Intermolecular interactions involving C-H bonds, 3, Structure and energetics of the interaction between CH{sub 4} and CN{sup {minus}}

Energy Technology Data Exchange (ETDEWEB)

Novoa, J.J.; Whangbo, Myung-Hwan [North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemistry; Williams, J.M. [Argonne National Lab., IL (United States)

1991-12-31

On the basis of SCF and single reference MP2 calculations, the full potential energy surface of the interaction between CH{sub 4} and CN{sup {minus}} was studied using extended basis sets of up to near Hartree-Fock limit quality. Colinear arrangements C-N{sup {minus}}{hor_ellipsis}H-CH{sub 3} and N-C{sup {minus}}{hor_ellipsis}H-CH{sub 3} are found to be the only two energy minima. The binding energies of these two structures are calculated to be 2.5 and 2.1 kcal/mol, respectively, at the MP2 level. The full vibrational analyses of two structures show a red shift of about 30 cm{sup {minus}1} for the v{sub s} C-H stretching.

Atmospheric Chemistry of CH3CH2OCH3

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Bjørn Svendsen, Sissel; Østerstrøm, Freja From

2017-01-01

The atmospheric chemistry of methyl ethyl ether, CH3CH2OCH3, was examined using FT-IR/relative-rate methods. Hydroxyl radical and chlorine atom rate coefficients of k(CH3CH2OCH3+OH) = (7.53 ± 2.86) × 10−12 cm3 molecule−1 s−1 and k(CH3CH2OCH3+Cl) = (2.35 ± 0.43) × 10−10 cm3 molecule−1 s−1 were...

Syntheses and multi-NMR study of fac- and mer-OsO(3)F(2)(NCCH(3)) and the X-ray crystal structure (n = 2) and Raman spectrum (n = 0) of fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN.

Science.gov (United States)

Hughes, Michael J; Gerken, Michael; Mercier, Hélène P A; Schrobilgen, Gary J

2010-06-07

Dissolution of the infinite chain polymer, (OsO(3)F(2))(infinity), in CH(3)CN solvent at -40 degrees C followed by solvent removal under vacuum at -40 degrees C yielded fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN (n >/= 2). Continued pumping at -40 degrees C with removal of uncoordinated CH(3)CN yielded fac-OsO(3)F(2)(NCCH(3)). Both fac-OsO(3)F(2)(NCCH(3)).nCH(3)CN and fac-OsO(3)F(2)(NCCH(3)) are yellow-brown solids and were characterized by low-temperature (-150 degrees C) Raman spectroscopy. The crystal structure (-173 degrees C) of fac-OsO(3)F(2)(NCCH(3)).2CH(3)CN consists of two co-crystallized CH(3)CN molecules and a pseudo-octahedral OsO(3)F(2).NCCH(3) molecule in which three oxygen atoms are in a facial arrangement and CH(3)CN is coordinated trans to an oxygen atom in an end-on fashion. The Os---N bond length (2.205(3) A) is among the shortest M---N adduct bonds observed for a d(0) transition metal oxide fluoride. The (19)F NMR spectrum of (OsO(3)F(2))(infinity) in CH(3)CN solvent (-40 degrees C) is a singlet (-99.6 ppm) corresponding to fac-OsO(3)F(2)(NCCH(3)). The (1)H, (15)N, (13)C, and (19)F NMR spectra of (15)N-enriched OsO(3)F(2)(NCCH(3)) were recorded in SO(2)ClF solvent (-84 degrees C). Nitrogen-15 enrichment resulted in splitting of the (19)F resonance of fac-OsO(3)F(2)((15)NCCH(3)) into a doublet ((2)J((15)N-(19)F), 21 Hz). In addition, a doublet of doublets ((2)J((19)F(ax)-(19)F(eq)), 134 Hz; (2)J((15)N-(19)F(eq)), 18 Hz) and a doublet ((2)J((19)F(ax)-(19)F(eq)), 134 Hz) were observed in the (19)F NMR spectrum that have been assigned to mer-OsO(3)F(2)((15)NCCH(3)); however, coupling of (15)N to the axial fluorine-on-osmium environment could not be resolved. The nitrogen atom of CH(3)CN is coordinated trans to a fluorine ligand in the mer-isomer. Quantum-chemical calculations at the SVWN and B3LYP levels of theory were used to calculate the energy-minimized gas-phase geometries, vibrational frequencies of fac- and mer-OsO(3)F(2)(NCCH(3)) and of CH(3)CN. The

Millimeter/submillimeter spectroscopy of PH{sub 2}CN ( X-tilde {sup 1}A') and CH{sub 3}PH{sub 2} ( X-tilde {sup 1}A'): probing the complexity of interstellar phosphorus chemistry

Energy Technology Data Exchange (ETDEWEB)

Halfen, D. T.; Ziurys, L. M. [Department of Chemistry and Biochemistry, Department of Astronomy, Arizona Radio Observatory, and Steward Observatory, University of Arizona, Tucson, AZ 85721 (United States); Clouthier, D. J., E-mail: halfendt@as.arizona.edu [Department of Chemistry, University of Kentucky, Lexington, KY 40506 (United States)

2014-11-20

Millimeter/submillimeter spectra of PH{sub 2}CN ( X-tilde {sup 1}A') and CH{sub 3}PH{sub 2} ( X-tilde {sup 1}A') have been recorded for the first time using direct absorption techniques. This work extends previous measurements of both molecules beyond the 10-50 GHz range. Both species were created in the presence of an AC discharge by the reaction of phosphorus vapor and either cyanogen and hydrogen (PH{sub 2}CN) or methane (CH{sub 3}PH{sub 2}). Twelve rotational transitions of PH{sub 2}CN were recorded over the region 305-422 GHz for asymmetry components K{sub a} = 0 through 8. For CH{sub 3}PH{sub 2}, eight rotational transitions were measured from 210-470 GHz with K{sub a} = 0 through 16; these spectra exhibited greater complexity due to the presence of internal rotation, which splits the K{sub a} = 1, 2, and 3 asymmetry components into A and E states. Combined analyses of the millimeter/submillimeter and previous microwave data were performed for both molecules. For PH{sub 2}CN, the spectra were fit with a Watson S-reduced asymmetric top Hamiltonian, resulting in more accurate rotational and centrifugal distortion constants. In the case of CH{sub 3}PH{sub 2}, an asymmetric top internal-rotation Hamiltonian was employed in the analysis, significantly improving the rotational and torsional parameters over previous microwave estimates. Searches for both molecules were subsequently conducted toward Sgr B2(N), using the 12 m telescope of the Arizona Radio Observatory (ARO). Neither species was identified, with abundance upper limits, relative to H{sub 2}, of f (PH{sub 2}CN/H{sub 2}) < 7.0 × 10{sup –12} and f (CH{sub 3}PH{sub 2}/H{sub 2}) < 8.4 × 10{sup –12}. The nitrogen analogs NH{sub 2}CN and CH{sub 3}NH{sub 2} are therefore more abundant in Sgr B2(N) by factors of >2 and >200, respectively.

Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

Science.gov (United States)

Hudson, R. L.; Moore, M. H.

2004-12-01

Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH 3CN, CH 3CH 2CN, CH 2CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH 3) 2CHCN and (CH 3) 3CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH 3CN, CH 3CH 2CN, and (CH 3) 2CHCN also formed ketenimines. In the presence of H 2O, no isonitriles were detected but rather the cyanate ion (OCN -) was seen in all cases. Although isonitriles, ketenimines, and OCN - were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

Science.gov (United States)

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

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

The uranium(VI) oxoazides [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN], [(bipy){sub 2}(UO{sub 2}){sub 2}(N{sub 3}){sub 4}], [(bipy)UO{sub 2}(N{sub 3}){sub 3}]{sup -}, [UO{sub 2}(N{sub 3}){sub 4}]{sup 2-}, and [(UO{sub 2}){sub 2}(N{sub 3}){sub 8}]{sup 4-}

Energy Technology Data Exchange (ETDEWEB)

Haiges, Ralf; Christe, Karl O. [Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, CA (United States); Vasiliu, Monica; Dixon, David A. [Department of Chemistry, The University of Alabama, Tuscaloosa, AL (United States)

2017-01-12

The reaction between [UO{sub 2}F{sub 2}] and an excess of Me{sub 3}SiN{sub 3} in acetonitrile solution results in fluoride-azide exchange and the uranium(VI) dioxodiazide adduct [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN] was isolated in quantitative yield. The subsequent reaction of [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN] with 2,2{sup '}-bipyridine (bipy) resulted in the formation of the azido-bridged binuclear complex [(bipy){sub 2}(UO{sub 2}){sub 2}(N{sub 3}){sub 4}]. The triazido anion [(bipy)UO{sub 2}(N{sub 3}){sub 3}]{sup -} was obtained by the reaction of [UO{sub 2}(N{sub 3}){sub 2}.CH{sub 3}CN] with stoichiometric amounts of bipy and the ionic azide [PPh{sub 4}][N{sub 3}]. The reaction of [UO{sub 2}(N{sub 3}){sub 2}] with two equivalents of the [PPh{sub 4}][N{sub 3}] resulted in the formation of the mononuclear tetraazido anion [UO{sub 2}(N{sub 3}){sub 4}]{sup 2-} as well as the azido-bridged binuclear anion [(UO{sub 2}){sub 2}(N{sub 3}){sub 8}]{sup 4-}. The novel uranium oxoazides were characterized by their vibrational spectra and in the case of [(bipy){sub 2}(UO{sub 2}){sub 2}(N{sub 3}){sub 4}].CH{sub 3}CN, [PPh{sub 4}][(bipy)UO{sub 2}(N{sub 3}){sub 3}], [PPh{sub 4}]{sub 2}[UO{sub 2}(N{sub 3}){sub 4}], [PPh{sub 4}]{sub 2}[UO{sub 2}(N{sub 3}){sub 4}].2CH{sub 3}CN, and [PPh{sub 4}]{sub 4}[(UO{sub 2}){sub 2}(N{sub 3}){sub 8}].4CH{sub 3}CN by their X-ray crystal structures. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Capture and dissociation in the complex-forming CH + H2 → CH2 + H, CH + H2 reactions.

