of sufficient amount of antiparticles and the method of antiproton beam ''cooling'' for the purpose of reduction of its random movements. The stochastic method was suggested by van der Meer in 1968 as one of possible cooling methods. Several large detectors were designed for searching intermediate vector bosons

  17. Gravity with Intermediate Goods Trade

    Directory of Open Access Journals (Sweden)

    Sujin Jang

    2017-12-01

    Full Text Available This paper derives the gravity equation with intermediate goods trade. We extend a standard monopolistic competition model to incorporate intermediate goods trade, and show that the gravity equation with intermediates trade is identical to the one without it except in that gross output should be used as the output measure instead of value added. We also show that the output elasticity of trade is significantly underestimated when value added is used as the output measure. This implies that with the conventional gravity equation, the contribution of output growth can be substantially underestimated and the role of trade costs reduction can be exaggerated in explaining trade expansion, as we demonstrate for the case of Korea's trade growth between 1995 and 2007.

  18. Donor free radical explosive composition

    Science.gov (United States)

    Walker, Franklin E. [15 Way Points Rd., Danville, CA 94526; Wasley, Richard J. [4290 Colgate Way, Livermore, CA 94550

    1980-04-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising an organic compound or mixture of organic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and which is not an explosive, or an inorganic compound or mixture of inorganic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and selected from ammonium or alkali metal persulfates.

  19. Radical feminists & trans activists truce

    OpenAIRE

    Mackay, F.

    2014-01-01

    #GenderWeek: Truce! When radical feminists and trans feminists empathise\\ud Feminist Times\\ud By Finn Mackay \\ud read all #GenderWeek articles.\\ud We wanted to explore the ground between the polarised, entrenched positions in the so-called “TERF-war”. Radical feminists on one pole, trans-inclusionary feminists and trans activists on the other. The disputed territory being women-only space, language and the ever changing legal framework surrounding gender.\\ud Entrenchment leads to stalemate. S...

  20. Plasma-assisted ignition and combustion: nanosecond discharges and development of kinetic mechanisms

    Science.gov (United States)

    Starikovskaia, S. M.

    2014-09-01

    This review covers the results obtained in the period 2006-2014 in the field of plasma-assisted combustion, and in particular the results on ignition and combustion triggered or sustained by pulsed nanosecond discharges in different geometries. Some benefits of pulsed high voltage discharges for kinetic study and for applications are demonstrated. The necessity of and the possibility of building a particular kinetic mechanism of plasma-assisted ignition and combustion are discussed. The most sensitive regions of parameters for plasma-combustion kinetic mechanisms are selected. A map of the pressure and temperature parameters (P-T diagram) is suggested, to unify the available data on ignition delay times, ignition lengths and densities of intermediate species reported by different authors.

  1. Free radical reactions of hematoporphyrin: a pulse radiolysis study

    International Nuclear Information System (INIS)

    Ahmed, Mohammed; Guleria, Apurav; Singh, Ajay K.; Sarkar, S.K.

    2011-01-01

    Radiation chemistry of porphyrin derivatives has been given much attention in recent years. Although till date photo dynamic therapy (PDT) with Hematoporphyrin (HP) has already proved its effectiveness in the treatment of cancer, the molecular mechanisms by which this therapy-destroys tumour cells as well as its optimal physical parameters are still not fully understood. Thus it becomes necessary to understand the interaction of different free radicals with HP. Pulse radiolysis studies have been performed to understand the interaction of different free radicals with HP. The product formation along with bleaching and presence of a number of transients makes it difficult to pin point the mode and site of free radical attack. The radiation-induced formation of various transients (HP-OH, HO - , HP + ) in aqueous solution was investigated at various pHs by pulse radiolysis technique by means of N 3 , O - and CCl 3 O 2 radicals with and without triethyl-amine, under different dose conditions. The observed intermediates are characterized by their kinetic and spectroscopic data. The absorption spectrum of each transient could be differentiated from each other by their absorption maxima, extinction coefficients and kinetics. A clear indication of product formation has also been observed by employing continuous electron pulse and the solution shows a green coloration. It is conceivable that under certain conditions, similar transients may be produced when HP is used as a sensitizer in radiation chemotherapy of cancer patients. Our study may throw some light into the breakdown mechanism of haemoglobin to BV in addition to the understanding of free radical interaction of HP. (author)

  2. Computational Modeling of Turbulent Spray Combustion

    NARCIS (Netherlands)

    Ma, L.

    2016-01-01

    The objective of the research presented in this thesis is development and validation of predictive models or modeling approaches of liquid fuel combustion (spray combustion) in hot-diluted environments, known as flameless combustion or MILD combustion. The goal is to combine good physical insight,

  3. Measures for a quality combustion (combustion chamber exit and downstream); Mesures pour une combustion de qualite (sortie de chambre de combustion et en aval)

    Energy Technology Data Exchange (ETDEWEB)

    Epinat, G. [APAVE Lyonnaise, 69 (France)

    1996-12-31

    After a review of the different pollutants related to the various types of stationary and mobile combustion processes (stoichiometric, reducing and oxidizing combustion), measures and analyses than may be used to ensure the quality and efficiency of combustion processes are reviewed: opacimeters, UV analyzers, etc. The regulation and control equipment for combustion systems are then listed, according to the generator capacity level

  4. Fuels and Combustion | Transportation Research | NREL

    Science.gov (United States)

    Fuels and Combustion Fuels and Combustion This is the March 2015 issue of the Transportation and , combustion strategy, and engine design hold the potential to maximize vehicle energy efficiency and performance of low-carbon fuels in internal combustion engines with a whole-systems approach to fuel chemistry

  5. Radically Different Kinetics at Low Temperatures

    Science.gov (United States)

    Sims, Ian

    2014-06-01

    The use of the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, or Reaction Kinetics in Uniform Supersonic Flow) technique coupled with pulsed laser photochemical kinetics methods has shown that reactions involving radicals can be very rapid at temperatures down to 10 K or below. The results have had a major impact in astrochemistry and planetology, as well as proving an exacting test for theory. The technique has also been applied to the formation of transient complexes of interest both in atmospheric chemistry and combustion. Until now, all of the chemical reactions studied in this way have taken place on attractive potential energy surfaces with no overall barrier to reaction. The F + H2 {→} HF + H reaction does possess a substantial energetic barrier ({\\cong} 800 K), and might therefore be expected to slow to a negligible rate at very low temperatures. In fact, this H-atom abstraction reaction does take place efficiently at low temperatures due entirely to tunneling. I will report direct experimental measurements of the rate of this reaction down to a temperature of 11 K, in remarkable agreement with state-of-the-art quantum reactive scattering calculations by François Lique (Université du Havre) and Millard Alexander (University of Maryland). It is thought that long chain cyanopolyyne molecules H(C2)nCN may play an important role in the formation of the orange haze layer in Titan's atmosphere. The longest carbon chain molecule observed in interstellar space, HC11N, is also a member of this series. I will present new results, obtained in collaboration with Jean-Claude Guillemin (Ecole de Chimie de Rennes) and Stephen Klippenstein (Argonne National Labs), on reactions of C2H, CN and C3N radicals (using a new LIF scheme by Hoshina and Endo which contribute to the low temperature formation of (cyano)polyynes. H. Sabbah, L. Biennier, I. R. Sims, Y. Georgievskii, S. J. Klippenstein, I. W. M. Smith, Science 317, 102 (2007). S. D. Le Picard, M

  6. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part I: Furan.

    Science.gov (United States)

    Liu, Dong; Togbé, Casimir; Tran, Luc-Sy; Felsmann, Daniel; Oßwald, Patrick; Nau, Patrick; Koppmann, Julia; Lackner, Alexander; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2014-03-01

    Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has - to the best of our knowledge - not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (φ=1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combustion and Flame 158 (2011) 756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the

  7. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part I: Furan

    Science.gov (United States)

    Liu, Dong; Togbé, Casimir; Tran, Luc-Sy; Felsmann, Daniel; Oßwald, Patrick; Nau, Patrick; Koppmann, Julia; Lackner, Alexander; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2013-01-01

    Fuels of the furan family, i.e. furan itself, 2-methylfuran (MF), and 2,5-dimethylfuran (DMF) are being proposed as alternatives to hydrocarbon fuels and are potentially accessible from cellulosic biomass. While some experiments and modeling results are becoming available for each of these fuels, a comprehensive experimental and modeling analysis of the three fuels under the same conditions, simulated using the same chemical reaction model, has – to the best of our knowledge – not been attempted before. The present series of three papers, detailing the results obtained in flat flames for each of the three fuels separately, reports experimental data and explores their combustion chemistry using kinetic modeling. The first part of this series focuses on the chemistry of low-pressure furan flames. Two laminar premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of furan were studied at two equivalence ratios (φ=1.0 and 1.7) using an analytical combination of high-resolution electron-ionization molecular-beam mass spectrometry (EI-MBMS) in Bielefeld and gas chromatography (GC) in Nancy. The time-of-flight MBMS with its high mass resolution enables the detection of both stable and reactive species, while the gas chromatograph permits the separation of isomers. Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. A single kinetic model was used to predict the flame structure of the three fuels: furan (in this paper), 2-methylfuran (in Part II), and 2,5-dimethylfuran (in Part III). A refined sub-mechanism for furan combustion, based on the work of Tian et al. [Combustion and Flame 158 (2011) 756-773] was developed which was then compared to the present experimental results. Overall, the agreement is encouraging. The main reaction pathways involved in furan combustion were delineated computing the rates of formation and consumption of all species. It is seen that the

  8. Excitation energies, photoionization cross sections, and asymmetry parameters of the methyl and silyl radicals.

    Science.gov (United States)

    Velasco, A M; Lavín, C; Dolgounitcheva, O; Ortiz, J V

    2014-08-21

    Vertical excitation energies of the methyl and silyl radicals were inferred from ab initio electron propagator calculations on the electron affinities of CH3(+) and SiH3(+). Photoionization cross sections and angular distribution of photoelectrons for the outermost orbitals of both CH3 and SiH3 radicals have been obtained with the Molecular Quantum Defect Orbital method. The individual ionization cross sections corresponding to the Rydberg channels to which the excitation of the ground state's outermost electron gives rise are reported. Despite the relevance of methyl radical in atmospheric chemistry and combustion processes, only data for the photon energy range of 10-11 eV seem to be available. Good agreement has been found with experiment for photoionization cross section of this radical. To our knowledge, predictions of the above mentioned photoionization parameters on silyl radical are made here for the first time, and we are not aware of any reported experimental measurements. An analysis of our results reveals the presence of a Cooper minimum in the photoionization of the silyl radical. The adequacy of the two theoretical procedures employed in the present work is discussed.

  9. Properties of the radicals formed by one-electron oxidation of acetaminophen - a pulse radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Bisby, R H; Tabassum, N

    1988-07-15

    The semi-iminoquinone radical of acetaminophen, which has previously been proposed as a possible hepatotoxic intermediate in the cytochrome P-450 catalysed oxidation of acetaminophen, has been generated and studied by pulse radiolysis. In the absence of other reactive solutes, the radical decays rapidly by second order kinetics with a rate constant (2k/sub 2/) of (2.2 +- 0.4) x 10/sup 9/ M/sup -1/ sec/sup -1/. In alkaline solutions the radical deprotonates with a pK of 11.1 +- 0.1 to form a radical-anion. The acetaminophen radical-anion reacts with resorcinol at high pH values, leading to the formation of a transient equilibrium from which the one-electron reduction potential of the semi-iminoquinone radical of acetaminophen is estimated to be + 0.707 +- 0.01 V at pH 7. This value predicts that acetaminophen should be oxidised by thiyl radicals. This was confirmed by pulse radiolysis experiments for reaction of the cysteinyl radical, for which rate constants of 7 x 10/sup 6/ M/sup -1/ sec/sup -1/ at pH7 and 2.7 x 10/sup 8/ M/sup -1/ sec/sup -1/ at pH 11.3 were obtained. The reaction of O/sub 2/ with the acetaminophen semi-iminoquinone radical could not be detected by pulse radiolysis, and alternative mechanisms for superoxide radical formation are discussed.

  10. Sulfate radical-based degradation of polychlorinated biphenyls: Effects of chloride ion and reaction kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Guo-Dong [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Dionysiou, Dionysios D. [Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-0071 (United States); Wang, Yu [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China); Graduate School of the Chinese Academy of Sciences, Beijing 100049 (China); Al-Abed, Souhail R. [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States); Zhou, Dong-Mei, E-mail: dmzhou@issas.ac.cn [Key Laboratory of Soil Environment and Pollution Remediation, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008 (China)

    2012-08-15

    Highlights: Black-Right-Pointing-Pointer A kinetic model was used to predict the radical species and their distributions. Black-Right-Pointing-Pointer The generated radical species were identified by EPR. Black-Right-Pointing-Pointer The second-order rate constants of sulfate radical with PCBs were determined. - Abstract: Advanced oxidation processes (AOPs) based on sulfate radical (SO{sub 4}{center_dot}{sup -}) have been recently used for soil and groundwater remediation. The presence of chloride ion in natural or wastewater decreases the reactivity of sulfate radical system, but explanations for this behavior were inconsistent, and the mechanisms are poorly understood. Therefore, in this paper we investigated the effect of chloride ion on the degradation of 2,4,4 Prime -CB (PCB28) and biphenyl (BP) by persulfate, based on the produced SO{sub 4}{center_dot}{sup -}. The results showed that the presence of chloride ion greatly inhibited the transformation of PCB28 and BP. Transformation intermediates of BP were monitored, suggesting that the chloride ion can react with SO{sub 4}{center_dot}{sup -} to produce chlorine radical, which reacts with BP to generate chlorinated compounds. To better understand the underlying mechanisms of these processes, a kinetic model was developed for predicting the effect of chloride ion on the types of radical species and their distributions. The results showed that chloride ion could influence the selectivity of radical species and their distribution, and increase the concentration of the sum of radical species. In addition, the second-order rate constants of sulfate radical with PCBs were determined, and quantum-chemical descriptors were introduced to predict the rate constants of other PCBs based on our experimental data.

  11. Combustion modeling in waste tanks

    International Nuclear Information System (INIS)

    Mueller, C.; Unal, C.; Travis, J.R.; Forschungszentrum Karlsruhe

    1997-01-01

    This paper has two objectives. The first one is to repeat previous simulations of release and combustion of flammable gases in tank SY-101 at the Hanford reservation with the recently developed code GASFLOW-II. The GASFLOW-II results are compared with the results obtained with the HMS/TRAC code and show good agreement, especially for non-combustion cases. For combustion GASFLOW-II predicts a steeper pressure rise than HMS/TRAC. The second objective is to describe a so-called induction parameter model which was developed and implemented into GASFLOW-II and reassess previous calculations of Bureau of Mines experiments for hydrogen-air combustion. The pressure time history improves compared with the one-step model, and the time rate of pressure change is much closer to the experimental data

  12. Environmental sensing and combustion diagnostics

    International Nuclear Information System (INIS)

    Santoleri, J.J.

    1991-01-01

    This book contains proceedings of Environmental Sensing and Combustion Diagnostics. Topics covered include: Incineration Systems Applications, Permitting, And Monitoring Overview; Infrared Techniques Applied to Incineration Systems; Continuous Emission Monitors; Analyzers and Sensors for Process Control And Environmental Monitoring

  13. Sodium nitrate combustion limit tests

    International Nuclear Information System (INIS)

    Beitel, G.A.

    1976-04-01

    Sodium nitrate is a powerful solid oxidant. Energetically, it is capable of exothermically oxidizing almost any organic material. Rate-controlling variables such as temperature, concentration of oxidant, concentration of fuel, thermal conductivity, moisture content, size, and pressure severely limit the possibility of a self-supported exothermic reaction (combustion). The tests reported in this document were conducted on one-gram samples at atmospheric pressure. Below 380 0 C, NaNO 3 was stable and did not support combustion. At moisture concentrations above 22 wt percent, exothermic reactions did not propagate in even the most energetic and reactive compositions. Fresh resin and paraffin were too volatile to enable a NaNO 2 -supported combustion process to propagate. Concentrations of NaNO 3 above 95 wt percent or below 35 wt percent did not react with enough energy release to support combustion. The influence of sample size and confining pressure, both important factors, was not investigated in this study

  14. 75 FR 3881 - Combustible Dust

    Science.gov (United States)

    2010-01-25

    ..., rubber, drugs, dried blood, dyes, certain textiles, and metals (such as aluminum and magnesium..., furniture manufacturing, metal processing, fabricated metal products and machinery manufacturing, pesticide... standard that will comprehensively address the fire and explosion hazards of combustible dust. The Agency...

  15. Reaction between protein radicals and other biomolecules

    DEFF Research Database (Denmark)

    Østdal, H.; Davies, M.J.; Andersen, Henrik Jørgen

    2002-01-01

    The present study investigates the reactivity of bovine serum albumin (BSA) radicals towards different biomolecules (urate, linoleic acid, and a polypeptide, poly(Glu-Ala-Tyr)). The BSA radical was formed at room temperature through a direct protein-to-protein radical transfer from H(2)O(2....... Subsequent analysis showed a decrease in the concentration of urate upon reaction with the BSA radical, while the BSA radical in the presence of poly(Glu-Ala-Tyr) resulted in increased formation of the characteristic protein oxidation product, dityrosine. Reaction between the BSA radical and a linoleic acid...

  16. Modeling of microgravity combustion experiments

    Science.gov (United States)

    Buckmaster, John

    1995-01-01

    This program started in February 1991, and is designed to improve our understanding of basic combustion phenomena by the modeling of various configurations undergoing experimental study by others. Results through 1992 were reported in the second workshop. Work since that time has examined the following topics: Flame-balls; Intrinsic and acoustic instabilities in multiphase mixtures; Radiation effects in premixed combustion; Smouldering, both forward and reverse, as well as two dimensional smoulder.

  17. Quantifying emissions from spontaneous combustion

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2013-09-01

    Spontaneous combustion can be a significant problem in the coal industry, not only due to the obvious safety hazard and the potential loss of valuable assets, but also with respect to the release of gaseous pollutants, especially CO2, from uncontrolled coal fires. This report reviews methodologies for measuring emissions from spontaneous combustion and discusses methods for quantifying, estimating and accounting for the purpose of preparing emission inventories.

  18. Laparoscopically assisted vaginal radical trachelectomy

    International Nuclear Information System (INIS)

    Bielik, T.; Karovic, M.; Trska, R.

    2013-01-01

    Purpose: Radical trachelectomy is a fertility-sparing procedure with the aim to provide adequate oncological safety to patients with cervical cancer while preserving their fertility. The purpose of this study was to retrospectively evaluate, in a series of 3 patients, the feasibility, morbidity, and safety of laparoscopically assisted vaginal radical trachelectomy for early cervical cancer. Patients and Methods: Three non consecutive patients with FIGO stage IA1 and IB1 cervical cancer was evaluated in a period of years 2008 - 2011. The patients underwent a laparoscopic pelvic lymphadenectomy and radical parametrectomy class II procedure according to the Piver classification. The section of vaginal cuff, trachelectomy, permanent cerclage and isthmo-vaginal anastomosis ware realised by vaginal approach. Results: The median operative time, the median blood loss and the mean number of resected pelvic nodes was comparable with published data. Major intraoperative complications did not occur and no patient required a blood transfusion. The median follow-up time was 33 (38-59) months. One vaginal recurrence occurred in 7 months after primary surgery. The patient was underwent a radicalisation procedure and adjuvant oncologic therapy and now is free of disease. Conclusions: Laparoscopically assisted vaginal radical trachelectomy (LAVRT)may be an alternative in fertility-preserving surgery for early cervical cancer. The procedure offers patients potential benefits of minimally invasive surgery with adequate oncological safety, but it should be reserved for oncologic surgeons trained in advanced laparoscopic procedures. (author)

  19. Is Radical Innovation Management Misunderstood?

    DEFF Research Database (Denmark)

    Kristiansen, Jimmi Normann; Gertsen, Frank

    2015-01-01

    This paper poses a critical view on radical innovation (RI) management research and practice. The study investigates how expected RI performance influences firms’ under- standing of their RI capability. RI performance is often based on output measures such as market shares or fiscal return...

  20. Exploring the Theories of Radicalization

    Directory of Open Access Journals (Sweden)

    Maskaliūnaitė Asta

    2015-12-01

    Full Text Available After the London bombings in July 2005, the concern of terrorism scholars and policy makers has turned to “home-grown” terrorism and potential for political violence from within the states. “Radicalization” became a new buzz word. This article follows a number of reviews of the literature on radicalization and offers another angle for looking at this research. First, it discusses the term “radicalization” and suggests the use of the following definition of radicalization as a process by which a person adopts belief systems which justify the use of violence to effect social change and comes to actively support as well as employ violent means for political purposes. Next, it proposes to see the theories of radicalization focusing on the individual and the two dimensions of his/her motivation: whether that motivation is internal or external and whether it is due to personal choice or either internal (due to some psychological traits or external compulsion. Though not all theories fall neatly within these categories, they make it possible to make comparisons of contributions from a variety of different areas thus reflecting on the interdisciplinary nature of the study of terrorism in general and radicalization as a part of it.

  1. Ultrasound-induced radical polymerization

    NARCIS (Netherlands)

    Kuijpers, M.W.A.; Kemmere, M.F.; Keurentjes, J.T.F.

    2004-01-01

    Sonochemistry comprises all chemical effects that are induced by ultrasound. Most of these effects are caused by cavitations, ie, the collapse of microscopic bubbles in a liquid. The chemical effects of ultrasound include the formation of radicals and the enhancement of reaction rates at ambient

  2. Erectile function after radical prostatectomy

    DEFF Research Database (Denmark)

    Fode, Mikkel; Frey, Anders; Jakobsen, Henrik

    2016-01-01

    collected database and a cross-sectional, questionnaire-based study in patients following radical prostatectomy. Erectile function was assessed with the IIEF-5 and the question "Is your erectile function as good as before the surgery (yes/no)". Patients were included if they were sexually active before...

  3. Degradation of acetic acid with sulfate radical generated by persulfate ions photolysis.

    Science.gov (United States)

    Criquet, Justine; Leitner, Nathalie Karpel Vel

    2009-09-01

    The photolysis of S(2)O(8)(2-) was studied for the removal of acetic acid in aqueous solution and compared with the H(2)O(2)/UV system. The SO(4)(-) radicals generated from the UV irradiation of S(2)O(8)(2-) ions yield a greater mineralization of acetic acid than the ()OH radicals. Acetic acid is oxidized by SO(4)(-) radicals without significant formation of intermediate by-products. Increasing system pH results in the formation of ()OH radicals from SO(4)(-) radicals. Maximum acetic acid degradation occurred at pH 5. The results suggest that above this pH, competitive reactions with the carbon mineralized inhibit the reaction of the solute with SO(4)(-) and also ()OH radicals. Scavenging effects of two naturally occurring ions were tested; in contrast to HCO(3)(-) ions, the presence of Cl(-) ions enhances the efficiency of the S(2)O(8)(2-)/UV process towards the acetate removal. It is attributed to the formation of the Cl() radical and its great reactivity towards acetate.

  4. Larval helminths in intermediate hosts

    DEFF Research Database (Denmark)

    Fredensborg, Brian Lund; Poulin, R

    2005-01-01

    Density-dependent effects on parasite fitness have been documented from adult helminths in their definitive hosts. There have, however, been no studies on the cost of sharing an intermediate host with other parasites in terms of reduced adult parasite fecundity. Even if larval parasites suffer a ...