Science.gov (United States)

González, Miguel; Saracibar, Amaia; Garcia, Ernesto

2011-02-28

The rate coefficients for the capture process CH + H(2)→ CH(3) and the reactions CH + H(2)→ CH(2) + H (abstraction), CH + H(2) (exchange) have been calculated in the 200-800 K temperature range, using the quasiclassical trajectory (QCT) method and the most recent global potential energy surface. The reactions, which are of interest in combustion and in astrochemistry, proceed via the formation of long-lived CH(3) collision complexes, and the three H atoms become equivalent. QCT rate coefficients for capture are in quite good agreement with experiments. However, an important zero point energy (ZPE) leakage problem occurs in the QCT calculations for the abstraction, exchange and inelastic exit channels. To account for this issue, a pragmatic but accurate approach has been applied, leading to a good agreement with experimental abstraction rate coefficients. Exchange rate coefficients have also been calculated using this approach. Finally, calculations employing QCT capture/phase space theory (PST) models have been carried out, leading to similar values for the abstraction rate coefficients as the QCT and previous quantum mechanical capture/PST methods. This suggests that QCT capture/PST models are a good alternative to the QCT method for this and similar systems.

Vibrational Mode-Specific Autodetachment and Coupling of CH2CN-

Science.gov (United States)

Lyle, Justin; Mabbs, Richard

2017-06-01

The Cyanomethyl Anion, CH_{2}CN-, and neutral radical have been studied extensively, with several findings of autodetachment about the totally symmetric transition, as well as high resolution experiments revealing symmetrically forbidden and weak vibrational features. We report photoelectron spectra using the Velocity-Mapped Imaging Technique in 1-2 \\wn increments over a range of 13460 to 15384 \\wn that has not been previously examined. These spectra include excitation of the ground state cyanomethyl anion into the direct detachment thresholds of previously reported vibrational modes for the neutral radical. Significant variations from Franck-Condon behavior were observed in the branching ratios for resolved vibrational features for excitation in the vicinity of the thresholds involving the νb{3} and νb{5} modes. These are consistent with autodetachment from rovibrational levels of a dipole bound state acting as a resonance in the detachment continuum. The autodetachment channels involve single changes in vibrational quantum number, consistent with the vibrational propensity rule but in some cases reveal relaxation to a different vibrational mode indicating coupling between the modes and/or a breakdown of the normal mode approximation.

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

Science.gov (United States)

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

2018-04-25

Xenondifluoride, XeF2, has been photolysed in the presence of methanol, CH3OH. Two reaction pathways are possible: F + CH3OH → CH2OH + HF and F + CH3OH → CH3O + HF. Both products, CH2OH and CH3O, will be converted to HO2 in the presence of O2. The rate constants for the reaction of both radicals with O2 differ by more than 3 orders of magnitude, which allows an unequivocal distinction between the two reactions when measuring HO2 concentrations in the presence of different O2 concentrations. The following yields have then been determined from time-resolved HO2 profiles: φCH2OH = (0.497 ± 0.013) and φCH3O = (0.503 ± 0.013). Experiments under low O2 concentrations lead to reaction mixtures containing nearly equal amounts of HO2 (converted from the first reaction) and CH3O (from the second reaction). The subsequent HO2 decays are very sensitive to the rate constants of the reaction between these two radicals and the following rate constants have been obtained: k(CH3O + CH3O) = (7.0 ± 1.4) × 10-11 cm3 s-1 and k(CH3O + HO2) = (1.1 ± 0.2) × 10-10 cm3 s-1. The latter reaction has also been theoretically investigated on the CCSD(T)//M06-2X/aug-cc-pVTZ level of theory and CH3OH + O2 have been identified as the main products. Using μVTST, a virtually pressure independent rate constant of k(CH3O + HO2) = 4.7 × 10-11 cm3 s-1 has been obtained, in good agreement with the experiment.

Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.

Science.gov (United States)

Sebbar, N; Bozzelli, J W; Bockhorn, H

2014-01-09

Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.

Theoretical studies of one- and two-photon absorption properties for three molecules with different centers (B and N) and peripheral substituted groups [N(CH{sub 3}){sub 2} and CN

Energy Technology Data Exchange (ETDEWEB)

Han Deming [State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023 (China); Feng Jikang, E-mail: jikangf@yahoo.co [State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023 (China); College of Chemistry, Jilin University, Changchun 130023 (China); Ren Aimin [State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023 (China); Shang Xiaohong [College of Chemistry, Jilin University, Changchun 130023 (China); Liu Xiaojuan [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China)

2009-08-15

Three molecules with different centers (boron and nitrogen) and peripheral substituted groups [N(CH{sub 3}){sub 2} and CN] have been theoretically studied with B3LYP/6-31G(d) associated with ZINDO and sum-over-states methods. The maximum two-photon absorption cross-section delta{sub max} of the molecule with boron (B) center and N(CH{sub 3}){sub 2} peripheral group is larger than that of the molecule with nitrogen (N) center and N(CH{sub 3}){sub 2} peripheral group. As for the two molecules with N center, the delta{sub max} is obviously increased with the change from N(CH{sub 3}){sub 2} to CN group. This indicates that the large intramolecular charge transfer is in favor of the TPA response.

Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

Science.gov (United States)

Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

2016-09-19

Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reacción de ligandos azufrados con el complejo au2pt (ch2p(Sph24,cl2

Directory of Open Access Journals (Sweden)

Guillermo Garzón

2010-07-01

Full Text Available Se describe la reacción de intercambio del cloro en el complejo au2pt (ch2p(Sph24,cl2 por los ligandos SCH2Ph-,S2CN(CH2CH3,2- y SCN-. Los nuevos derivados azufrados se caracterizan por análisis químico, espectroscopia infrarroja, electrónica y resonancia magnética nuclear protónica. Los ligandos se coordinan por el azufre a los dos átomos sw oro metálico en forma simétrica. El análisis elemental concuerda con las estequiomctrías y estructuras propuestas.

Formation of doubly and triply bonded unsaturated compounds HCN, HNC, and CH2NH via N + CH4 low-temperature solid state reaction: from molecular clouds to solar system objects

Science.gov (United States)

Mencos, Alejandro; Krim, Lahouari

2018-06-01

We show in the current study carried out in solid phase at cryogenic temperatures that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC, and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN-, and three nitrogen hydrides NH, NH2, and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2, and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects, and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species, such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

Effects of Boreal Lake Wetlands on Atmospheric 13CH3D and 12CH2D2

Science.gov (United States)

Haghnegahdar, M. A.; Kohl, I. E.; Schauble, E. A.; Walter Anthony, K. M.; Young, E. D.

2017-12-01

Recently, we developed a theoretical model to investigate the potential use of 13CH3D and 12CH2D2 as tools for tracking atmospheric methane budget. We used electronic structure methods to estimate kinetic isotope fractionations associated with the major sink reactions of CH4 in air (reactions with •OH and Cl•), and literature data with reconnaissance measurements of the relative abundances of 13CH3D and 12CH2D2 to estimate the compositions of the largest atmospheric sources. Here we present new methane rare isotopologue data from boreal wetlands, comprising one of the most important sources, in order to evaluate the robustness of the model. Boreal wetlands (>55° N) account for more than half of the wetland area in the Northern hemisphere. We analyzed methane samples from high latitude lakes representing different geographical regions, geological and ecological contexts, methane fluxes, and isotopic signatures. Using clumped isotopes of CH4 we are able to determine the likely production mechanism for natural CH4 samples. So far, all of our analyzed samples except one plot in the microbial pure-culture methanogenesis field (Young et al. 2017) with ranges of -0.2‰ to +1.2‰ for Δ13CH3D, and -29.6‰ to -18.2‰ for Δ12CH2D2. These compositions are far from equilibrium. The one exception, from Lake Doughnut, Alaska, exhibits Δ13CH3D and Δ12CH2D2 values of +5.2‰ and +18.7‰, respectively, which fall near ambient thermodynamic equilibrium values. This may be an effect of methanotrophy. Mean Δ13CH3D and Δ12CH2D2 for all lake samples are +1.7‰ and -15.4‰ respectively, compared to our original estimate of +6.1‰ and +21.2‰ for the wetland methane source based on an assumption of equilibrium. If we assume that these samples are representative of the overall wetland source, Δ13CH3D decreases by 0.8‰ and Δ12CH2D2 decreases by 0.6‰ in our model of bulk atmospheric methane. Δ13CH3D and Δ12CH2D2 values of air (including •OH and Cl• sink

Interstellar C2, CH, and CN in translucent molecular clouds

NARCIS (Netherlands)

Dishoeck, van E.F.; Black, J.H.

1989-01-01

Optical absorption-line techniques have been applied to the study of a number of translucent molecular clouds in which the total column densities are large enough that substantial molecular abundances can be maintained. Results are presented for a survey of absorption lines of interstellar C2, CH,

[(PhCH2O2P(CH32CHNCH(CH32]2PdCl2/CuI as Cocatalyst for Coupling-Cyclization of 2-Iodophenol with Terminal Alkynes in Water

Directory of Open Access Journals (Sweden)

Panli Jiang

2018-03-01

Full Text Available A new and efficient [(PhCH2O2P(CH32CHNCH(CH32]2PdCl2/CuI-co-catalyzed coupling-cyclization reactions of 2-iodophenol with terminal alkynes is described. Different 2-substitued benzo[b]furan derivatives are obtained in good to excellent yields. This protocol employs a relatively low palladium(II catalyst loading in water under air conditions.

Conformational and spectroscopic study of xanthogen ethyl formates, ROC(S)SC(O)OCH2CH3. Isolation of CH3CH2OC(O)SH

Science.gov (United States)

Juncal, Luciana C.; Cozzarín, Melina V.; Romano, Rosana M.

2015-03-01

ROC(S)SC(O)OCH2CH3, with R = CH3sbnd , (CH3)2CHsbnd and CH3(CH2)2sbnd , were obtained through the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3. The liquid compounds were identified and characterized by 1H and 13C NMR and mass spectrometry. The conformations adopted by the molecules were studied by DFT methods. 6 conformers were theoretically predicted for R = CH3sbnd and (CH3)2CHsbnd , while the conformational flexibility of the n-propyl substituent increases the total number of feasible rotamers to 21. For the three molecules, the conformers can be associated in 3 groups, being the most stable the AS forms - the Cdbnd S double bond anti (A) with respect to the Csbnd S single bond and the Ssbnd C single bond syn (S) with respect to the Cdbnd O double bond - followed by AA and SS conformers. The vibrational spectra were interpreted in terms of the predicted conformational equilibrium, presenting the ν(Cdbnd O) spectral region signals corresponding to the three groups of conformers. A moderated pre-resonance Raman enhancement of the ν(Cdbnd S) vibrational mode of CH3(CH2)2OC(S)SC(O)OCH2CH3 was detected, when the excitation radiation approaches the energy of a n → π∗ electronic transition associated with the Cdbnd S chromophore. UV-visible spectra in different solvents were measured and interpreted in terms of TD-DFT calculations. The unknown molecule CH3CH2OC(O)SH was isolated by the UV-visible photolysis of CH3OC(S)SC(O)OCH2CH3 isolated in Ar matrix, and also obtained as a side-product of the reaction between potassium xanthate salts, ROC(S)SK, and ethyl chloroformate, ClC(O)OCH2CH3.

Evolution of CH3NO2/Si interfacial chemistry under reaction conditions: a combined experimental and theoretical study.

Science.gov (United States)

Zhang, Xueqiang; Wang, Chen-Guang; Ji, Wei; Ptasinska, Sylwia

2017-03-16

Dissociative adsorption of CH 3 NO 2 onto a Si(100)-2 × 1 surface is studied using ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT) calculations. The unprecedented scission of the C-N bond in CH 3 NO 2 and the formation of a Si-CH 3 surface species are observed at elevated CH 3 NO 2 pressure (0.5 mbar) and temperature (>573 K).

Photodissociation and photoisomerization dynamics of CH2=CHCHO in solution

International Nuclear Information System (INIS)

Wu Weiqiang; Yang Chunfan; Zhao Hongmei; Liu Kunhui; Su Hongmei

2010-01-01

By means of time-resolved Fourier transform infrared absorption spectroscopy, we have investigated the 193 nm photodissociation and photoisomerization dynamics of the prototype molecule of α,β-enones, acrolein (CH 2 =CHCHO) in CH 3 CN solution. The primary photolysis channels and absolute branching ratios are determined. The most probable reaction mechanisms are clarified by control experiments monitoring the product yields varied with the triplet quencher addition. The predominant channel is the 1,3-H migration yielding the rearrangement product CH 3 CH=C=O with a branching ratio of 0.78 and the less important channel is the α cleavage of C-H bond yielding radical fragments CH 2 =CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet 3 (ππ * ) state rather than the ground S 0 state and the α cleavage of C-H bond is more likely to proceed in the singlet S 1 1 (nπ * ) state. From the solution experiments we have not only acquired clues clarifying the previous controversial mechanisms, but also explored different photochemistry in solution. Compared to the gas phase photolysis which is dominated by photodissociation channels, the most important channel in solution is the photoisomerization of 1,3-H migration. The reason leading to the different photochemistry in solution is further ascribed to the solvent cage effect.

The rate of charge tunneling is insensitive to polar terminal groups in self-assembled monolayers in Ag(TS)S(CH2)(n)M(CH2)(m)T//Ga2O3/EGaIn junctions.

Science.gov (United States)

Yoon, Hyo Jae; Bowers, Carleen M; Baghbanzadeh, Mostafa; Whitesides, George M

2014-01-08

This paper describes a physical-organic study of the effect of uncharged, polar, functional groups on the rate of charge transport by tunneling across self-assembled monolayer (SAM)-based large-area junctions of the form Ag(TS)S(CH2)(n)M(CH2)(m)T//Ga2O3/EGaIn. Here Ag(TS) is a template-stripped silver substrate, -M- and -T are "middle" and "terminal" functional groups, and EGaIn is eutectic gallium-indium alloy. Twelve uncharged polar groups (-T = CN, CO2CH3, CF3, OCH3, N(CH3)2, CON(CH3)2, SCH3, SO2CH3, Br, P(O)(OEt)2, NHCOCH3, OSi(OCH3)3), having permanent dipole moments in the range 0.5 < μ < 4.5, were incorporated into the SAM. A comparison of the electrical characteristics of these junctions with those of junctions formed from n-alkanethiolates led to the conclusion that the rates of charge tunneling are insensitive to the replacement of terminal alkyl groups with the terminal polar groups in this set. The current densities measured in this work suggest that the tunneling decay parameter and injection current for SAMs terminated in nonpolar n-alkyl groups, and polar groups selected from common polar organic groups, are statistically indistinguishable.

Rate Constants for the Reactions of OH with CH(sub 3)Cl, CH(sub 2) C1(sub 2), CHC1(sub 3)and CH(sub 3)Br

Science.gov (United States)

Hsu, H-J.; DeMore, W.

1994-01-01

Rate constants for the reactions of OH with CH3C1, CH2Cl2, CHCl3 and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2)and for CH2Cl2, HFC-161 (CH3CH2F).

Highly efficient alkane oxidation catalyzed by [Mn(V)(N)(CN)4](2-). Evidence for [Mn(VII)(N)(O)(CN)4](2-) as an active intermediate.

Science.gov (United States)

Ma, Li; Pan, Yi; Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Chen, Gui; Lau, Kai-Chung; Lau, Tai-Chu

2014-05-28

The oxidation of various alkanes catalyzed by [Mn(V)(N)(CN)4](2-) using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4](2-) and H2O2 or Ce(IV), followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn═O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4](2-) in CF3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4](-)·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [Mn(V)(N)(CN)4](2-)/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4](2-) to generate a manganese(VII) nitrido oxo active species, [Mn(VII)(N)(O)(CN)4](2-), which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.

Dynamics of the F(-) + CH3I → HF + CH2I(-) Proton Transfer Reaction.

Science.gov (United States)

Zhang, Jiaxu; Xie, Jing; Hase, William L

2015-12-17

Direct chemical dynamics simulations, at collision energies Erel of 0.32 and 1.53 eV, were performed to obtain an atomistic understanding of the F(-) + CH3I reaction dynamics. There is only the F(-) + CH3I → CH3F + I(-) bimolecular nucleophilic substitution SN2 product channel at 0.32 eV. Increasing Erel to 1.53 eV opens the endothermic F(-) + CH3I → HF + CH2I(-) proton transfer reaction, which is less competitive than the SN2 reaction. The simulations reveal proton transfer occurs by two direct atomic-level mechanisms, rebound and stripping, and indirect mechanisms, involving formation of the F(-)···HCH2I complex and the roundabout. For the indirect trajectories all of the CH2I(-) is formed with zero-point energy (ZPE), while for the direct trajectories 50% form CH2I(-) without ZPE. Without a ZPE constraint for CH2I(-), the reaction cross sections for the rebound, stripping, and indirect mechanisms are 0.2 ± 0.1, 1.2 ± 0.4, and 0.7 ± 0.2 Å(2), respectively. Discarding trajectories that do not form CH2I(-) with ZPE reduces the rebound and stripping cross sections to 0.1 ± 0.1 and 0.7 ± 0.5 Å(2). The HF product is formed rotationally and vibrationally unexcited. The average value of J is 2.6 and with histogram binning n = 0. CH2I(-) is formed rotationally excited. The partitioning between CH2I(-) vibration and HF + CH2I(-) relative translation energy depends on the treatment of CH2I(-) ZPE. Without a CH2I(-) ZPE constraint the energy partitioning is primarily to relative translation with little CH2I(-) vibration. With a ZPE constraint, energy partitioning to CH2I(-) rotation, CH2I(-) vibration, and relative translation are statistically the same. The overall F(-) + CH3I rate constant at Erel of both 0.32 and 1.53 eV is in good agreement with experiment and negligibly affected by the treatment of CH2I(-) ZPE, since the SN2 reaction is the major contributor to the total reaction rate constant. The potential energy surface and reaction dynamics for F

Methanesulfonates of high-valent metals. Syntheses and structural features of MoO_2(CH_3SO_3)_2, UO_2(CH_3SO_3)_2, ReO_3(CH_3SO_3), VO(CH_3SO_3)_2, and V_2O_3(CH_3SO_3)_4 and their thermal decomposition under N_2 and O_2 atmosphere

International Nuclear Information System (INIS)

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S.

2011-01-01

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO_3, UO_2(CH_3COO)_2.2 H_2O, Re_2O_7(H_2O)_2, and V_2O_5 with CH_3SO_3H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO_2(CH_3SO_3)_2 (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm"3, Z=8) contains [MoO_2] moieties connected by [CH_3SO_3] ions to form layers parallel to (100). UO_2(CH_3SO_3)_2 (P2_1/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1) "c"i"r"c"l"e, V=1.8937(3) nm"3, Z=8) consists of linear UO_2"2"+ ions coordinated by five [CH_3SO_3] ions, forming a layer structure. VO(CH_3SO_3)_2 (P2_1/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1) "c"i"r"c"l"e, V=0.8290(2) nm"3, Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO_3(CH_3SO_3) (P anti 1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2) "c"i"r"c"l"e, V=1.1523(4) nm"3, Z=8) a chain structure exhibiting infinite O-[ReO_2]-O-[ReO_2]-O chains is formed. Each [ReO_2]-O-[ReO_2] unit is coordinated by two bidentate [CH_3SO_3] ions. V_2O_3(CH_3SO_3)_4 (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm"3, Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH_3SO_3] ligands. Additional methanesulfonate ions connect the [V_2O_3] groups along [001]. Thermal decomposition of the compounds was monitored under N_2 and O_2 atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N_2 the decomposition proceeds with reduction of the metal leading to the oxides MoO_2, U_3O_7, V_4O_7, and VO_2; for MoO_2(CH_3SO_3)_2, a small amount of MoS_2 is formed. If the thermal decomposition is carried out in a atmosphere of O_2 the oxides MoO_3 and V_2O_5 are formed. (Copyright copyright 2011 WILEY-VCH Verlag

Flash and Continuous Photolysis Studies of the Thionitrosyl Complex Cr(CH3CN)5(NS)2+ and the Nitric Oxide Analogs. Reactions of Nitrogen Monosulfide in Solution

DEFF Research Database (Denmark)

Dethlefsen, Johannes Wied; Hedegård, Erik; Rimmer, R. Dale

2009-01-01

Photolysis of the thionitrosyl complex Cr(CH3CN)5(NS)2+ (1) in acetonitrile solution leads to the dissociation of nitrogen monosulfide (NS).  In deaerated solution, this reaction is reversible, and flash photolysis studies demonstrate that NS reacts with Cr(CH3CN)62+ according to the rate law d[1...... dependent quantum yields of 0.3-1.0 mol/Einstein. Mass spectroscopic studies of the product solutions demonstrate formation of S8, presumably from the decomposition of NS. The quantitative photochemical behaviors of 1 and the nitrosyl analog 2 are compared. Udgivelsesdato: Jan....

Methane Provenance Determined by CH2D2 and 13CH3D Abundances

Science.gov (United States)

Kohl, I. E.; Giunta, T.; Warr, O.; Ash, J. L.; Ruffine, L.; Sherwood Lollar, B.; Young, E. D.