  5. Intermediate statistics in quantum maps

    Energy Technology Data Exchange (ETDEWEB)

    Giraud, Olivier [H H Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Marklof, Jens [School of Mathematics, University of Bristol, University Walk, Bristol BS8 1TW (United Kingdom); O' Keefe, Stephen [School of Mathematics, University of Bristol, University Walk, Bristol BS8 1TW (United Kingdom)

    2004-07-16

    We present a one-parameter family of quantum maps whose spectral statistics are of the same intermediate type as observed in polygonal quantum billiards. Our central result is the evaluation of the spectral two-point correlation form factor at small argument, which in turn yields the asymptotic level compressibility for macroscopic correlation lengths. (letter to the editor)

  6. Intermediality and the Child Performer

    Science.gov (United States)

    Budd, Natasha

    2016-01-01

    This report details examples of praxis in the creation and presentation of "Joy Fear and Poetry": an intermedial theatre performance in which children aged 7-12 years generated aesthetic gestures using a range of new media forms. The impetus for the work's development was a desire to make an intervention into habituated patterns of…

  7. Material Voices: Intermediality and Autism

    Science.gov (United States)

    Trimingham, Melissa; Shaughnessy, Nicola

    2016-01-01

    Autism continues to be regarded enigmatically; a community that is difficult to access due to perceived disruptions of interpersonal connectedness. Through detailed observations of two children participating in the Arts and Humanities Research Council funded project "Imagining Autism: Drama, Performance and Intermediality as Interventions for…

  8. Combustion means for solid fuels

    Energy Technology Data Exchange (ETDEWEB)

    Murase, D.

    1987-09-23

    A combustion device for solid fuel, suitable for coal, coke, charcoal, coal-dust briquettes etc., comprising:- a base stand with an opening therein, an imperforate heat resistant holding board locatable to close said opening; a combustion chamber standing on the base stand with the holding board forming the base of the combustion chamber; a wiper arm pivoted for horizontal wiping movement over the upper surface of the holding board; an inlet means at a lower edge of said chamber above the base stand, and/or in a surrounding wall of said chamber, whereby combustion air may enter as exhaust gases leave the combustion chamber; an exhaust pipe for the exhaust gases; generally tubular gas-flow heat-exchange ducting putting the combustion chamber and exhaust pipe into communication; and means capable of moving the holding board into and out of the opening for removal of ash or other residue. The invention can be used for a heating system in a house or in a greenhouse or for a boiler.

  9. Numerical simulation of pulverized coal combustion to reduce pollutants

    International Nuclear Information System (INIS)

    Mohammad Bagher Ayani; Behnam Rahmanian

    2010-01-01

    Full text: In this research, the numerical simulation of pollutant reduction and in a pulverized coal combustion at 2D combustion chamber have been studied. Finite volume method using structured grid arrangement was utilized for modeling the pulverized coal combustion. The pressure base algorithm and implicit solver has been employed to simulate non-premix combustion model. The air was diluted by some participative gaseous such as whose percentages varied from 0 % to 20 %. Participative gases and air were preheated by a high-temperature gas generator, and the preheated oxidizer temperature could achieve. The combustion simulation with the generalized finite rate chemistry model, referred to as the Magnussen model and the reacting flow with the mixture fraction PDF/ equilibrium chemistry model, referred to as the PDF model are studied. Quick scheme was adopted for the discretization of all convective terms of the advective transport equations. So, as a result of addition participative gases into oxidizer the rate of formation of pollutants as well as NO x suppressed. The addition only a few percent of halogen components can make some systems nonflammable. The effects of addition halogen components and non-reaction gaseous such as Helium and Argon are fuel dilution and its acts as catalysts in reducing the H atom concentration necessary for the chain branching reaction sequence. Moreover, they act like surface and they make the increment of surface ratio versus volume. Because of this, the number of radical conflicts and hence destruction them will be increase. Furthermore, the rate of formation of pollutants will be decreased if the halogen components and non-reaction gaseous injection will be increased. However, as a result of this research, in the case of injection in pulverized coal combustion the flame temperature is lower than Steam, Argon and Helium. So, the emission levels of carbon dioxide is significantly lower than other participative gases, but in this

  10. Classical model of intermediate statistics

    International Nuclear Information System (INIS)

    Kaniadakis, G.

    1994-01-01

    In this work we present a classical kinetic model of intermediate statistics. In the case of Brownian particles we show that the Fermi-Dirac (FD) and Bose-Einstein (BE) distributions can be obtained, just as the Maxwell-Boltzmann (MD) distribution, as steady states of a classical kinetic equation that intrinsically takes into account an exclusion-inclusion principle. In our model the intermediate statistics are obtained as steady states of a system of coupled nonlinear kinetic equations, where the coupling constants are the transmutational potentials η κκ' . We show that, besides the FD-BE intermediate statistics extensively studied from the quantum point of view, we can also study the MB-FD and MB-BE ones. Moreover, our model allows us to treat the three-state mixing FD-MB-BE intermediate statistics. For boson and fermion mixing in a D-dimensional space, we obtain a family of FD-BE intermediate statistics by varying the transmutational potential η BF . This family contains, as a particular case when η BF =0, the quantum statistics recently proposed by L. Wu, Z. Wu, and J. Sun [Phys. Lett. A 170, 280 (1992)]. When we consider the two-dimensional FD-BE statistics, we derive an analytic expression of the fraction of fermions. When the temperature T→∞, the system is composed by an equal number of bosons and fermions, regardless of the value of η BF . On the contrary, when T=0, η BF becomes important and, according to its value, the system can be completely bosonic or fermionic, or composed both by bosons and fermions

  11. Energy from Waste--clean, efficient, renewable: transitions in combustion efficiency and NOx control.

    Science.gov (United States)

    Waldner, M H; Halter, R; Sigg, A; Brosch, B; Gehrmann, H J; Keunecke, M

    2013-02-01

    Traditionally EfW (Energy from Waste) plants apply a reciprocating grate to combust waste fuel. An integrated steam generator recovers the heat of combustion and converts it to steam for use in a steam turbine/generator set. This is followed by an array of flue gas cleaning technologies to meet regulatory limitations. Modern combustion applies a two-step method using primary air to fuel the combustion process on the grate. This generates a complex mixture of pyrolysis gases, combustion gases and unused combustion air. The post-combustion step in the first pass of the boiler above the grate is intended to "clean up" this mixture by oxidizing unburned gases with secondary air. This paper describes modifications to the combustion process to minimize exhaust gas volumes and the generation of noxious gases and thus improving the overall thermal efficiency of the EfW plant. The resulting process can be coupled with an innovative SNCR (Selective Non-Catalytic Reduction) technology to form a clean and efficient solid waste combustion system. Measurements immediately above the grate show that gas compositions along the grate vary from 10% CO, 5% H(2) and 0% O(2) to essentially unused "pure" air, in good agreement with results from a mathematical model. Introducing these diverse gas compositions to the post combustion process will overwhelm its ability to process all these gas fractions in an optimal manner. Inserting an intermediate step aimed at homogenizing the mixture above the grate has shown to significantly improve the quality of combustion, allowing for optimized process parameters. These measures also resulted in reduced formation of NO(x) (nitrogenous oxides) due to a lower oxygen level at which the combustion process was run (2.6 vol% O(2,)(wet) instead of 6.0 vol% O(2,)(wet)). This reduction establishes optimal conditions for the DyNOR™ (Dynamic NO(x) Reduction) NO(x) reduction process. This innovative SNCR technology is adapted to situations typically

  12. Database of Small Molecule Thermochemistry for Combustion

    KAUST Repository

    Goldsmith, C. Franklin; Magoon, Gregory R.; Green, William H.

    2012-01-01

    High-accuracy ab initio thermochemistry is presented for 219 small molecules relevant in combustion chemistry, including many radical, biradical, and triplet species. These values are critical for accurate kinetic modeling. The RQCISD(T)/cc-PV∞QZ//B3LYP/6-311++G(d,p) method was used to compute the electronic energies. A bond additivity correction for this method has been developed to remove systematic errors in the enthalpy calculations, using the Active Thermochemical Tables as reference values. On the basis of comparison with the benchmark data, the 3σ uncertainty in the standard-state heat of formation is 0.9 kcal/mol, or within chemical accuracy. An uncertainty analysis is presented for the entropy and heat capacity. In many cases, the present values are the most accurate and comprehensive numbers available. The present work is compared to several published databases. In some cases, there are large discrepancies and errors in published databases; the present work helps to resolve these problems. © 2012 American Chemical Society.

  13. Database of Small Molecule Thermochemistry for Combustion

    KAUST Repository

    Goldsmith, C. Franklin

    2012-09-13

    High-accuracy ab initio thermochemistry is presented for 219 small molecules relevant in combustion chemistry, including many radical, biradical, and triplet species. These values are critical for accurate kinetic modeling. The RQCISD(T)/cc-PV∞QZ//B3LYP/6-311++G(d,p) method was used to compute the electronic energies. A bond additivity correction for this method has been developed to remove systematic errors in the enthalpy calculations, using the Active Thermochemical Tables as reference values. On the basis of comparison with the benchmark data, the 3σ uncertainty in the standard-state heat of formation is 0.9 kcal/mol, or within chemical accuracy. An uncertainty analysis is presented for the entropy and heat capacity. In many cases, the present values are the most accurate and comprehensive numbers available. The present work is compared to several published databases. In some cases, there are large discrepancies and errors in published databases; the present work helps to resolve these problems. © 2012 American Chemical Society.

  14. Effect of energetic electrons on combustion of premixed burner flame

    Science.gov (United States)

    Sasaki, Koichi

    2011-10-01

    In many studies of plasma-assisted combustion, authors superpose discharges onto flames to control combustion reactions. This work is motivated by more fundamental point of view. The standpoint of this work is that flames themselves are already plasmas. We irradiated microwave power onto premixed burner flame with the intention of heating electrons in it. The microwave power was limited below the threshold for a discharge. We obtained the enhancement of burning velocity by the irradiation of the microwave power, which was understood by the shortening of the flame length. At the same time, we observed the increases in the optical emission intensities of OH and CH radicals. Despite the increases in the optical emission intensities, the optical emission spectra of OH and CH were not affected by the microwave irradiation, indicating that the enhancement of the burning velocity was not attributed to the increase in the gas temperature. On the other hand, we observed significant increase in the optical emission intensity of the second positive system of molecular nitrogen, which is a clear evidence for electron heating in the premixed burner flame. Therefore, it is considered that the enhancement of the burning velocity is obtained by nonequilibrium combustion chemistry which is driven by energetic electrons. By irradiating pulsed microwave power, we examined the time constants for the increases and decreases in the optical emission intensities of N2, OH, CH, and continuum radiation.

  15. Techniques de combustion Combustin Techniques

    Directory of Open Access Journals (Sweden)

    Perthuis E.

    2006-11-01

    Full Text Available L'efficacité d'un processus de chauffage par flamme est étroitement liée à la maîtrise des techniques de combustion. Le brûleur, organe essentiel de l'équipement de chauffe, doit d'une part assurer une combustion complète pour utiliser au mieux l'énergie potentielle du combustible et, d'autre part, provoquer dans le foyer les conditions aérodynamiques les plus propices oux transferts de chaleur. En s'appuyant sur les études expérimentales effectuées à la Fondation de Recherches Internationales sur les Flammes (FRIF, au Groupe d'Étude des Flammes de Gaz Naturel (GEFGN et à l'Institut Français du Pétrole (IFP et sur des réalisations industrielles, on présente les propriétés essentielles des flammes de diffusion aux combustibles liquides et gazeux obtenues avec ou sans mise en rotation des fluides, et leurs répercussions sur les transferts thermiques. La recherche des températures de combustion élevées conduit à envisager la marche à excès d'air réduit, le réchauffage de l'air ou son enrichissement à l'oxygène. Par quelques exemples, on évoque l'influence de ces paramètres d'exploitation sur l'économie possible en combustible. The efficiency of a flame heating process is closely linked ta the mastery of, combustion techniques. The burner, an essential element in any heating equipment, must provide complete combustion sa as to make optimum use of the potential energy in the fuel while, at the same time, creating the most suitable conditions for heat transfers in the combustion chamber. On the basis of experimental research performed by FRIF, GEFGN and IFP and of industrial achievements, this article describesthe essential properties of diffusion flames fed by liquid and gaseous fuels and produced with or without fluid swirling, and the effects of such flames on heat transfers. The search for high combustion temperatures means that consideration must be given to operating with reduced excess air, heating the air or

  16. Radiation-induced free radical reactions in polymer/drug systems for controlled release: an EPR investigation

    Energy Technology Data Exchange (ETDEWEB)

    Faucitano, A. E-mail: chemrad@unipv.it; Buttafava, A.; Montanari, L.; Cilurzo, F.; Conti, B.; Genta, I.; Valvo, L

    2003-05-01

    The primary and secondary free radical intermediates in the gamma radiolysis of poly(D,L-lactide-co-glycolide) (PLGA) and clonazepam loaded PLGA microspheres were investigated by matrix EPR spectroscopy in the temperature range 77-298 K. Drug-polymer interactions were found to be important leading to significant deviations of the G(radicals) from the additivity law. In particular, in the mixed system a stabilization of the polymer matrix with respect to the radiation damage was detected, witnessed by a decrease of the overall polymer radicals yield which is accompanied by an increase of the drug radicals yield. These effects have been attributed to the scavenging properties of the nitro group with respect to electrons and polymer radicals. It is conceivable that such conclusions be of general application for all pharmaceutical formulations containing drugs bearing nitro groups in their chemical structure.