2017-12-01

Determining the provenance of naturally occurring methane gases is of major interest to energy companies and atmospheric climate modelers, among others. Bulk isotopic compositions and other geochemical tracers sometimes fail to provide definitive determinations of sources of methane due to complications from mixing and complicated chemical pathways of origin. Recent measurements of doubly-substituted isotopologues of methane, CH2D2 (UCLA) and 13CH3D (UCLA, CalTech, and MIT) have allowed for major improvements in sourcing natural methane gases. Early work has focused on formation temperatures obtained when the relative abundances of both doubly-substituted mass-18 species are consistent with internal equilibrium. When methane gases do not plot on the thermodynamic equilibrium curve in D12CH2D2 vs D13CH3D space, temperatures determined from D13CH3D values alone are usually spurious, even when appearing reasonable. We find that the equilibrium case is actually rare and almost exclusive to thermogenic gases produced at temperatures exceeding 100°C. All other relevant methane production processes appear to generate gases that are not in isotopologue-temperature equilibrium. When gases show departures from equilibrium as determined by the relationship between CH2D2 and 13CH3D abundances, data fall within empirically defined fields representing formation pathways. These fields are thus far consistent between different geological settings and and between lab experiments and natural samples. We have now defined fields for thermogenic gas production, microbial methanogenesis, low temperature abiotic (Sabatier) synthesis and higher temperature FTT synthesis. The majority of our natural methane data can be explained by mixing between end members originating within these production fields. Mixing can appear complex, resulting in both hyper-clumped and anti-clumped isotopologue abundances. In systems where mixtures dominate and end-members are difficult to sample, mixing models

Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

DEFF Research Database (Denmark)

Hurley, MD; Ball, JC; Wallington, TJ

2004-01-01

Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH...... respectively. Using relative rate techniques, a value of k(Cl + CF3(CF2)(3)CH2CHO) = (1.84 +/- 0.30) x 10(-11) cm(3) molecule(-1) s(-1) was determined. The yield of the perfluorinated acid, CF3(CF2)(3)COOH, from the 4:2 fluorotelomer alcohol increased with the diluent gas oxygen concentration......, and CF3(CF2)(3)CH2C(O)OOH are secondary oxidation products. Further irradiation results in the formation of CF3(CF2)(3)COOH, COF2, and CF3OH. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, and CF3(CF2)(3)CH2C(O)OOH are formed from CF3(CF2)(3)CH2CHO oxidation in yields of 46 27 and less than or equal to 27...

Electron energy loss spectroscopy of CH3N2CH3 adsorbed on Ni(100), Ni(111), Cr(100), Cr(111)

International Nuclear Information System (INIS)

Schulz, M.A.

1985-07-01

A study of the adsorption of CH 3 N 2 CH 3 on Ni(100), Ni(111), Cr(100), and Cr(111) using high resolution electron energy loss spectroscopy (EELS) is presented. Under approximately the same conditions of coverage, the vibrational spectra of CH 3 N 2 CH 3 on these four surfaces are quite distinct from one another, implying that the CH 3 N 2 CH 3 -substrate interaction is very sensitive to the physical and electronic structure of each surface. In addition to the room temperature studies, the evolution of surface species on the Ni(100) surface in the temperature range 300 to 425 K was studied. Analysis of the Ni(100) spectra indicates that molecular adsorption, probably through the N lone pair, occurs at room temperature. Spectra taken after annealing the CH 3 N 2 CH 3 -Ni(100) surfaces indicate that CH and CN bond scission occurred at the elevated temperatures. Decomposition of CH 3 N 2 CH 3 takes place on the Ni(111), Cr(100), and Cr(111) surfaces at room temperature, as evidenced by the intensity of the carbon-metal stretch in the corresponding spectra. Possible identities of coadsorbed dissociation products are considered. The stable coverage of surface species on all four surfaces at 300 K is less than one monolayer. A general description of an electron energy loss (EEL) spectrometer is given. Followed by a more specific discussion of some recent modifications to the EEL monochromator assembly used in this laboratory. Both the previous configuration of our monochromator and the new version are briefly described, as an aid to understanding the motivation for the changes as well as the differences in operation of the two versions. For clarity, the new monochromator design is referred to as variable pass, while the previous design is referred to as double pass. A modified tuning procedure for the new monochromator is also presented. 58 refs., 11 figs

A Survey of CH3CN and HC3N in Protoplanetary Disks

Science.gov (United States)

Bergner, Jennifer B.; Guzmán, Viviana G.; Öberg, Karin I.; Loomis, Ryan A.; Pegues, Jamila

2018-04-01

The organic content of protoplanetary disks sets the initial compositions of planets and comets, thereby influencing subsequent chemistry that is possible in nascent planetary systems. We present observations of the complex nitrile-bearing species CH3CN and HC3N toward the disks around the T Tauri stars AS 209, IM Lup, LkCa 15, and V4046 Sgr as well as the Herbig Ae stars MWC 480 and HD 163296. HC3N is detected toward all disks except IM Lup, and CH3CN is detected toward V4046 Sgr, MWC 480, and HD 163296. Rotational temperatures derived for disks with multiple detected lines range from 29 to 73 K, indicating emission from the temperate molecular layer of the disk. V4046 Sgr and MWC 480 radial abundance profiles are constrained using a parametric model; the gas-phase CH3CN and HC3N abundances with respect to HCN are a few to tens of percent in the inner 100 au of the disk, signifying a rich nitrile chemistry at planet- and comet-forming disk radii. We find consistent relative abundances of CH3CN, HC3N, and HCN between our disk sample, protostellar envelopes, and solar system comets; this is suggestive of a robust nitrile chemistry with similar outcomes under a wide range of physical conditions.

Ethanol oxidation reactions catalyzed by water molecules: CH3CH2OH+n H2O→ CH3CHO+ H2+n H2O (n=0,1,2)

Science.gov (United States)

Takahashi, H.; Hisaoka, S.; Nitta, T.

2002-09-01

Ab initio density functional theory calculations have been performed to investigate the catalytic role of water molecules in the oxidation reaction of ethanol: CH3CH2OH+n H2O→ CH3CHO+ H2+n H2O (n=0,1,2) . The results show that the potential energy barrier for the reaction is 88.0 kcal/mol in case of n=0, while it is reduced by ˜34 kcal/mol when two water molecules are involved ( n=2) in the reaction. As a result, the rate constant increases to 3.31×10 -4 s-1, which shows a significant catalytic role of water molecules in the ethanol oxidation reactions.

THE POSSIBLE INTERSTELLAR ANION CH2CN–: SPECTROSCOPIC CONSTANTS, VIBRATIONAL FREQUENCIES, AND OTHER CONSIDERATIONS

International Nuclear Information System (INIS)

Fortenberry, Ryan C.; Lee, Timothy J.; Crawford, T. Daniel

2013-01-01

The A 1 B 1 ⇽ X-tilde 1 A' excitation into the dipole-bound state of the cyanomethyl anion (CH 2 CN – ) has been hypothesized as the carrier for one diffuse interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study, we are employing the use of proven quartic force fields and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for X-tilde 1 A' CH 2 CN – in order to assist in laboratory studies and astronomical observations.

SYNTHESIS AND CHARACTERIZATION OF (MU-5-C5ME5)2TI(R)CL (R = ME, ET, NORMAL-PR, CH=CH2, PH, O-NORMAL-PR) AND THEIR SALT METATHESIS REACTIONS - THERMAL-DECOMPOSITION PATHWAYS OF (MU-5-C5ME5)2TI(ME)R' (R' = ET, CH=CH2, PH, CH2PH)

NARCIS (Netherlands)

LUINSTRA, GA; TEUBEN, JH

Complexes Cp*2Ti(R)Cl (Cp* = eta-5-C5Me5; R = Me (1), Et (2), n-Pr (3), CH=CH2 (4), Ph (5), O-n-Pr (6)) have been prepared by oxidation Of CP*2TiR with lead dichloride. Not every compound Cp*2Ti(R)Cl was accessible and for R = CH2CMe3 and CH2Ph reduction to Cp*2TiCl and R. was observed. Homolysis of

Synthesis and Characterization of (η5-C5Me5)2Ti(R)Cl (R = Me, Et, n-Pr, CH=CH2, Ph, O-n-Pr) and Their Salt Metathesis Reactions. Thermal Decomposition Pathways of (η5-C5Me5)2Ti(Me)R' (R' = Et, CH=CH2, Ph, CH2Ph)

NARCIS (Netherlands)

Luinstra, Gerrit A.; Teuben, Jan H.

1992-01-01

Complexes Cp*2Ti(R)Cl (Cp* = η5-C5Me5; R = Me (1), Et (2), n-Pr (3), CH=CH2 (41, Ph (5), O-n-Pr (6)) have been prepared by oxidation of Cp*2TiR with lead dichloride. Not every compound Cp*2Ti(R)Cl was accessible and for R = CH2CMe3 and CH2Ph reduction to Cp*2TiCl and R· was observed. Homolysis of

VACUUM ULTRAVIOLET PHOTOABSORPTION SPECTRA OF NITRILE ICES FOR THEIR IDENTIFICATION ON PLUTO

International Nuclear Information System (INIS)

Sivaraman, B.; Pavithraa, S.; Lo, J.-I.; Cheng, B.-M.; Sekhar, B. N. Raja; Hill, H.; Mason, N. J.

2016-01-01

Icy bodies, such as Pluto, are known to harbor simple and complex molecules. The recent New Horizons flyby of Pluto has revealed a complex surface composed of bright and dark ice surfaces, indicating a rich chemistry based on nitrogen (N 2 ), methane (CH 4 ), and carbon monoxide (CO). Nitrile (CN) containing molecules such as acetonitrile (CH 3 CN), propionitrile (CH 3 CH 2 CN), butyronitrile (CH 3 CH 2 CH 2 CN), and isobutyronitrile ((CH 3 ) 2 CHCN) are some of the nitrile molecules that are known to be synthesized by radiative processing of such simple ices. Through the provision of a spectral atlas for such compounds we propose that such nitriles may be identified from the ALICE payload on board New Horizons .

Atmospheric chemistry of CH3CHF2 (R-152a): mechanism of the CH3CF2O2+HO2 reaction

DEFF Research Database (Denmark)

Hashikawa, Y; Kawasaki, M; Andersen, Mads Peter Sulbæk

2004-01-01

FTIR smog chamber techniques have been used to investigate the mechanism of the reaction of CH3CF2O2 with HO2 radicals in 100-700 Torr of synthetic air at 296 K. The reaction gives CH3CF2OOH and COF2 in molar yields of 0.53 +/- 0.05 and 0.47 +/- 0.05, respectively. Results are discussed with resp......FTIR smog chamber techniques have been used to investigate the mechanism of the reaction of CH3CF2O2 with HO2 radicals in 100-700 Torr of synthetic air at 296 K. The reaction gives CH3CF2OOH and COF2 in molar yields of 0.53 +/- 0.05 and 0.47 +/- 0.05, respectively. Results are discussed...

Ultraviolet absorption spectra and kinetics of CH3S and CH2SH radicals

DEFF Research Database (Denmark)

Anastasi, C.; Broomfield, M.; Nielsen, O.J.

1991-01-01

The ultraviolet absorption spectra of CH3S and CH2SH radicals have been measured between 215 and 380 nm using the pulse-radiolysis/kinetic-absorption method. One absorption band between 250 and 300 nm and one around 215 nm have been tentatively assigned to the CH2SH and CH3S radicals, respectively....... This spectrum has been used to measure the self-reaction rates of these radicals. Rate constants of 4 x 10(-11) and 7 x 10(-11) cm3 molecule-1 s-1 have been measured at 298 K for CH3S and CH2SH recombination, respectively. The possible reaction pathways are discussed....

Submillimeter laboratory identification of CH{sup +} and CH{sub 2}D{sup +}

Energy Technology Data Exchange (ETDEWEB)

Amano, T. [Department of Chemistry and Department of Physics and Astronomy, University of Waterloo, Waterloo, ON N2L 3G1 (Canada)

2015-01-22

Laboratory identification of two basic and important interstellar molecular ions is presented. The J = 1 - 0 rotational transition of {sup 12}CH{sup +} together with those of {sup 13}CH{sup +} and {sup 12}CD{sup +} was observed in the laboratory. The newly obtained frequencies were found to be different from those reported previously. Various experimental evidences firmly support the new measurements. In addition, the Zeeman effect and the spin-rotation hyperfine interaction enforce the laboratory identification with no ambiguity. Rotational lines of CH{sub 2}D{sup +} were observed in the submillimeter-wave region. This laboratory observation is consistent with a recent tentative identification of CH{sub 2}D{sup +} toward Ori IRc2.

CH2 molecular beam source

International Nuclear Information System (INIS)

Porter, R.A.R.; Grosser, A.E.

1980-01-01

A molecular beam source of CH 2 is described. Coaxial beams of methylene halide and alkali metal react and the mixture is formed into a molecular beam. Passage through a mechanical velocity selector rotating at a suitably high speed purifies the beam, separating light, fast CH 2 from heavier, slower contaminating species

Infrared Spectra and Structures of SiH{sub 2}-(CH{sub 2}){sub 2} and CH{sub 2}=CH-SiH{sub 3} Intermediates Prepared in Reactions of Laser-ablated Silicon Atoms with Ethane

Energy Technology Data Exchange (ETDEWEB)

Cho, Han-Gook [Incheon National University, Incheon (Korea, Republic of); Andrews, Lester [University of Virginia, Charlottesville (United States)

2016-03-15

SiH{sub 2}-(CH{sub 2}){sub 2} and CH{sub 2}=CH-SiH{sub 3} were observed in the matrix IR spectra following reactions of laser-ablated Si atoms with ethane on the basis of correlation with computed frequencies. Evidently photon energy is required for the formation of the cyclic Si compound. These Si complexes are similar to the primary products in the previous studies of group 4 metals, in line with the previous results that s{sup 2}p{sup 2} and s{sup 2}d{sup 2} electronic configurations yield similar products. The relatively long C–C bond in the cyclic Si product reflects the structural strain, and the short C-Si and C-C bonds of CH{sub 3}CH=SiH{sub 2} and CH{sub 2}=CH-SiH{sub 3} show that they are true double bonds in line with the natural bond orders. Reactions of transition-metal atoms with small alkanes and halomethanes have been studied in a series of recent investigations. High oxidation-state products (methylidenes and methylidynes) along with insertion complexes were identified in the matrix spectra. It is interesting whether or not Si, a group 14 metalloid, undergoes similar reactions with larger hydrocarbons to provide higher oxidation-state compounds.

Post-transition state dynamics and product energy partitioning following thermal excitation of the F⋯HCH2CN transition state: Disagreement with experiment.

Science.gov (United States)

Pratihar, Subha; Ma, Xinyou; Xie, Jing; Scott, Rebecca; Gao, Eric; Ruscic, Branko; Aquino, Adelia J A; Setser, Donald W; Hase, William L

2017-10-14

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH 3 CN → HF + CH 2 CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. The experiments were performed at 300 K, and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F⋯HCH 2 CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH 2 CN and then trapping in the CH 2 CN⋯HF post-reaction potential energy well of ∼10 kcal/mol with respect to the HF + CH 2 CN products. In contrast to this IRC, five different trajectory types were observed: the majority proceeded by direct H-atom transfer and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH 2 CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. Simulations with an anharmonic zero-point energy constraint gave product distributions for relative translation, HF rotation, HF vibration, CH 2 CN rotation, and CH 2 CN vibration as 5%, 11%, 60%, 7%, and 16%, respectively. In contrast, the experimental energy partitioning percentages to HF rotation and vibration are 6% and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH 3 CN �

Post-transition state dynamics and product energy partitioning following thermal excitation of the F⋯HCH2CN transition state: Disagreement with experiment

Science.gov (United States)

Pratihar, Subha; Ma, Xinyou; Xie, Jing; Scott, Rebecca; Gao, Eric; Ruscic, Branko; Aquino, Adelia J. A.; Setser, Donald W.; Hase, William L.

2017-10-01

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH3CN → HF + CH2CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. The experiments were performed at 300 K, and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F⋯HCH2CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH2CN and then trapping in the CH2CN⋯HF post-reaction potential energy well of ˜10 kcal/mol with respect to the HF + CH2CN products. In contrast to this IRC, five different trajectory types were observed: the majority proceeded by direct H-atom transfer and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH2CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. Simulations with an anharmonic zero-point energy constraint gave product distributions for relative translation, HF rotation, HF vibration, CH2CN rotation, and CH2CN vibration as 5%, 11%, 60%, 7%, and 16%, respectively. In contrast, the experimental energy partitioning percentages to HF rotation and vibration are 6% and 41%. Comparisons are made between the current simulation and those for other F + H-atom abstraction reactions. The simulation product energy partitioning and HF vibrational population for F + CH3CN → HF + CH2CN

CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4: Infrared spectra, radiative efficiencies, and global warming potentials

International Nuclear Information System (INIS)

Wallington, Timothy J.; Pivesso, Bruno Pasquini; Lira, Alane Moura; Anderson, James E.; Nielsen, Claus Jørgen; Andersen, Niels Højmark; Hodnebrog, Øivind

2016-01-01

Infrared spectra for the title compounds were measured experimentally in 700 Torr of air at 295 K and systematically modeled in B3LYP, M06-2X and MP2 calculations employing various basis sets. Calibrated infrared spectra over the wavenumber range 600–3500 cm"−"1 are reported and combined with literature data to provide spectra for use in experimental studies and radiative transfer calculations. Integrated absorption cross sections are (units of cm"−"1 molecule"−"1): CH_3Cl, 660–780 cm"−"1, (3.89±0.19)×10"−"1"8; CH_2Cl_2, 650–800 cm"−"1, (2.16±0.11)×10"−"1"7; CHCl_3, 720–810 cm"−"1, (4.08±0.20)×10"−"1"7; and CCl_4, 730–825 cm"−"1, (6.30±0.31)×10"−"1"7. CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 have radiative efficiencies of 0.004, 0.028, 0.070, and 0.174 W m"−"2 ppb"−"1 and global warming potentials (100 year horizon) of 5, 8, 15, and 1775, respectively. Quantum chemistry calculations generally predict larger band intensities than the experimental values. The best agreement with experiments is obtained in MP2(Full) calculations employing basis sets of at least triple-zeta quality augmented by diffuse functions. The B3LYP functional is found ill-suited for calculating vibrational frequencies and infrared intensities of halocarbons. - Highlights: • Infrared spectra reported for CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4. • REs of CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 are 0.004, 0.028, 0.070, and 0.174 W m"−"2 ppb"−"1, respectively. • GWPs of CH_3Cl, CH_2Cl_2, CHCl_3, and CCl_4 are 5, 8, 15, and 1775, respectively.

Activation of sp3-CH Bonds in a Mono(pentamethylcyclopentadienyl)yttrium Complex. X-ray Crystal Structures and Dynamic Behavior of Cp*Y(o-C6H4CH2NMe2)2 and Cp*Y[o-C6H4CH2NMe(CH2-μ)][μ-o-C6H4CH2NMe(CH2-μ)]YCp*[THF

NARCIS (Netherlands)

Booij, Martin; Kiers, Niklaas H.; Meetsma, Auke; Teuben, Jan H.; Smeets, Wilberth J.J.; Spek, Anthony L.

1989-01-01

Reaction of Y(o-C6H4CH2NMe2)3 (1) with Cp*H gives Cp*Y(o-C6H4CH2NMe2)2 (2), which crystallizes in the monoclinic space group P21/n (No. 14) with a = 18.607 (4) Å, b = 15.633 (3) Å, c = 8.861 (3) Å, β = 102.73 (3)°, and Z = 4. Least-squares refinement with 3006 independent reflections (F > 4.0σ(F))

Ab Initio Chemical Kinetics for the CH3 + O((3)P) Reaction and Related Isomerization-Decomposition of CH3O and CH2OH Radicals.