  17. Effect of air preheat temperature on the MILD combustion of syngas

    International Nuclear Information System (INIS)

    Huang, Mingming; Zhang, Zhedian; Shao, Weiwei; Xiong, Yan; Liu, Yan; Lei, Fulin; Xiao, Yunhan

    2014-01-01

    Highlights: • MILD combustion is achieved with reaction zone covering the entire combustion chamber. • Critical equivalence ratio for the occurrence of MILD combustion is identified. • MILD regime can be established for syngas fuel under air preheating conditions. - Abstract: The effect of air preheat temperature on MILD (Moderate or Intense Low-oxygen Dilution) combustion of coal-derived syngas was examined in parallel jet forward flow combustor. The results were presented on flow field using numerical simulations and on global flame signatures, OH ∗ radicals distribution and exhaust emissions using experiments. The discrete and high speed air/fuel injections into the combustor is necessary for the establishment of MILD conditions, because they cause strong gas recirculation and form large mixing region between the air and fuel jets. The critical equivalence ratio above which MILD combustion occurred was identified. The MILD regime was established for syngas fuel under air preheating conditions with lean operational limit and suppressed NO x and CO emissions. In the MILD combustion regime, the air preheating resulted in higher NO x but lower CO emissions, while the increase of equivalence ratio led to the increase of NO x and the decrease of CO emissions

  18. Flavonoids as scavengers of nitric oxide radical.

    NARCIS (Netherlands)

    van Acker, S.A.B.E.; Tromp, M.N.J.L.; Haenen, G.R.M.M.; van der Vijgh, W.J.F.; Bast, A.

    1995-01-01

    Flavonoids are a group of naturally occurring compounds used, e.g., in the treatment of vascular endothelial damage. They are known to be excellent scavengers of oxygen free radicals. Since the nitric oxide radical (

  19. Combustion Byproducts Recycling Consortium

    Energy Technology Data Exchange (ETDEWEB)

    Paul Ziemkiewicz; Tamara Vandivort; Debra Pflughoeft-Hassett; Y. Paul Chugh; James Hower

    2008-08-31

    The Combustion Byproducts Recycling Consortium (CBRC) program was developed as a focused program to remove and/or minimize the barriers for effective management of over 123 million tons of coal combustion byproducts (CCBs) annually generated in the USA. At the time of launching the CBRC in 1998, about 25% of CCBs were beneficially utilized while the remaining was disposed in on-site or off-site landfills. During the ten (10) year tenure of CBRC (1998-2008), after a critical review, 52 projects were funded nationwide. By region, the East, Midwest, and West had 21, 18, and 13 projects funded, respectively. Almost all projects were cooperative projects involving industry, government, and academia. The CBRC projects, to a large extent, successfully addressed the problems of large-scale utilization of CCBs. A few projects, such as the two Eastern Region projects that addressed the use of fly ash in foundry applications, might be thought of as a somewhat smaller application in comparison to construction and agricultural uses, but as a novel niche use, they set the stage to draw interest that fly ash substitution for Portland cement might not attract. With consideration of the large increase in flue gas desulfurization (FGD) gypsum in response to EPA regulations, agricultural uses of FGD gypsum hold promise for large-scale uses of a product currently directed to the (currently stagnant) home construction market. Outstanding achievements of the program are: (1) The CBRC successfully enhanced professional expertise in the area of CCBs throughout the nation. The enhanced capacity continues to provide technology and information transfer expertise to industry and regulatory agencies. (2) Several technologies were developed that can be used immediately. These include: (a) Use of CCBs for road base and sub-base applications; (b) full-depth, in situ stabilization of gravel roads or highway/pavement construction recycled materials; and (c) fired bricks containing up to 30%-40% F

  20. O conceito de mal radical The concept of radical evil

    Directory of Open Access Journals (Sweden)

    Adriano Correia

    2005-01-01

    Full Text Available A noção de mal radical aparece em Kant no contexto da discussão da religião nos limites da simples razão e busca dar conta da complexa relação entre o respeito pela lei moral e o amor-próprio na definição do móbil para a ação. Na busca por identificar o fundamento da propensão para o mal no homem, Kant se vê diante da dificuldade de ter de articular natureza e liberdade, e ainda que a noção de mal radical possa conservar algumas ambigüidades, permite conceber uma noção de responsabilidade compatível com uma inata propensão para o mal. Neste texto busco explicitar alguns passos fundamentais na construção do conceito por Kant.The concept of radical evil appears in Kant's theory when he discusses the religion in the limits of the mere reason and aims explain the complex relationship between respect for the moral law and the self-love, for establish the motive of the action. By aiming identify the basis of human inclination to evil, Kant is faced with the trouble of have to put nature and freedom in connection. Despite of the concept of radical evil retain some ambiguity, it allows conceive a notion of responsibility suitable to an inherent inclination to evil. In this paper is my purpose to explain some basic moments of Kantian formulation of that notion.

  1. Oxidation of free, peptide and protein tryptophan residues mediated by AAPH-derived free radicals: role of alkoxyl and peroxyl radicals

    DEFF Research Database (Denmark)

    Fuentes-Lemus, E.; Dorta, E.; Escobar, E.

    2016-01-01

    The oxidation of tryptophan (Trp) residues, mediated by peroxyl radicals (ROOc), follows a complex mechanism involving free radical intermediates, and short chain reactions. The reactivity of Trp towards ROOc should be strongly affected by its inclusion in peptides and proteins. To examine...... the latter, we investigated (by fluorescence) the kinetic of the consumption of free, peptide- and protein-Trp residues towards AAPH (2,20 -azobis(2-amidinopropane)dihydrochloride)-derived free radicals. Interestingly, the initial consumption rates (Ri ) were only slightly influenced by the inclusion of Trp...... concentrations (10–50 mM), the values of Ri were nearly constant; and at high Trp concentrations (50 mM to 1 mM), a slower increase of Ri than expected for chain reactions. Similar behavior was detected for all three systems (free Trp, and Trp in peptides and proteins). For the first time we are showing...

  2. HERCULES Advanced Combustion Concepts Test Facility: Spray/Combustion Chamber

    Energy Technology Data Exchange (ETDEWEB)

    Herrmann, K. [Eidgenoessische Technische Hochschule (ETH), Labor fuer Aerothermochemie und Verbrennungssysteme, Zuerich (Switzerland)

    2004-07-01

    This yearly report for 2004 on behalf of the Swiss Federal Office of Energy (SFOE) at the Laboratory for Aero-thermochemistry and Combustion Systems at the Federal Institute of Technology ETH in Zurich, Switzerland, presents a review of work being done within the framework of HERCULES (High Efficiency R and D on Combustion with Ultra Low Emissions for Ships) - the international R and D project concerning new technologies for ships' diesels. The work involves the use and augmentation of simulation models. These are to be validated using experimental data. The report deals with the development of an experimental set-up that will simulate combustion in large two-stroke diesel engines and allow the generation of reference data. The main element of the test apparatus is a spray / combustion chamber with extensive possibilities for optical observation under variable flow conditions. The results of first simulations confirm concepts and shall help in further work on the project. The potential offered by high-speed camera systems was tested using the institute's existing HTDZ combustion chamber. Further work to be done is reviewed.

  3. Jet plume injection and combustion system for internal combustion engines

    Science.gov (United States)

    Oppenheim, Antoni K.; Maxson, James A.; Hensinger, David M.

    1993-01-01

    An improved combustion system for an internal combustion engine is disclosed wherein a rich air/fuel mixture is furnished at high pressure to one or more jet plume generator cavities adjacent to a cylinder and then injected through one or more orifices from the cavities into the head space of the cylinder to form one or more turbulent jet plumes in the head space of the cylinder prior to ignition of the rich air/fuel mixture in the cavity of the jet plume generator. The portion of the rich air/fuel mixture remaining in the cavity of the generator is then ignited to provide a secondary jet, comprising incomplete combustion products which are injected into the cylinder to initiate combustion in the already formed turbulent jet plume. Formation of the turbulent jet plume in the head space of the cylinder prior to ignition has been found to yield a higher maximum combustion pressure in the cylinder, as well as shortening the time period to attain such a maximum pressure.

  4. Combustion Kinetic Studies of Gasolines and Surrogates

    KAUST Repository

    Javed, Tamour

    2016-11-01

    Future thrusts for gasoline engine development can be broadly summarized into two categories: (i) efficiency improvements in conventional spark ignition engines, and (ii) development of advance compression ignition (ACI) concepts. Efficiency improvements in conventional spark ignition engines requires downsizing (and turbocharging) which may be achieved by using high octane gasolines, whereas, low octane gasolines fuels are anticipated for ACI concepts. The current work provides the essential combustion kinetic data, targeting both thrusts, that is needed to develop high fidelity gasoline surrogate mechanisms and surrogate complexity guidelines. Ignition delay times of a wide range of certified gasolines and surrogates are reported here. These measurements were performed in shock tubes and rapid compression machines over a wide range of experimental conditions (650 – 1250 K, 10 – 40 bar) relevant to internal combustion engines. Using the measured the data and chemical kinetic analyses, the surrogate complexity requirements for these gasolines in homogeneous environments are specified. For the discussions presented here, gasolines are classified into three categories: (i)\\tLow octane gasolines including Saudi Aramco’s light naphtha fuel (anti-knock index, AKI = (RON + MON)/2 = 64; Sensitivity (S) = RON – MON = 1), certified FACE (Fuels for Advanced Combustion Engines) gasoline I and J (AKI ~ 70, S = 0.7 and 3 respectively), and their Primary Reference Fuels (PRF, mixtures of n-heptane and iso-octane) and multi-component surrogates. (ii)\\t Mid octane gasolines including FACE A and C (AKI ~ 84, S ~ 0 and 1 respectively) and their PRF surrogates. Laser absorption measurements of intermediate and product species formed during gasoline/surrogate oxidation are also reported. (iii)\\t A wide range of n-heptane/iso-octane/toluene (TPRF) blends to adequately represent the octane and sensitivity requirements of high octane gasolines including FACE gasoline F and G

  5. Muonium radicals in benzene-styrene mixtures

    International Nuclear Information System (INIS)

    Ng, B.W.; Stadlbauer, J.W.; Walker, D.C.

    1984-01-01

    Muonium radicals were observed through their μ + SR precession frequencies in high transverse magnetic fields in pure benzene, pure styrene and their mixtures, all as liquids at room temperature. In benzene-styrene mixtures, the radicals obtained in each pure liquid are both present, so no slow (10 -9 -10 -5 s) intermolecular exchange occurs; but strong selectivity was found with the formation of the radical from styrene being about eight-times more probable than the radical from benzene. (Auth.)

  6. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography - Part III: 2,5-Dimethylfuran.

    Science.gov (United States)

    Togbé, Casimir; Tran, Luc-Sy; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2014-03-01

    This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model.