Science.gov (United States)

Xu, Z F; Raghunath, P; Lin, M C

2015-07-16

The kinetics and mechanism of the CH3 + O reaction and related isomerization-decomposition of CH3O and CH2OH radicals have been studied by ab initio molecular orbital theory based on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVTZ, CCSD/aug-cc-pVDZ, and G2M//B3LYP/6-311+G(3df,2p) levels of theory. The predicted potential energy surface of the CH3 + O reaction shows that the CHO + H2 products can be directly generated from CH3O by the TS3 → LM1 → TS7 → LM2 → TS4 path, in which both LM1 and LM2 are very loose and TS7 is roaming-like. The result for the CH2O + H reaction shows that there are three low-energy barrier processes including CH2O + H → CHO + H2 via H-abstraction and CH2O + H → CH2OH and CH2O + H → CH3O by addition reactions. The predicted enthalpies of formation of the CH2OH and CH3O radicals at 0 K are in good agreement with available experimental data. Furthermore, the rate constants for the forward and some key reverse reactions have been predicted at 200-3000 K under various pressures. Based on the new reaction pathway for CH3 + O, the rate constants for the CH2O + H and CHO + H2 reactions were predicted with the microcanonical variational transition-state/Rice-Ramsperger-Kassel-Marcus (VTST/RRKM) theory. The predicted total and individual product branching ratios (i.e., CO versus CH2O) are in good agreement with experimental data. The rate constant for the hydrogen abstraction reaction of CH2O + H has been calculated by the canonical variational transition-state theory with quantum tunneling and small-curvature corrections to be k(CH2O + H → CHO + H2) = 2.28 × 10(-19) T(2.65) exp(-766.5/T) cm(3) molecule(-1) s(-1) for the 200-3000 K temperature range. The rate constants for the addition giving CH3O and CH2OH and the decomposition of the two radicals have been calculated by the microcanonical RRKM theory with the time-dependent master equation solution of the multiple quantum well system in the 200-3000 K temperature range at 1 Torr to

SYNTHESIS OF NEW BIS(CYCLOPENTADIENYL)YTTRIUM COMPLEXES WITH ETHER FUNCTIONALIZED CYCLOPENTADIENYL LIGANDS - CRYSTAL-STRUCTURE OF [(C(5)H(4)CH(2)CH(2)OME)(2)Y(MU-H)(2)BH2

NARCIS (Netherlands)

LASKE, DA; DUCHATEAU, R; TEUBEN, JH; SPEK, AL

1993-01-01

Treatment of C(5)H(4)CH(2)CH(2)OMe.Li(TMEDA) (TMEDA = N, N, N', N' tetramethylethylenediamine) with half an equivalent of YCl3(THF)(3.5) in toluene afforded the salt- and solvent-free dimeric biscyclopentadienyl yttrium chloride [(C(5)H(4)CH(2)CH(2)OMe)(2)Y-(mu-Cl)](2) (1). Reaction of 1 with one

CH2 - Lighting and Physiology

Directory of Open Access Journals (Sweden)

Sergio Altomonte

2012-11-01

Full Text Available This paper explains the designed performances of the new CH2 building in Melbourne, Australia. CH2 is an environmentally significant project that involves biomimicry of natural systems to produce indoor conditions that are conducive to user comfort, health and productivity. This paper focuses on lighting and physiology and examines the solutions chosen for artificial and natural lighting and the likely effects these will have on building occupants. The purpose of the paper is to critically comment on the adopted strategy and, cognisance of contemporary thinking in lighting design, to judge the effectiveness of this aspect of the project with a view to later verification and post-occupancy review. The paper concludes that CH2 is an exemplar of lighting innovation that provides valuable lessons to designers of office buildings, particularly in the Melbourne CSD.

ChIPBase v2.0: decoding transcriptional regulatory networks of non-coding RNAs and protein-coding genes from ChIP-seq data.

Science.gov (United States)

Zhou, Ke-Ren; Liu, Shun; Sun, Wen-Ju; Zheng, Ling-Ling; Zhou, Hui; Yang, Jian-Hua; Qu, Liang-Hu

2017-01-04

The abnormal transcriptional regulation of non-coding RNAs (ncRNAs) and protein-coding genes (PCGs) is contributed to various biological processes and linked with human diseases, but the underlying mechanisms remain elusive. In this study, we developed ChIPBase v2.0 (http://rna.sysu.edu.cn/chipbase/) to explore the transcriptional regulatory networks of ncRNAs and PCGs. ChIPBase v2.0 has been expanded with ∼10 200 curated ChIP-seq datasets, which represent about 20 times expansion when comparing to the previous released version. We identified thousands of binding motif matrices and their binding sites from ChIP-seq data of DNA-binding proteins and predicted millions of transcriptional regulatory relationships between transcription factors (TFs) and genes. We constructed 'Regulator' module to predict hundreds of TFs and histone modifications that were involved in or affected transcription of ncRNAs and PCGs. Moreover, we built a web-based tool, Co-Expression, to explore the co-expression patterns between DNA-binding proteins and various types of genes by integrating the gene expression profiles of ∼10 000 tumor samples and ∼9100 normal tissues and cell lines. ChIPBase also provides a ChIP-Function tool and a genome browser to predict functions of diverse genes and visualize various ChIP-seq data. This study will greatly expand our understanding of the transcriptional regulations of ncRNAs and PCGs. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

Simulasi Numeris Karakteristik Pembakaran CH4/CO2/Udara dan CH4/CO2/O2 pada Counterflow Premixed Burner

Directory of Open Access Journals (Sweden)

Hangga Wicaksono

2017-08-01

Full Text Available The high amount of CO2 produced in a conventional biogas reactor needs to be considered. A further analysis is needed in order to investigate the effect of CO2 addition especially in thermal and chemical kinetics aspect. This numerical study has been held to analyze the effect of CO2 in CH4/CO2/O­2 and CH4/CO2/Air premixed combustion. In this study one dimensional analisys in a counterflow burner has been performed. The volume fraction of CO2 used in this study was 0%-40% from CH4’s volume fraction, according to the amount of CO2 in general phenomenon. Based on the flammability limits data, the volume fraction of CH4 used was 5-61% in O2 environment and 5-15% in air environment. The results showed a decreasing temperature along with the increasing percentage of CO2 in each mixtures, but the effect was quite smaller especially in stoichiometric and lean mixture. CO2 could affects thermally (by absorbing heat due to its high Cp and also made the production of unburnt fuel species such as CO relatively higher.

Contrast between the mechanisms for dissociative electron attachment to CH3SCN and CH3NCS

Science.gov (United States)

Miller, Thomas M.; Viggiano, Albert A.; Shuman, Nicholas S.

2018-05-01

The kinetics of thermal electron attachment to methyl thiocyanate (CH3SCN), methyl isothiocyanate (CH3NCS), and ethyl thiocyanate (C2H5SCN) were measured using flowing afterglow-Langmuir probe apparatuses at temperatures between 300 and 1000 K. CH3SCN and C2H5SCN undergo inefficient dissociative attachment to yield primarily SCN- at 300 K (k = 2 × 10-10 cm3 s-1), with increasing efficiency as temperature increases. The increase is well described by activation energies of 0.17 eV (CH3SCN) and 0.14 eV (C2H5SCN). CN- product is formed at product but at a rate at 300 K that is below our detection threshold (k differentiating the two mechanisms. The kinetic modeling reproduces the CH3NCS data only if dissociation through the transient anion is considered.

Photodissociation and photoisomerization dynamics of CH2=CHCHO in solution

Science.gov (United States)

Wu, Weiqiang; Yang, Chunfan; Zhao, Hongmei; Liu, Kunhui; Su, Hongmei

2010-03-01

By means of time-resolved Fourier transform infrared absorption spectroscopy, we have investigated the 193 nm photodissociation and photoisomerization dynamics of the prototype molecule of α,β-enones, acrolein (CH2CHCHO) in CH3CN solution. The primary photolysis channels and absolute branching ratios are determined. The most probable reaction mechanisms are clarified by control experiments monitoring the product yields varied with the triplet quencher addition. The predominant channel is the 1,3-H migration yielding the rearrangement product CH3CHCO with a branching ratio of 0.78 and the less important channel is the α cleavage of CH bond yielding radical fragments CH2CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet (ππ ∗)3 state rather than the ground S0 state and the α cleavage of CH bond is more likely to proceed in the singlet S1 (nπ∗)1 state. From the solution experiments we have not only acquired clues clarifying the previous controversial mechanisms, but also explored different photochemistry in solution. Compared to the gas phase photolysis which is dominated by photodissociation channels, the most important channel in solution is the photoisomerization of 1,3-H migration. The reason leading to the different photochemistry in solution is further ascribed to the solvent cage effect.

Thermodynamic activity of saturated solutions of CsClO4 in ethylene glycol and its analogs of the HOCH2(CH2CH2O)nCH2OH series

International Nuclear Information System (INIS)

Krasnoperova, A.P.; Ivanova, E.F.; Kijko, S.M.; Yukhno, G.D.

1997-01-01

Solubility of CsClO 4 in ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with molar mass 300 and 400 in the temperature range of 273.15-318.15 K has been ascertained by the method of radioactive indicators. Dependence of saturated solutions activity on temperature, dielectric permittivity and the number of (CH 2 CH 2 O) ether groups in glycols is discussed

Bimolecular reaction of CH3 + CO in solid p-H2: Infrared absorption of acetyl radical (CH3CO) and CH3-CO complex

Science.gov (United States)

Das, Prasanta; Lee, Yuan-Pern

2014-06-01

We have recorded infrared spectra of acetyl radical (CH3CO) and CH3-CO complex in solid para-hydrogen (p-H2). Upon irradiation at 248 nm of CH3C(O)Cl/p-H2 matrices, CH3CO was identified as the major product; characteristic intense IR absorption features at 2990.3 (ν9), 2989.1 (ν1), 2915.6 (ν2), 1880.5 (ν3), 1419.9 (ν10), 1323.2 (ν5), 836.6 (ν7), and 468.1 (ν8) cm-1 were observed. When CD3C(O)Cl was used, lines of CD3CO at 2246.2 (ν9), 2244.0 (ν1), 1866.1 (ν3), 1046.7 (ν5), 1029.7 (ν4), 1027.5 (ν10), 889.1 (ν6), and 723.8 (ν7) cm-1 appeared. Previous studies characterized only three vibrational modes of CH3CO and one mode of CD3CO in solid Ar. In contrast, upon photolysis of a CH3I/CO/p-H2 matrix with light at 248 nm and subsequent annealing at 5.1 K before re-cooling to 3.2 K, the CH3-CO complex was observed with characteristic IR features at 3165.7, 3164.5, 2150.1, 1397.6, 1396.4, and 613.0 cm-1. The assignments are based on photolytic behavior, observed deuterium isotopic shifts, and a comparison of observed vibrational wavenumbers and relative IR intensities with those predicted with quantum-chemical calculations. This work clearly indicates that CH3CO can be readily produced from photolysis of CH3C(O)Cl because of the diminished cage effect in solid p-H2 but not from the reaction of CH3 + CO because of the reaction barrier. Even though CH3 has nascent kinetic energy greater than 87 kJ mol-1 and internal energy ˜42 kJ mol-1 upon photodissociation of CH3I at 248 nm, its energy was rapidly quenched so that it was unable to overcome the barrier height of ˜27 kJ mol-1 for the formation of CH3CO from the CH3 + CO reaction; a barrierless channel for formation of a CH3-CO complex was observed instead. This rapid quenching poses a limitation in production of free radicals via bimolecular reactions in p-H2.