  7. Combustion chemistry and flame structure of furan group biofuels using molecular-beam mass spectrometry and gas chromatography – Part III: 2,5-Dimethylfuran

    Science.gov (United States)

    Togbé, Casimir; Tran, Luc-Sy; Liu, Dong; Felsmann, Daniel; Oßwald, Patrick; Glaude, Pierre-Alexandre; Sirjean, Baptiste; Fournet, René; Battin-Leclerc, Frédérique; Kohse-Höinghaus, Katharina

    2013-01-01

    This work is the third part of a study focusing on the combustion chemistry and flame structure of furan and selected alkylated derivatives, i.e. furan in Part I, 2-methylfuran (MF) in Part II, and 2,5-dimethylfuran (DMF) in the present work. Two premixed low-pressure (20 and 40 mbar) flat argon-diluted (50%) flames of DMF were studied with electron-ionization molecular-beam mass spectrometry (EI-MBMS) and gas chromatography (GC) under two equivalence ratios (φ=1.0 and 1.7). Mole fractions of reactants, products, and stable and radical intermediates were measured as a function of the distance to the burner. Kinetic modeling was performed using a reaction mechanism that was further developed in the present series, including Part I and Part II. A reasonable agreement between the present experimental results and the simulation is observed. The main reaction pathways of DMF consumption were derived from a reaction flow analysis. Also, a comparison of the key features for the three flames is presented, as well as a comparison between these flames of furanic compounds and those of other fuels. An a priori surprising ability of DMF to form soot precursors (e.g. 1,3-cyclopentadiene or benzene) compared to less substituted furans and to other fuels has been experimentally observed and is well explained in the model. PMID:24518851

  8. Biochemical failure after radical external beam radiotherapy for prostate cancer

    International Nuclear Information System (INIS)

    Nomoto, Satoshi; Imada, Hajime; Kato, Fumio; Yahara, Katsuya; Morioka, Tomoaki; Ohguri, Takayuki; Nakano, Keita; Korogi, Yukunori

    2005-01-01

    The purpose of this study was to evaluate biochemical failures after radical external beam radiotherapy for prostate cancer. A total of 143 patients with prostate cancer (5 cases in stage A2, 95 in stage B and 43 in stage C; 18 in low risk group, 37 in intermediate risk group, 67 in high risk group and 21 in unknown group) were included in this study. Patients of stage A2 and B underwent external irradiation of 46 Gy to the prostate gland and seminal vesicle and additional 20 Gy to the prostate gland, while patients of stage C underwent external irradiation of 66 Gy to the prostate gland and seminal vesicle including 46 Gy to the pelvis. Neoadjuvant hormonal therapy was done in 66 cases, and long-term hormonal therapy in 75 cases; two cases were treated with radiation therapy alone. The 3-year relapse free survival rates by stage A2, B and C were 100%, 96.7% and 88.1%, respectively. The 3-year relapse free survival rates by low, intermediate and high risk groups were 100%, 92.3% and 89.7%, respectively. Biochemical failure was noted in nine cases during the average observation term of 32.2 months; in this group the median of prostate specific antigen (PSA) value was 2.6 ng/ml, the doubling time was 8.6 months, and the term of biochemical failure was 33.2 months. Six of eight cases with biochemical failure were the neoadjuvant hormonal therapy group, but biochemical no evidence of disease (bNED) curve showed no significant difference between neoadjuvant and long-term hormonal groups. It is supposed that unnecessary hormonal therapies were performed based on the nonspecific diagnosis of biochemical failure after radical radiotherapy in our group of patients. A precise criterion of biochemical failure after radical radiotherapy for prostate cancer is necessary. (author)

  9. Manganese-Catalyzed Cross-Coupling of Aryl Halides and Grignard Reagents by a Radical Mechanism

    DEFF Research Database (Denmark)

    Antonacci, Giuseppe; Ahlburg, Andreas; Fristrup, Peter

    2017-01-01

    The substrate scope and the mechanism have been investigated for the MnCl2-catalyzed cross-coupling reaction between aryl halides and Grignard reagents. The transformation proceeds rapidly and in good yield when the aryl halide component is an aryl chloride containing a cyano or an ester group....... Two radical-clock experiments were carried out, and in both cases an intermediate aryl radical was successfully trapped. The cross-coupling reaction is therefore believed to proceed by an SRN1 mechanism, with a triorganomanganate complex serving as the most likely nucleophile and single-electron donor...

  10. Free radicals in health and disease

    International Nuclear Information System (INIS)

    Gonet, B.

    1993-01-01

    Free radicals appear in the cells as the result of exogenic factors (ionizing radiation, UV) or reactions naturally occurring in the cell. Free radical reactions may cause destruction of macromolecules (DNA, lipids, proteins). Free radical pathology is important in many diseases and aging processes in organisms

  11. Oxygen free radicals in rheumatoid arthritis

    NARCIS (Netherlands)

    P. Biemond (Pieter)

    1986-01-01

    textabstractCurrent knowledge strongly suggests that oxygen free radicals are involved in the pathogenesis of RA. Additional information about the mechanism of free radical attack is necessary in order to find out if interaction with the mechanism of free radical damage can be used in the treatment

  12. Radical carbonylations using a continuous microflow system

    Directory of Open Access Journals (Sweden)

    Takahide Fukuyama

    2009-07-01

    Full Text Available Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and three-component coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.

  13. Twenty-fifth symposium (international) on combustion

    International Nuclear Information System (INIS)

    Anon.

    1994-01-01

    Approximately two-thirds of the papers presented at this conference are contained in this volume. The other one-third appear in special issues of ''Combustion and Flame'', Vol. 99, 1994 and Vol. 100, 1995. Papers are divided into the following sections: Supersonic combustion; Detonations and explosions; Internal combustion engines; Practical aspects of combustion; Incineration and wastes; Sprays and droplet combustion; Coal and organic solids combustion; Soot and polycyclic aromatic hydrocarbons; Reaction kinetics; NO x ; Turbulent flames; Turbulent combustion; Laminar flames; Flame spread, fire and halogenated fire suppressants; Global environmental effects; Ignition; Two-phase combustion; Solid propellant combustion; Materials synthesis; Microgravity; and Experimental diagnostics. Papers have been processed separately for inclusion on the data base

  14. chemical kinetic study of nitrogen oxides formation in methane flameless combustion

    International Nuclear Information System (INIS)

    Alvarado T, Pedro N; Cadavid S, Francisco; Mondragon, P Fanor; Ruiz, Wilson

    2009-01-01

    The present paper deals with the nitrogen oxides formation in a flameless combustion process characterized for using air highly diluted and preheated at high temperatures. The combustion model used in this study was the one dimensional counterflow methane air diffusion flame. The NOx production rate analysis showed that the thermal and prompt mechanisms are the most important for the formation and consumption of NO under dilution conditions for the oxidant in N 2 and combustion products. These mechanisms are related since the starting reaction for NO formation (N2 molecular dissociation) belongs to the prompt mechanism while the NO formation is reported mainly for the thermal mechanism reactions. On the other hand, the NO - NO 2 equilibrium showed that the reaction rates are comparable to that obtained by the thermal and prompt mechanisms, but its global contribution to NO formation are almost insignificant due to the oxidation reaction with radicals HO 2 .

  15. Correlated Default and Financial Intermediation

    OpenAIRE

    Gregory Phelan

    2015-01-01

    Financial intermediation naturally arises when knowledge about the aggregate state is valuable for managing investments and lenders cannot easily observe the aggregate state. I show this using a costly enforcement model in which lenders need ex-post incentives to enforce payments from defaulted loans and borrowers' payoffs are correlated. When projects have correlated outcomes, learning the state of one project (via enforcement) provides information about the states of other projects. A large...

  16. A muoniated radical in selenium

    International Nuclear Information System (INIS)

    Reid, I.D.; Cox, S.F.J.; Jayasooriya, U.A.; Zimmermann, U.

    2003-01-01

    We report new 0.3 T transverse-field μSR experiments in crystalline Se which show only a small, slowly relaxing muon signal at 300 K, accounting for about 30% of the incoming muon polarization. However, at 90 K signals are observed around 74 and 157 MHz, characteristic of a radical with a hyperfine coupling of 231 MHz. Very fast relaxation which increases with temperature makes these signals impossible to follow beyond 200 K. Above 400 K a quickly relaxing diamagnetic signal becomes visible, its relaxation falling with increasing temperature. In the melt (>490 K) just a single non-relaxing diamagnetic signal is seen. These observations may be explained by electron spin-exchange with a muoniated radical

  17. Low temperature spray combustion of acetone–butanol–ethanol (ABE) and diesel blends

    International Nuclear Information System (INIS)

    Zhou, Nan; Huo, Ming; Wu, Han; Nithyanandan, Karthik; Lee, Chia-fon F.; Wang, Qingnian

    2014-01-01

    Highlights: • Combustion characteristics of acetone–butanol–ethanol (ABE) and diesel blends. • Feasibility of ABE to be blended directly with diesel in engine. • Conventional and low temperature combustion in constant volume chamber. • ABE–diesel blends can suppress the soot formation and achieve better combustion. - Abstract: The combustion characteristics of acetone–butanol–ethanol (ABE) and diesel blends were studied in a constant volume chamber under both conventional diesel combustion and low temperature combustion (LTC) conditions. In this work, 20 vol.% ABE without water (ABE20) was mixed with diesel and the vol.% of acetone, butanol and ethanol were kept at 30%, 60% and 10% respectively. The advantageous combustion characteristics of ABE-diesel include higher oxygen content which promotes soot oxidation compared to pure diesel; longer ignition delay and soot lift-off length allowing more air entrainment upstream of the spray jet thus providing better air–fuel mixing. Based on the analysis, it is found that at low ambient temperature of 800 K and ambient oxygen of 11%, ABE20 presented close-to-zero soot luminosity with better combustion efficiency compared to D100 suggesting that ABE, an intermediate product during ABE fermentation, is a very promising alternative fuel to be directly used in diesel engines especially under LTC conditions. Meanwhile, ABE–diesel blends contain multiple components possessing drastically different volatilities, which greatly favor the occurrence of micro-explosion. This feature may result in better atomization and air–fuel mixing enhancement, which all contribute to the better combustion performance of ABE20 at LTC conditions

  18. DNA Binding Hydroxyl Radical Probes

    OpenAIRE

    Tang, Vicky J; Konigsfeld, Katie M; Aguilera, Joe A; Milligan, Jamie R

    2012-01-01

    The hydroxyl radical is the primary mediator of DNA damage by the indirect effect of ionizing radiation. It is a powerful oxidizing agent produced by the radiolysis of water and is responsible for a significant fraction of the DNA damage associated with ionizing radiation. There is therefore an interest in the development of sensitive assays for its detection. The hydroxylation of aromatic groups to produce fluorescent products has been used for this purpose. We have examined four different c...

  19. Anatomical landmarks of radical prostatecomy.

    Science.gov (United States)

    Stolzenburg, Jens-Uwe; Schwalenberg, Thilo; Horn, Lars-Christian; Neuhaus, Jochen; Constantinides, Costantinos; Liatsikos, Evangelos N

    2007-03-01

    In the present study, we review current literature and based on our experience, we present the anatomical landmarks of open and laparoscopic/endoscopic radical prostatectomy. A thorough literature search was performed with the Medline database on the anatomy and the nomenclature of the structures surrounding the prostate gland. The correct handling of puboprostatic ligaments, external urethral sphincter, prostatic fascias and neurovascular bundle is necessary for avoiding malfunction of the urogenital system after radical prostatectomy. When evaluating new prostatectomy techniques, we should always take into account both clinical and final oncological outcomes. The present review adds further knowledge to the existing "postprostatectomy anatomical hazard" debate. It emphasizes upon the role of the puboprostatic ligaments and the course of the external urethral sphincter for urinary continence. When performing an intrafascial nerve sparing prostatectomy most urologists tend to approach as close to the prostatic capsula as possible, even though there is no concurrence regarding the nomenclature of the surrounding fascias and the course of the actual neurovascular bundles. After completion of an intrafascial technique the specimen does not contain any periprostatic tissue and thus the detection of pT3a disease is not feasible. This especially becomes problematic if the tumour reaches the resection margin. Nerve sparing open and laparoscopic radical prostatectomy should aim in maintaining sexual function, recuperating early continence after surgery, without hindering the final oncological outcome to the procedure. Despite the different approaches for radical prostatectomy the key for better results is the understanding of the anatomy of the bladder neck and the urethra.

  20. Radical Smiles Rearrangement: An Update

    Directory of Open Access Journals (Sweden)

    Ingrid Allart-Simon

    2016-07-01

    Full Text Available Over the decades the Smiles rearrangement and its variants have become essential synthetic tools in modern synthetic organic chemistry. In this mini-review we summarized some very recent results of the radical version of these rearrangements. The selected examples illustrate the synthetic power of this approach, especially if it is incorporated into a domino process, for the preparation of polyfunctionalized complex molecules.

  1. Free radical reactions of daunorubicin

    International Nuclear Information System (INIS)

    Houee-Levin, C.

    1991-01-01

    Daunorubicin is an antitumor antibiotic activated in vivo by reduction. Its mechanism of action involves DNA and topoisomerase attack, but side effects are cytotoxicity related to free radical formation. Therefore the mechanism of the one-electron reduction of the drug and the reactions of the daunorubicin transients towards compounds of biological interest have been studied by the methods of radiolysis, in order to provide possible explanations of the drug mechanism of action. Their relative importance in cellular conditions is discussed [fr

  2. Geoscientists and the Radical Middle

    Science.gov (United States)

    Tinker, S. W.

    2015-12-01

    Addressing the great challenges facing society requires industry, government, and academia to work together. I call this overlap space, where compromises are made and real solutions determined, the Radical Middle. Radical because it can appear at times as if the loudest and most publicly influential voices lie outside of the actual solution space, content to provoke but not problem-solve. One key area where geoscientists can play a lead role in the Radical Middle is in the overlap between energy, the environment, and the economy. Globally, fossil fuels still represent 85% of the aggregate energy mix. As existing conventional oil and natural-gas reservoir production continues to slowly decline, unconventional reservoirs, led today by shale and other more expensive resources, will represent a growing part of the oil and gas production mix. Many of these unconventional reservoirs require hydraulic fracturing. The positive economic impact of hydraulic fracturing and associated natural gas and oil production on the United States economy is well documented and undeniable. Yet there are environmental concerns about fracking, and some states and nations have imposed moratoria. This energy-environment-economy space is ideal for leadership from the geosciences. Another such overlap space is the potential for geoscience leadership in relations with China, whose economy and global presence continue to expand. Although China is building major hydropower and natural-gas power plants, as well as nuclear reactors, coal is still king—with the associated environmental impacts. Carbon sequestration—onshore in brine and to enhance oil recovery, as well as offshore—could prove viable. It is vital that educated and objective geoscientists from industry, government, and academia leave their corners and work together in the Radical Middle to educate the public and develop and deliver balanced, economically sensible energy and environmental strategies.

  3. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Carraher, Jack McCaslin [Iowa State Univ., Ames, IA (United States)

    2014-01-01

    Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding ‘greener’ sources of commodity chemicals and fuels.

  4. MHD intermediate shock discontinuities: Pt. 1

    International Nuclear Information System (INIS)

    Kennel, C.F.; Blandford, R.D.; Coppi, P.

    1989-01-01

    Recent numerical investigations have focused attention once more on the role of intermediate shocks in MHD. Four types of intermediate shock are identified using a graphical representation of the MHD Rankine-Hugoniot conditions. This same representation can be used to exhibit the close relationship of intermediate shocks to switch-on shocks and rotational discontinuities. The conditions under which intermediate discontinuities can be found are elucidated. The variations in velocity, pressure, entropy and magnetic-field jumps with upstream parameters in intermediate shocks are exhibited graphically. The evolutionary arguments traditionally advanced against intermediate shocks may fail because the equations of classical MHD are not strictly hyperbolic. (author)

  5. Fundamental and semi-global kinetic mechanisms for hydrocarbon combustion. Final report, March 1977-October 1980

    Energy Technology Data Exchange (ETDEWEB)

    Dryer, F L; Glassman, I; Brezinsky, K

    1981-03-01

    Over the past three and one half years, substantial research efforts of the Princeton Fuels Research Group have been directed towards the development of simplified mechanisms which would accurately describe the oxidation of hydrocarbons fuels. The objectives of this combustion research included the study of semi-empirical modeling (that is an overall description) of the chemical kinetic mechanisms of simple hydrocarbon fuels. Such fuels include the alkanes: ethane, propane, butane, hexane and octane as well as the critically important alkenes: ethene, propene and butene. As an extension to this work, the study of the detailed radical species characteristics of combustion systems was initiated as another major aspect of the program, with emphasis on the role of the OH and HO/sub 2/ radicals. Finally, the studies of important alternative fuel problems linked the program to longer range approaches to the energy supply question. Studies of alternative fuels composed the major elements of this area of the program. The efforts on methanol research were completed, and while the aromatics aspects of the DOE work have been a direct extension of efforts supported by the Air Force Office of Scientific Research, they represented a significant part of the overall research effort. The emphasis in the proposed program is to provide further fundamental understanding of the oxidation of hydrocarbon fuels which will be useful in guiding engineering approaches. Although the scope of program ranges from the fundamentals of chemical kinetics to that of alternative fuel combustion, the objective in mind is to provide insight and guidance to the understanding of practical combustion environments. The key to our approach has been our understanding of the fundamental combustion chemistry and its relation to the important practical combustion problems which exist in implementing energy efficient, alternate fuels technologies.

  6. EPR spin trapping of protein radicals

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan; Hawkins, Clare Louise

    2004-01-01

    Electron paramagnetic resonance (EPR) spin trapping was originally developed to aid the detection of low-molecular-mass radicals formed in chemical systems. It has subsequently found widespread use in biology and medicine for the direct detection of radical species formed during oxidative stress...... tumbling radicals are often broad and relatively poor in distinctive features, a number of techniques have been developed that allow a wealth of information to be obtained about the nature, site, and reactions of such radicals. This article summarizes recent developments in this area and reviews selected...... examples of radical formation on proteins....

  7. Studies of free radicals by ultraviolet excimer laser photolysis. Progress report, 1 April 1980-1 November 1980

    International Nuclear Information System (INIS)

    Leone, S.R.

    1980-01-01

    An experimental technique has been developed to produce and directly study vibrationally excited free radicals. Pulses of light from an ultraviolet excimer laser are used to photodissociate small molecules to generate free radicals with high internal excitation. The radicals are detected directly by the technique of time and wavelength-resolved infrared emission spectroscopy using a background-limited copper-doped germanium infrared detector. New results have been obtained on the CH 3 radical. A complete spectrum of the CH 3 umbrella band reveals for the first time accurate positions of the vibrational progression in this band. Photofragmentation of (CH 3 ) 2 Hg has yielded detailed information on the vibrational distribution, rotational temperature, and deactivation rates of the CH 3 stretch mode. A technique to study chemical chain reactions using low power, radical-specific, laser initiation and realtime kinetics detection had previously been demonstrated. The results provide a general method to study a large number of chain reaction combustion systems in greater detail. New results on more complex chain reactions such as Cl 2 /butane reveal that highly detailed infrared emission spectra of various products of the chain and their time evolution is possible. Partitioning of energy between vibrational degrees of freedom and translational heating is obtained over the course of the combustion

  8. Is Adjuvant Chemoradiotherapy Overtreatment in Cervical Cancer Patients With Intermediate Risk Factors?

    International Nuclear Information System (INIS)

    Ryu, Sang-Young; Park, Sang-Il; Nam, Byung-Ho; Cho, Chul-Koo; Kim, Kidong; Kim, Beob-Jong; Kim, Moon-Hong; Choi, Seok-Cheol; Lee, Eui-Don; Lee, Kyoung-Hee

    2011-01-01

    Purpose: To determine whether adjuvant chemoradiotherapy (CRT) improves the outcome of cervical cancer patients with intermediate risk factors. Methods and Materials: Between January 2000 and June 2006, the medical records of 735 patients who had undergone radical surgery for Stage IB-IIA cervical cancer were reviewed retrospectively. Of the 735 patients, 172 with two or more intermediate risk factors (i.e., lymphovascular space involvement, deep stromal invasion, and tumor size ≥2 cm) were grouped as follows according to the adjuvant treatment received: 34 patients, no further treatment; 49 patients, RT; and 89 patients, CRT. The significance of the clinical parameters and recurrence-free survival of each group were analyzed. Results: Of the 172 patients with any of the intermediate risk factors, 137 (79.6%) had two or more intermediate risk factors. Of the 172 patients, 12 developed recurrences (6.4%)->(7.0%), with 6 in the pelvis and 6 in distant sites. All 12 recurrences occurred in those who had two or more intermediate risk factors (sensitivity, 100%); however, only six recurrences were detected in patients who met the Gynecologic Oncology Group criteria for the intermediate-risk group (sensitivity, 50%; Z test, p .05). Conclusion: Postoperative adjuvant CRT can improve the outcome of cervical cancer patients with intermediate risk factors, with low increase in toxicity.

  9. Characterisation of wood combustion ashes

    DEFF Research Database (Denmark)

    Maresca, Alberto

    The combustion of wood chips and wood pellets for the production of renewable energy in Denmark increased from 5.7 PJ to 16 PJ during the period 2000-2015, and further increases are expected to occur within the coming years. In 2012, about 22,300 tonnes of wood ashes were generated in Denmark....... Currently, these ashes are mainly landfilled, despite Danish legislation allowing their application onto forest and agricultural soils for fertilising and/or liming purposes. During this PhD work, 16 wood ash samples generated at ten different Danish combustion plants were collected and characterised...... for their composition and leaching properties. Despite the relatively large variations in the contents of nutrients and trace metals, the overall levels were comparable to typical ranges reported in the literature for other wood combustion ashes, as well as with regards to leaching. In general, the composition...

  10. Novel Active Combustion Control Valve

    Science.gov (United States)

    Caspermeyer, Matt

    2014-01-01

    This project presents an innovative solution for active combustion control. Relative to the state of the art, this concept provides frequency modulation (greater than 1,000 Hz) in combination with high-amplitude modulation (in excess of 30 percent flow) and can be adapted to a large range of fuel injector sizes. Existing valves often have low flow modulation strength. To achieve higher flow modulation requires excessively large valves or too much electrical power to be practical. This active combustion control valve (ACCV) has high-frequency and -amplitude modulation, consumes low electrical power, is closely coupled with the fuel injector for modulation strength, and is practical in size and weight. By mitigating combustion instabilities at higher frequencies than have been previously achieved (approximately 1,000 Hz), this new technology enables gas turbines to run at operating points that produce lower emissions and higher performance.

  11. Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates

    KAUST Repository

    Zhang, Tao

    2016-05-04

    Benzothiazole (BTH) and its derivatives, 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA) and 2-hydroxybenzothiazole (OHBT), are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e. Rct) of this process is a constant which is related to reaction condition and can be easily determined. Reaction rate constants of these benzothiazoles towards sulfate radical are (3.3 ± 0.3) × 109, (1.4 ± 0.3) × 109, (1.5 ± 0.1) × 109 and (4.7 ± 0.5) × 109 M-1s-1, respectively (pH 7 and 20 oC). Based on Rct and these rate constants, their degradation in the presence of organic matter can be well predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates which are reactive towards common oxidants. For OHBT oxidation, it prefers to break down the thiazole ring. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low DOC waters like urban runoff or polluted groundwater.

  12. Oxidation of Refractory Benzothiazoles with PMS/CuFe2O4: Kinetics and Transformation Intermediates

    KAUST Repository

    Zhang, Tao; Chen, Yin; Leiknes, TorOve

    2016-01-01

    Benzothiazole (BTH) and its derivatives, 2-(methylthio)bezothiazole (MTBT), 2-benzothiazolsulfonate (BTSA) and 2-hydroxybenzothiazole (OHBT), are refractory pollutants ubiquitously existing in urban runoff at relatively high concentrations. Here, we report their oxidation by CuFe2O4-activated peroxomonosulfate (PMS/CuFe2O4), focusing on kinetics and transformation intermediates. These benzothiazoles can be efficiently degraded by this oxidation process which is confirmed to generate mainly sulfate radicals (with negligible hydroxyl-radical formation) under slightly acidic to neutral pH conditions. The molar exposure ratio of sulfate radical to residual PMS (i.e. Rct) of this process is a constant which is related to reaction condition and can be easily determined. Reaction rate constants of these benzothiazoles towards sulfate radical are (3.3 ± 0.3) × 109, (1.4 ± 0.3) × 109, (1.5 ± 0.1) × 109 and (4.7 ± 0.5) × 109 M-1s-1, respectively (pH 7 and 20 oC). Based on Rct and these rate constants, their degradation in the presence of organic matter can be well predicted. A number of transformation products were detected and tentatively identified using triple-quadruple/linear ion trap MS/MS and high-resolution MS. It appears that sulfate radicals attack BTH, MTBT and BTSA on their benzo ring via electron transfer, generating multiple hydroxylated intermediates which are reactive towards common oxidants. For OHBT oxidation, it prefers to break down the thiazole ring. Due to competitions of the transformation intermediates, a minimum PMS/pollutant molar ratio of 10-20 is required for effective degradation. The flexible PMS/CuFe2O4 could be a useful process to remove the benzothiazoles from low DOC waters like urban runoff or polluted groundwater.