On the use of satellite-derived CH4 : CO2 columns in a joint inversion of CH4 and CO2 fluxes

NARCIS (Netherlands)

Pandey, S.

2015-01-01

We present a method for assimilating total column CH4 : CO2 ratio measurements from satellites for inverse modeling of CH4 and CO2 fluxes using the variational approach. Unlike conventional approaches, in which retrieved CH4 : CO2 are multiplied by model-derived total column CO2 and only the

Kinetics of the R + HBr ↔ RH + Br (CH3CHBr, CHBr2 or CDBr2) equilibrium. Thermochemistry of the CH3CHBr and CHBr2 radicals

International Nuclear Information System (INIS)

Seetula, Jorma A.; Eskola, Arkke J.

2008-01-01

The kinetics of the reaction of the CH 3 CHBr, CHBr 2 or CDBr 2 radicals, R, with HBr have been investigated in a temperature-controlled tubular reactor coupled to a photoionization mass spectrometer. The CH 3 CHBr (or CHBr 2 or CDBr 2 ) radical was produced homogeneously in the reactor by a pulsed 248 nm exciplex laser photolysis of CH 3 CHBr 2 (or CHBr 3 or CDBr 3 ). The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature. The reactions were studied separately from 253 to 344 K (CH 3 CHBr + HBr) and from 288 to 477 K (CHBr 2 + HBr) and in these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1σ + Student's t values, units in cm 3 molecule -1 s -1 , no error limits for the third reaction): k(CH 3 CHBr + HBr) = (1.7 ± 1.2) x 10 -13 exp[+ (5.1 ± 1.9) kJ mol -1 /RT], k(CHBr 2 + HBr) = (2.5 ± 1.2) x 10 -13 exp[-(4.04 ± 1.14) kJ mol -1 /RT] and k(CDBr 2 + HBr) = 1.6 x 10 -13 exp(-2.1 kJ mol -1 /RT). The energy barriers of the reverse reactions were taken from the literature. The enthalpy of formation values of the CH 3 CHBr and CHBr 2 radicals and an experimental entropy value at 298 K for the CH 3 CHBr radical were obtained using a second-law method. The result for the entropy value for the CH 3 CHBr radical is 305 ± 9 J K -1 mol -1 . The results for the enthalpy of formation values at 298 K are (in kJ mol -1 ): 133.4 ± 3.4 (CH 3 CHBr) and 199.1 ± 2.7 (CHBr 2 ), and for α-C-H bond dissociation energies of analogous compounds are (in kJ mol -1 ): 415.0 ± 2.7 (CH 3 CH 2 Br) and 412.6 ± 2.7 (CH 2 Br 2 ), respectively

The {sup 12}C/{sup 13}C Ratio in Sgr B2(N): Constraints for Galactic Chemical Evolution and Isotopic Chemistry

Energy Technology Data Exchange (ETDEWEB)

Halfen, D. T.; Ziurys, L. M. [Department of Chemistry and Biochemistry, University of Arizona, 1305 E. 4th Street, Tucson, AZ 85719 (United States); Woolf, N. J., E-mail: halfend@email.arizona.edu [Department of Astronomy, Arizona Radio Observatory, University of Arizona, 933 North Cherry Avenue, Tucson, AZ 85721 (United States)

2017-08-20

A study has been conducted of {sup 12}C/{sup 13}C ratios in five complex molecules in the Galactic center. H{sub 2}CS, CH{sub 3}CCH, NH{sub 2}CHO, CH{sub 2}CHCN, and CH{sub 3}CH{sub 2}CN and their {sup 13}C-substituted species have been observed in numerous transitions at 1, 2, and 3 mm, acquired in a spectral-line survey of Sgr B2(N), conducted with the telescopes of the Arizona Radio Observatory (ARO). Between 22 and 54 individual, unblended lines for the {sup 12}C species and 2–54 for {sup 13}C-substituted analogs were modeled in a global radiative transfer analysis. All five molecules were found to consistently exhibit two velocity components near V {sub LSR} ∼ 64 and 73 km s{sup −1}, with column densities ranging from N {sub tot} ∼ 3 × 10{sup 14} − 4 × 10{sup 17} cm{sup −2} and ∼2 × 10{sup 13} − 1 × 10{sup 17} cm{sup −2} for the {sup 12}C and {sup 13}C species, respectively. Based on 14 different isotopic combinations, ratios were obtained in the range {sup 12}C/{sup 13}C = 15 ± 5 to 33 ± 13, with an average value of 24 ± 7, based on comparison of column densities. These measurements better anchor the {sup 12}C/{sup 13}C ratio at the Galactic center, and suggest a slightly revised isotope gradient of {sup 12}C/{sup 13}C = 5.21(0.52) D {sub GC} + 22.6(3.3). As indicated by the column densities, no preferential {sup 13}C enrichment was found on the differing carbon sites of CH{sub 3}CCH, CH{sub 2}CHCN, and CH{sub 3}CH{sub 2}CN. Because of the elevated temperatures in Sgr B2(N), {sup 13}C isotopic substitution is effectively “scrambled,” diminishing chemical fractionation effects. The resulting ratios thus reflect stellar nucleosynthesis and Galactic chemical evolution, as is likely the case for most warm clouds.

Atmospheric chemistry of cyc-CF2CF2CF2CH=CH-: Kinetics, products, and mechanism of gas-phase reaction with OH radicals, and atmospheric implications

Science.gov (United States)

Guo, Qin; Zhang, Ni; Uchimaru, Tadafumi; Chen, Liang; Quan, Hengdao; Mizukado, Junji

2018-04-01

The rate constants for the gas-phase reactions of cyc-CF2CF2CF2CH=CH- with OH radicals were determined by a relative rate method between 253 and 328 K. The rate constant k1 at 298 K was measured to be (1.08 ± 0.04) × 10-13 cm3 molecule-1 s-1, and the Arrhenius expression was k1 = (3.72 ± 0.14) × 10-13 exp [(-370 ± 12)/T]. The atmospheric lifetime of cyc-CF2CF2CF2CH=CH- was calculated to be 107 d. The products and mechanism for the reaction of cyc-CF2CF2CF2CH=CH- with OH radicals were also investigated. CO, CO2, and COF2 were identified as the main carbon-containing products following the OH-initiated reaction. Moreover, the radiative efficiency (RE) was determined to be 0.143 W m-2 ppb-1, and the global warming potentials (GWPs) for 20, 100, and 500 yr were 54, 15, and 4, respectively. The photochemical ozone creation potential of the title compound was estimated to be 1.3.

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.

Post-transition state dynamics and product energy partitioning following thermal excitation of the F∙∙∙HCH₂ CN transition state: Disagreement with experiment

Energy Technology Data Exchange (ETDEWEB)

Pratihar, Subha [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Ma, Xinyou [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Xie, Jing [Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA; Scott, Rebecca [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Gao, Eric [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; Ruscic, Branko [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA and Computation Institute, University of Chicago, Chicago, Illinois 60637, USA; Aquino, Adelia J. A. [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA; School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, People’s Republic of China; Institute for Soil Research University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, A-1190 Vienna, Austria; Setser, Donald W. [Institute for Soil Research University of Natural Resources and Life Sciences Vienna, Peter-Jordan-Strasse 82, A-1190 Vienna, Austria; Hase, William L. [Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061, USA

2017-10-14

Born-Oppenheimer direct dynamics simulations were performed to study atomistic details of the F + CH₃CN → HF + CH₂CN H-atom abstraction reaction. The simulation trajectories were calculated with a combined M06-2X/MP2 algorithm utilizing the 6-311++G** basis set. In accord with experiment and assuming the accuracy of transition state theory (TST), the trajectories were initiated at the F-HCH₂CN abstraction TS with a 300 K Boltzmann distribution of energy and directed towards products. Recrossing of the TS was negligible, confirming the accuracy of TST for the simulation. HF formation was rapid, occurring within 0.014 ps of the trajectory initiation. The intrinsic reaction coordinate (IRC) for reaction involves rotation of HF about CH₂CN and then trapping in the CH₂CN-HF post-reaction potential energy well of ~10 kcal/mol with respect to the HF + CH₂CN products. In contrast to this IRC, five different trajectory types were observed, with the majority involving direct dissociation and only 11% approximately following the IRC. The HF vibrational and rotational quantum numbers, n and J, were calculated when HF was initially formed and they increase as potential energy is released in forming the HF + CH₂CN products. The population of the HF product vibrational states is only in qualitative agreement with experiment, with the simulations showing depressed and enhanced populations of the n = 1 and 2 states as compared to experiment. From the simulations and with an anharmonic zero-point energy constraint, the percentage partitioning of the product energy to relative translation, HF rotation, HF vibration, CH₂CN rotation and CH₂CN vibration is 5, 11, 60, 7, and 16%, respectively. In contrast the experimental energy partitioning percentages to HF rotation and vibration are 6 and 41%. Comparisons are made between the current simulation and those for other F + H

Origin of selenium–gold interaction in F2CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH3): Synergistic effects

International Nuclear Information System (INIS)

Guo, Xin; Yang, Yu-Ping; Li, Qing-Zhong; Li, Hai-Bei

2016-01-01

Selenium–gold interaction plays an important role in crystal materials, molecular self-assembly, and pharmacochemistry involving gold. In this paper, we unveiled the mechanism and nature of selenium–gold interaction by studying complexes F 2 CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH 3 ). The results showed that the formation of selenium–gold interaction is mainly attributed to the charge transfer from the lone pair of Se atom to the Au—Y anti-bonding orbital. Energy decomposition analysis indicated that the polarization energy is nearly equivalent to or exceeds the electrostatic term in the selenium–gold interaction. Interestingly, the chalcogen–gold interaction becomes stronger with the increase of chalcogen atomic mass in F 2 CX⋯AuCN (X = O, S, Se, and Te). The cyclic ternary complexes are formed with the introduction of NH 3 into F 2 CSe⋯AuY, in which selenium–gold interaction is weakened and selenium–nitrogen interaction is strengthened due to the synergistic effects.

Raman study of vibrational dephasing in liquid CH3CN and CD3CN

International Nuclear Information System (INIS)

Schroeder, J.; Schiemann, V.H.; Sharko, P.T.; Jonas, J.