  13. Combustion instability modeling and analysis

    Energy Technology Data Exchange (ETDEWEB)

    Santoro, R.J.; Yang, V.; Santavicca, D.A. [Pennsylvania State Univ., University Park, PA (United States); Sheppard, E.J. [Tuskeggee Univ., Tuskegee, AL (United States). Dept. of Aerospace Engineering

    1995-12-31

    It is well known that the two key elements for achieving low emissions and high performance in a gas turbine combustor are to simultaneously establish (1) a lean combustion zone for maintaining low NO{sub x} emissions and (2) rapid mixing for good ignition and flame stability. However, these requirements, when coupled with the short combustor lengths used to limit the residence time for NO formation typical of advanced gas turbine combustors, can lead to problems regarding unburned hydrocarbons (UHC) and carbon monoxide (CO) emissions, as well as the occurrence of combustion instabilities. The concurrent development of suitable analytical and numerical models that are validated with experimental studies is important for achieving this objective. A major benefit of the present research will be to provide for the first time an experimentally verified model of emissions and performance of gas turbine combustors. The present study represents a coordinated effort between industry, government and academia to investigate gas turbine combustion dynamics. Specific study areas include development of advanced diagnostics, definition of controlling phenomena, advancement of analytical and numerical modeling capabilities, and assessment of the current status of our ability to apply these tools to practical gas turbine combustors. The present work involves four tasks which address, respectively, (1) the development of a fiber-optic probe for fuel-air ratio measurements, (2) the study of combustion instability using laser-based diagnostics in a high pressure, high temperature flow reactor, (3) the development of analytical and numerical modeling capabilities for describing combustion instability which will be validated against experimental data, and (4) the preparation of a literature survey and establishment of a data base on practical experience with combustion instability.

  14. Youth De-Radicalization: A Canadian Framework

    Directory of Open Access Journals (Sweden)

    Hafal (Haval Ahmad

    2017-09-01

    Full Text Available Youth radicalization leading to violence has become a growing fear among Canadians, as terrorist attacks are carried out in Western states. Although Canada has suffered relatively fewer acts of violence, this fear has intensified and a de-radicalization strategy is needed in the Canadian context. In a qualitative case study methodology, interviews were conducted with school counsellors, religious leaders, and academics to explore solutions to youth radicalization. Youth de-radicalization approaches from the United Kingdom were analyzed and found that community-based initiatives were missing from programming. Social identity theory is used to explain that youth join radicalized groups to feel a sense of belonging and have to be provided an alternative and moderate group identity to de-radicalize. This study found youth de-radicalization in Canada is best served through a community collaboration approach.

  15. Chemical repair of trypsin-histidinyl radical

    International Nuclear Information System (INIS)

    Jovanovic, S.V.; Ruvarac, I.; Jankovic, I.; Josimovic, L.

    1991-01-01

    Oxyl radicals, such as hydroxyl, alkoxyl and peroxyl, react with biomolecules to produce bioradicals. Unless chemically repaired by suitable antioxidants, these bioradicals form stable products. This leads to loss of biological function of parent biomolecules with deleterious biological results, such as mutagenesis and cancer. Consequently, the understanding of the mechanisms of oxyl radical damage to biomolecules and chemical repair of such damage is crucial for the development of strategies for anticarcinogenesis and radioprotection. In this study the chemical repair of the histidinyl radical generated upon the trichloromethylperoxyl radical reaction with trypsin vas investigated by gamma radiolysis. The trypsin histidinyl radical is a resonance-stabilized heterocyclic free radical which was found to be unreactive with oxygen. The efficacy of the chemical repair of the trypsin-histidinyl radical by endogenous antioxidants which are electron donors (e.g. 5-hydroxytryptophan, uric acid) is compared to that of antioxidants which are H-atom donors (e. g. glutathione). 9 refs., 2 figs., 1 tab

  16. A Study of Pollutant Formation from the Lean Premixed Combustion of Gaseous Fuel Alternatives to Natural Gas

    Science.gov (United States)

    Fackler, Keith Boyd, Jr.

    , temperature, and species structure within the reactor. Since the two dimensional model is far more computationally efficient, it is employed to study various fuel mixtures with more sophisticated chemical mechanisms. The CFD results from the LPM combustion of H2, H2/CO, and CH4 with NOx formation are presented. A three dimensional CFD simulation is run for LPM CH4 combustion that uses a global CH4 oxidation mechanism. While this model does not predict intermediate radicals and NOx, the CO contours and flow field can be used as guidelines to develop a chemical reactor network (CRN), which can incorporate detailed chemistry. In addition, this model runs quickly enough that it is a good way to initialize the temperature and flow field for simulations that do incorporate more complex chemistry. The two dimensional model is used to illustrate the difference in combustion behavior between the various fuels tested. In particular, it illustrates the geometric locations of the super-equilibrium radical fields and shows where and through which pathways NOx is formed. The pathway breakdowns show good agreement with the CRN modeling results. The main goal of the CFD modeling is to use the results of each model to develop Chemical Reactor Networks, CRNs, that are customized for a particular burner. The CRN can then be used to estimate the impacts due to fuel variation.

  17. Numerical simulation of premixed turbulent methane combustion

    International Nuclear Information System (INIS)

    Bell, John B.; Day, Marcus S.; Grcar, Joseph F.

    2001-01-01

    In this paper we study the behavior of a premixed turbulent methane flame in three dimensions using numerical simulation. The simulations are performed using an adaptive time-dependent low Mach number combustion algorithm based on a second-order projection formulation that conserves both species mass and total enthalpy. The species and enthalpy equations are treated using an operator-split approach that incorporates stiff integration techniques for modeling detailed chemical kinetics. The methodology also incorporates a mixture model for differential diffusion. For the simulations presented here, methane chemistry and transport are modeled using the DRM-19 (19-species, 84-reaction) mechanism derived from the GRIMech-1.2 mechanism along with its associated thermodynamics and transport databases. We consider a lean flame with equivalence ratio 0.8 for two different levels of turbulent intensity. For each case we examine the basic structure of the flame including turbulent flame speed and flame surface area. The results indicate that flame wrinkling is the dominant factor leading to the increased turbulent flame speed. Joint probability distributions are computed to establish a correlation between heat release and curvature. We also investigate the effect of turbulent flame interaction on the flame chemistry. We identify specific flame intermediates that are sensitive to turbulence and explore various correlations between these species and local flame curvature. We identify different mechanisms by which turbulence modulates the chemistry of the flame

  18. Improvement of fuel combustion technologies

    Energy Technology Data Exchange (ETDEWEB)

    Tumanovskii, A.G.; Babii, V.I.; Enyakin, Y.P.; Kotler, V.R.; Ryabov, G.V.; Verbovetskii, E.K.; Nadyrov, I.I. [All-Russian Thermal Engineering Institute, Moscow (Russian Federation)

    1996-07-01

    The main problems encountered in the further development of fuel combustion technologies at thermal power stations in Russia are considered. Experience is generalized and results are presented on the efficiency with which nitrogen oxide emissions are reduced by means of technological methods when burning natural gas, fuel oil, and coal. The problems that arise in the introduction of new combustion technologies and in using more promising grades of coal are considered. The results studies are presented that show that low grade Russian coals can be burnt in circulating fluidized bed boilers. 14 refs., 5 figs., 4 tabs.

  19. Chemical kinetics and combustion modeling

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.A. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    The goal of this program is to gain qualitative insight into how pollutants are formed in combustion systems and to develop quantitative mathematical models to predict their formation rates. The approach is an integrated one, combining low-pressure flame experiments, chemical kinetics modeling, theory, and kinetics experiments to gain as clear a picture as possible of the process in question. These efforts are focused on problems involved with the nitrogen chemistry of combustion systems and on the formation of soot and PAH in flames.

  20. A comprehensive combustion chemistry study of 2,5-dimethylhexane

    KAUST Repository

    Sarathy, Mani

    2014-06-01

    Iso-paraffinic molecular structures larger than seven carbon atoms in chain length are commonly found in conventional petroleum, Fischer-Tropsch (FT), and other alternative hydrocarbon fuels, but little research has been done on their combustion behavior. Recent studies have focused on either mono-methylated alkanes and/or highly branched compounds (e.g., 2,2,4-trimethylpentane). In order to better understand the combustion characteristics of real fuels, this study presents new experimental data for the oxidation of 2,5-dimethylhexane under a wide variety of temperature, pressure, and equivalence ratio conditions. This new dataset includes jet stirred reactor speciation, shock tube ignition delay, and rapid compression machine ignition delay, which builds upon recently published data for counterflow flame ignition, extinction, and speciation profiles. The low and high temperature oxidation of 2,5-dimethylhexane has been simulated with a comprehensive chemical kinetic model developed using established reaction rate rules. The agreement between the model and data is presented, along with suggestions for improving model predictions. The oxidation behavior of 2,5-dimethylhexane is compared with oxidation of other octane isomers to confirm the effects of branching on low and intermediate temperature fuel reactivity. The model is used to elucidate the structural features and reaction pathways responsible for inhibiting the reactivity of 2,5-dimethylhexane. © 2014 The Combustion Institute.

  1. A comprehensive combustion chemistry study of 2,5-dimethylhexane

    KAUST Repository

    Sarathy, Mani; Javed, Tamour; Karsenty, Florent; Heufer, Alexander; Wang, Weijing; Park, Sungwoo; Elwardani, Ahmed Elsaid; Farooq, Aamir; Westbrook, Charles K.; Pitz, William J.; Oehlschlaeger, Matthew A.; Dayma, Guillaume; Curran, Henry J.; Dagaut, P.

    2014-01-01

    Iso-paraffinic molecular structures larger than seven carbon atoms in chain length are commonly found in conventional petroleum, Fischer-Tropsch (FT), and other alternative hydrocarbon fuels, but little research has been done on their combustion behavior. Recent studies have focused on either mono-methylated alkanes and/or highly branched compounds (e.g., 2,2,4-trimethylpentane). In order to better understand the combustion characteristics of real fuels, this study presents new experimental data for the oxidation of 2,5-dimethylhexane under a wide variety of temperature, pressure, and equivalence ratio conditions. This new dataset includes jet stirred reactor speciation, shock tube ignition delay, and rapid compression machine ignition delay, which builds upon recently published data for counterflow flame ignition, extinction, and speciation profiles. The low and high temperature oxidation of 2,5-dimethylhexane has been simulated with a comprehensive chemical kinetic model developed using established reaction rate rules. The agreement between the model and data is presented, along with suggestions for improving model predictions. The oxidation behavior of 2,5-dimethylhexane is compared with oxidation of other octane isomers to confirm the effects of branching on low and intermediate temperature fuel reactivity. The model is used to elucidate the structural features and reaction pathways responsible for inhibiting the reactivity of 2,5-dimethylhexane. © 2014 The Combustion Institute.

  2. FAR RIGHT RADICALIZATION AND SOCIALIST RADICALIZATION IN INTERWAR ROMANIA

    Directory of Open Access Journals (Sweden)

    IONUŢ BUTOI

    2017-03-01

    Full Text Available In his comments on Mircea Vulcănescu. O microistorie a interbelicului românesc (Eikon, 2015, Emanuel Copilaş states that, regarding the cause of the far right radicalization manifested in the interwar Romania, I share the same historical explanation about fascism as Ernst Nolte. In this concise answer, I explain why this is an unsuitable comparison by summarizing the historiographical perspective I use in the cited volume. Nevertheless, Copilaş’s comments are reopening a debate about how to explain the Romanian fascism

  3. Structure reactivity relationship in the reaction of DNA guanyl radicals with hydroxybenzoates

    Energy Technology Data Exchange (ETDEWEB)

    Do, Trinh T.; Tang, Vicky J.; Aguilera, Joseph A. [Department of Radiology University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States); Milligan, Jamie R., E-mail: jmilligan@ucsd.ed [Department of Radiology University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0610 (United States)

    2010-11-15

    In DNA, guanine bases are the sites from which electrons are most easily removed. As a result of hole migration to this stable location on guanine, guanyl radicals are major intermediates in DNA damage produced by the direct effect of ionizing radiation (ionization of the DNA itself and not through the intermediacy of water radicals). We have modeled this process by employing gamma irradiation in the presence of thiocyanate ions, a method which also produces single electron oxidized guanyl radicals in plasmid DNA in aqueous solution. The stable products formed in DNA from these radicals are detected as strand breaks after incubation with the FPG protein. When a phenolic compound is present in the solution during gamma irradiation, the formation of guanyl radical species is decreased by electron donation from the phenol to the guanyl radical. We have quantified the rate of this reaction for four different phenolic compounds bearing carboxylate substituents as proton acceptors. A comparison of the rates of these reactions with the redox strengths of the phenolic compounds reveals that salicylate reacts ca. 10-fold faster than its structural analogs. This observation is consistent with a reaction mechanism involving a proton coupled electron transfer, because intra-molecular transfer of a proton from the phenolic hydroxyl group to the carboxylate group is possible only in salicylate, and is favored by the strong 6-membered ring intra-molecular hydrogen bond in this compound.

  4. Functionalised Oximes: Emergent Precursors for Carbon-, Nitrogen- and Oxygen-Centred Radicals

    Directory of Open Access Journals (Sweden)

    John C. Walton

    2016-01-01

    Full Text Available Oxime derivatives are easily made, are non-hazardous and have long shelf lives. They contain weak N–O bonds that undergo homolytic scission, on appropriate thermal or photochemical stimulus, to initially release a pair of N- and O-centred radicals. This article reviews the use of these precursors for studying the structures, reactions and kinetics of the released radicals. Two classes have been exploited for radical generation; one comprises carbonyl oximes, principally oxime esters and amides, and the second comprises oxime ethers. Both classes release an iminyl radical together with an equal amount of a second oxygen-centred radical. The O-centred radicals derived from carbonyl oximes decarboxylate giving access to a variety of carbon-centred and nitrogen-centred species. Methods developed for homolytically dissociating the oxime derivatives include UV irradiation, conventional thermal and microwave heating. Photoredox catalytic methods succeed well with specially functionalised oximes and this aspect is also reviewed. Attention is also drawn to the key contributions made by EPR spectroscopy, aided by DFT computations, in elucidating the structures and dynamics of the transient intermediates.

  5. The properties and Roles of Resonance-Stabilized Radicals in Photochemical Pathways in Titan's Atmosphere

    Science.gov (United States)

    Sebree, Joshua A.; Kidwell, Nathan; Zwier, Timothy

    2010-11-01

    In recent years, the Cassini satellite has been providing details about the composition of Titan's atmosphere. Recent data has shown the existence of polycyclic aromatic hydrocarbons (PAHs) at higher altitudes than previously expected including masses tentatively ascribed to naphthalene and anthracene. The formation of indene (C9H9) and naphthalene (C10H8), the simplest PAHs, and their derivatives are of great interest as similar mechanisms may lead to the formation of larger fused-ring systems. In recent years it has been proposed that resonance-stabilized radicals (RSRs) may play an important role as intermediates along these pathways. RSRs gain extra stability by delocalizing the unpaired electron through a neighboring conjugated π-system. Because of this extra stability, RSRs are able to build up in concentration, allowing for the creation of larger, more complex systems through their recombination with other RSRs. Mass-selective UV-visible spectra of two RSRs, phenylallyl and benzylallenyl radicals, have been recorded under jet-cooled conditions. These two radicals, while sharing the same radical conjugation, have unique properties. The roles these radicals may play in the formation of fused ring systems will be discussed along with recent photochemical results on reaction pathways starting from benzylallene through the benzylallenyl radical.

  6. Application of the FIRST Combustion model to Spray Combustion

    NARCIS (Netherlands)

    de Jager, B.; Kok, Jacobus B.W.

    2004-01-01

    Liquid fuel is of interest to apply to gas turbines. The large advantage is that liquids are easily storable as compared to gaseous fuels. Disadvantage is that liquid fuel has to be sprayed, vaporized and mixed with air. Combustion occurs at some stage of mixing and ignition. Depending on the

  7. Development of a Premixed Combustion Capability for Scramjet Combustion Experiments

    Science.gov (United States)

    Rockwell, Robert D.; Goyne, Christopher P.; Rice, Brian E.; Chelliah, Harsha; McDaniel, James C.; Edwards, Jack R.; Cantu, Luca M. L.; Gallo, Emanuela C. A.; Cutler, Andrew D.; Danehy, Paul M.

    2015-01-01

    Hypersonic air-breathing engines rely on scramjet combustion processes, which involve high speed, compressible, and highly turbulent flows. The combustion environment and the turbulent flames at the heart of these engines are difficult to simulate and study in the laboratory under well controlled conditions. Typically, wind-tunnel testing is performed that more closely approximates engine testing rather than a careful investigation of the underlying physics that drives the combustion process. The experiments described in this paper, along with companion data sets being developed separately, aim to isolate the chemical kinetic effects from the fuel-air mixing process in a dual-mode scramjet combustion environment. A unique fuel injection approach is taken that produces a nearly uniform fuel-air mixture at the entrance to the combustor. This approach relies on the precombustion shock train upstream of the dual-mode scramjet combustor. A stable ethylene flame anchored on a cavity flameholder with a uniformly mixed combustor inflow has been achieved in these experiments allowing numerous companion studies involving coherent anti-Stokes Raman scattering (CARS), particle image velocimetry (PIV), and planar laser induced fluorescence (PLIF) to be performed.

  8. Role of Intermediate Filaments in Vesicular Traffic

    Directory of Open Access Journals (Sweden)

    Azzurra Margiotta

    2016-04-01

    Full Text Available Intermediate filaments are an important component of the cellular cytoskeleton. The first established role attributed to intermediate filaments was the mechanical support to cells. However, it is now clear that intermediate filaments have many different roles affecting a variety of other biological functions, such as the organization of microtubules and microfilaments, the regulation of nuclear structure and activity, the control of cell cycle and the regulation of signal transduction pathways. Furthermore, a number of intermediate filament proteins have been involved in the acquisition of tumorigenic properties. Over the last years, a strong involvement of intermediate filament proteins in the regulation of several aspects of intracellular trafficking has strongly emerged. Here, we review the functions of intermediate filaments proteins focusing mainly on the recent knowledge gained from the discovery that intermediate filaments associate with key proteins of the vesicular membrane transport machinery. In particular, we analyze the current understanding of the contribution of intermediate filaments to the endocytic pathway.

  9. A limited role for adjuvant radiotherapy after the Wertheim/Okabayashi radical hysterectomy for cervical cancer confined to the cervix

    NARCIS (Netherlands)

    van der Velden, J.; Samlal, R.; Schilthuis, M. S.; Gonzalez, D. G.; ten Kate, F. J.; Lammes, F. B.

    1999-01-01

    The indications for radiotherapy after radical hysterectomy for early stage cervical cancer are changing. In the past only tumor outside the cervix was considered an indication for radiotherapy. Today adjuvant radiotherapy is also considered for an "intermediate-risk" group with tumor confined to

  10. Interactive wood combustion for botanical tree models

    KAUST Repository

    Pirk, Sö ren; Jarząbek, Michał; Hadrich, Torsten; Michels, Dominik L.; Palubicki, Wojciech

    2017-01-01

    We present a novel method for the combustion of botanical tree models. Tree models are represented as connected particles for the branching structure and a polygonal surface mesh for the combustion. Each particle stores biological and physical

  11. Free Energy and Internal Combustion Engine Cycles

    OpenAIRE

    Harris, William D.

    2012-01-01

    The performance of one type (Carnot) of Internal Combustion Engine (ICE) cycle is analyzed within the framework of thermodynamic free energies. ICE performance is different from that of an External Combustion Engine (ECE) which is dictated by Carnot's rule.

  12. Method for storing radioactive combustible waste

    Science.gov (United States)

    Godbee, H.W.; Lovelace, R.C.

    1973-10-01

    A method is described for preventing pressure buildup in sealed containers which contain radioactively contaminated combustible waste material by adding an oxide getter material to the container so as to chemically bind sorbed water and combustion product gases. (Official Gazette)

  13. Scramjet Combustion Stability Behavior Modeling, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — A recent breakthrough in combustion stability analysis (UCDS) offers the potential to predict the combustion stability of a scramjet. This capability is very...

  14. Scramjet Combustion Stability Behavior Modeling, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — A recent breakthrough in combustion stability analysis (UCDS) offers the means to accurately predict the combustion stability of a scramjet. This capability is very...

  15. Publication sites productive uses of combustion ash

    Science.gov (United States)

    Publication Sites Productive Uses of Combustion Ash For more information contact: e:mail: Public waste combustion ash in landfills. The new technology brief describes recent studies where ash was used

  16. Combustion Research Facility | A Department of Energy Office of Science

    Science.gov (United States)

    Collaborative Research Facility Back to Sandia National Laboratory Homepage Combustion Research Search the CRF Combustion Chemistry Flame Chemistry Research.Combustion_Chemistry.Flame_Chemistry Theory and Modeling Theory and Modeling Combustion Kinetics High Pressure Chemistry Chemistry of Autoignition

  17. Fuel Combustion and Engine Performance | Transportation Research | NREL

    Science.gov (United States)

    Fuel Combustion and Engine Performance Fuel Combustion and Engine Performance Photo of a gasoline emissions in advanced engine technologies. Photo by Dennis Schroeder, NREL NREL's combustion research and combustion and engine research activities include: Developing experimental and simulation research platforms

  18. ESL intermediate/advanced writing

    CERN Document Server

    Munoz Page, Mary Ellen; Jaskiewicz, Mary

    2011-01-01

    Master ESL (English as a Second Language) Writing with the study guide designed for non-native speakers of English. Skill-building lessons relevant to today's topics help ESL students write complete sentences, paragraphs, and even multi-paragraph essays. It's perfect for classroom use or self-guided writing preparation.DETAILS- Intermediate drills for improving skills with parallel structure, mood, correct shifting errors & dangling participles- Advanced essay drills focusing on narrative, descriptive, process, reaction, comparison and contrast- Superb preparation for students taking the TOEFL

  19. Photonuclear reactions at intermediate energy

    International Nuclear Information System (INIS)

    Koch, J.H.

    1982-01-01

    The dominant feature of photonuclear reactions at intermediate energies is the excitation of the δ resonance and one can therefore use such reactions to study the dynamics of δ propagation in a nucleus. Following an introductory section the author comments on photoabsorption on a single nucleon in Section II. A review of the δ-n Greens function and of the photonuclear amplitude is given in Section III. Results for photoabsorption on 4 He are shown in Section IV and compared with the data. Coherent π 0 photoproduction is discussed in Section V and calculations for 12 C are compared to recent measurements. (Auth.)

  20. Pelamis WEC - intermediate scale demonstration

    Energy Technology Data Exchange (ETDEWEB)

    Yemm, R.

    2003-07-01

    This report describes the successful building and commissioning of an intermediate 1/7th scale model of the Pelamis Wave Energy Converter (WEC) and its testing in the wave climate of the Firth of Forth. Details are given of the design of the semi-submerged articulated structure of cylindrical elements linked by hinged joints. The specific programme objectives and conclusions, development issues addressed, and key remaining risks are discussed along with development milestones to be passed before the Pelamis WEC is ready for full-scale prototype testing.