1977-01-01

The Raman line shapes of the ν 1 (a 1 ) C--H and C--D fundamentals in liquid acetonitrile and acetonitrile-d 3 have been measured as a function of pressure up to 4 kbar within the temperature interval 30--120 degreeC. Densities have also been determined. From the isotropic component of the vibrational Raman band shape the vibrational relaxation times have been obtained as a function of temperature and pressure (density). The experimental results can be summarized as follows: (i) as T increases at constant density rho, the vibrational relaxation rate (tau/sub vib/) -1 increases; (ii) at constant T as density is raised tau/sub vib/ -1 increases; (iii) at constant pressure the T increase produces higher tau/sub vib/ -1 , however, the change is more pronounced for the CD 3 CN liquid. Isotopic dilution studies of the CH 3 CN/CD 3 CN mixtures shows no significant effect on (tau/sub vib/ -1 ). The experimental data are interpreted in terms of the Kubo stochastic line shape theory and the dephasing model of Fischer and Laubereau. The results based on Kubo formalism indicate that dephasing is the dominant relaxation mechanism and that the modulation is fast. The isolated binary collision model proposed by Fischer and Laubereau for vibrational dephasing reproduces the essential features of the density and temperature dependence of the (tau/sub vib/) -1 and suggests that pure dephasing is the dominant broadening mechanism for the isotropic line shapes studied. In the calculation the elastic collision times were approximated by the Enskog relaxation times

(Phosphinoalkyl)silanes. 4.(1) Hydrozirconation as a Non-Photochemical Route to (Phosphinopropyl)silanes: Facile Assembly of the Bis(3-(diphenylphosphino)propyl)silyl ("biPSi") Ligand Framework. Access to the Related Poly(3-(dimethylsilyl)propyl)phosphines R(n)()P(CH(2)CH(2)CH(2)SiMe(2)H)(3)(-)(n)() (n = 1, R = Ph; n = 0).

Science.gov (United States)

Zhou, Xiaobing; Stobart, Stephen R.; Gossage, Robert A.

1997-08-13

Treatment of SiEt(3)(CH=CH(2)) with ZrCp(2)HCl (Schwartz's reagent) followed by reaction with PPh(2)Cl provides a high-yield (75%) route to Ph(2)PCH(2)CH(2)SiEt(3), and accordingly hydrozirconation of CH(2)=CHCH(2)SiHMe(2) affords the intermediate ZrCp(2)(CH(2)CH(2)CH(2)SiHMe(2))Cl (2). The latter, which is very sensitive to hydrolysis and reacts with HCl forming SiHMe(2)Pr(n)() and with NBS or I(2) affording SiHMe(2)CH(2)CH(2)CH(2)X (X = Br (3), I (4)), behaves similarly with PPh(2)Cl, PPhCl(2), or PBr(3) undergoing cleavage to the known Ph(2)PCH(2)CH(2)CH(2)SiMe(2)H (i.e. chelH, A) and the novel bis- and tris(silylpropyl)phosphines PhP(CH(2)CH(2)CH(2)SiMe(2)H)(2) (5) and P(CH(2)CH(2)CH(2)SiMe(2)H)(3) (6), respectively, with concomitant formation of ZrCp(2)Cl(2). Corresponding hydroboration of allylsilanes is facile, but subsequent phosphine halide cleavage yields (phosphinoalkyl)silanes only as constituents of intractable mixtures. Hydrozirconation followed by phosphination with PPh(2)Cl also converts SiHMe(CH(2)CH=CH(2))(2) to SiHMe(CH(2)CH(2)CH(2)PPh(2))(2) (i.e. biPSiH, B) together with a propyl analogue Ph(2)PCH(2)CH(2)CH(2)SiMe(Pr(n)())H (7) of A (ca. 2:1 ratio), as well as SiH(CH(2)CH=CH(2))(3) to a mixture (ca. 5:2:1 ratio) of SiH(CH(2)CH(2)CH(2)PPh(2))(3) (i.e. triPSiH, C), a new analogue SiH(Pr(n)())(CH(2)CH(2)CH(2)PPh(2))(2) (8) of B, and a further analogue Ph(2)PCH(2)CH(2)CH(2)SiHPr(n)()(2) (9) of A. A further analogue SiH(2)(CH(2)CH(2)CH(2)PPh(2))(2) (10) of biPSiH (B) is obtained similarly starting from SiH(2)(CH(2)CH=CH(2))(2). Steric control of silylalkyl cleavage from 2 is indicated by the fact that, like PPh(2)Cl (which forms B), two further biPSiH analogues SiH(Me)[CH(2)CH(2)CH(2)P(n-hex)(2)](2) (11) and SiH(Me)(CH(2)CH(2)CH(2)PPhBz)(2) (12) were obtained using P(n-hex)(2)Cl (i.e. n-hex = CH(3)(CH(2))(4)CH(2)-) or PPhBzCl (i.e. Bz = -CH(2)C(6)H(5)), respectively, whereas neither PPr(i)(2)Cl nor PBu(t)(2)Cl led to (phosphinoalkyl)silane formation

Replacing -CH2CH2- with -CONH- does not significantly change rates of charge transport through Ag(TS)-SAM//Ga2O3/EGaIn junctions.

Science.gov (United States)

Thuo, Martin M; Reus, William F; Simeone, Felice C; Kim, Choongik; Schulz, Michael D; Yoon, Hyo Jae; Whitesides, George M

2012-07-04

This paper describes physical-organic studies of charge transport by tunneling through self-assembled monolayers (SAMs), based on systematic variations of the structure of the molecules constituting the SAM. Replacing a -CH(2)CH(2)- group with a -CONH- group changes the dipole moment and polarizability of a portion of the molecule and has, in principle, the potential to change the rate of charge transport through the SAM. In practice, this substitution produces no significant change in the rate of charge transport across junctions of the structure Ag(TS)-S(CH(2))(m)X(CH(2))(n)H//Ga(2)O(3)/EGaIn (TS = template stripped, X = -CH(2)CH(2)- or -CONH-, and EGaIn = eutectic alloy of gallium and indium). Incorporation of the amide group does, however, increase the yields of working (non-shorting) junctions (when compared to n-alkanethiolates of the same length). These results suggest that synthetic schemes that combine a thiol group on one end of a molecule with a group, R, to be tested, on the other (e.g., HS~CONH~R) using an amide-based coupling provide practical routes to molecules useful in studies of molecular electronics.

Molecular Simulations and Theoretical Predictions for Adsorption and Diffusion of CH{sub 4}/H{sub 2} and CO{sub 2}/CH{sub 4} Mixtures in ZIFs

Energy Technology Data Exchange (ETDEWEB)

Liu, Jinchen; Keskin, Seda; Sholl, David S; Johnson, J. Karl

2011-05-01

Adsorption and diffusion of CO{sub 2}/CH{sub 4} and CH{sub 4}/H{sub 2} mixtures were computed in zeolite imidazolate frameworks (ZIFs), ZIF-68 and ZIF-70, using atomically detailed simulations. Adsorption selectivity, diffusion selectivity, and membrane selectivity of ZIFs were calculated based on the results of atomistic simulations. Mixture adsorption isotherms predicted by the ideal adsorbed solution theory agree well with the results of molecular simulations for both ZIFs. Mixture diffusivity calculations indicate that diffusion of CH{sub 4} is increased with increasing concentration of H{sub 2} in the CH{sub 4}/H{sub 2} mixture, while the diffusivity of H{sub 2} decreases with increasing CH{sub 4} concentration. In contrast, the diffusivity of CH{sub 4} is essentially independent of the concentration of CO{sub 2} in the CO{sub 2}/CH{sub 4} mixture, while CO{sub 2} diffusivity decreases with increased CH{sub 4} loading, even though the diffusivity of CH{sub 4} is substantially larger than that of CO{sub 2}. This unusual behavior can be explained in terms of differences in adsorption site preferences due to charge–quadrupole interactions.

The effects of CO addition on the autoignition of H-2, CH4 and CH4/H-2 fuels at high pressure in an RCM

NARCIS (Netherlands)

Gersen, Sander; Darmeveil, Harry; Levinsky, Howard

2012-01-01

Autoignition delay times of stoichiometric and fuel-lean (phi = 0.5) H-2, H-2/CO, CH4, CH4/CO, CH4/H-2 and CH4/CO/H-2 mixtures have been measured in an Rapid Compression Machine at pressures ranging from 20 to 80 bar and in the temperature range 900-1100K. The effects of CO addition on the ignition

Electrical Resistance of Ag-TS-S(CH2)(n-1)CH3//Ga2O3/EGaln Tunneling Junctions

NARCIS (Netherlands)

Cademartiri, Ludovico; Thuo, Martin M.; Nijhuis, Christian A.; Reus, William F.; Tricard, Simon; Barber, Jabulani R.; Sodhi, Rana N. S.; Brodersen, Peter; Kim, Choongik; Chiechi, Ryan C.; Whitesides, George M.

2012-01-01

Tunneling junctions having the structure Ag-TS-S(CH2)(n-1)CH3//Ga2O3/EGaIn allow physical-organic studies of charge transport across self-assembled monolayers (SAMs). In ambient conditions, the surface of the liquid metal electrode (EGaIn, 75.5 wt % Ga, 24.5 wt % In, mp 15.7 degrees C) oxidizes and

Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

Science.gov (United States)

Hoobler, Ray J.; Leone, Stephen R.

1997-01-01

Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

A new metal-organic framework for separation of C2H2/CH4 and CO2/CH4 at room temperature

Science.gov (United States)

Duan, Xing; Zhou, You; Lv, Ran; Yu, Ben; Chen, Haodong; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

2018-04-01

A 3D microporous metal-organic framework with open Cu2+ sites and suitable pore space, [Cu2(L)(H2O)2]·(H2O)4(DMF)8 (ZJU-15, H4L = 5,5‧-(9H-carbazole-2,7-diyl)diisophthalic acid; DMF = N,N-dimethylformamide; ZJU = Zhejiang University), has been constructed and characterized. The activated ZJU-15a has three different types of cages and exhibits BET surface area of 1660 m2 g-1, and can separate gas mixture of C2H2/CH4 and CO2/CH4 at room temperature.

On the feasibility of chemi-ion formation in the system CH2CH(ã 4A″)+O(3P)

Science.gov (United States)

Metropoulos, Aristophanes

2003-12-01

We have investigated theoretically the possibility that the CH2CH(ã 4A″) radical can generate the CH2CHO+(X1A') ion upon collisions with O(3P). We have concluded that this is very unlikely because the minimum of the ground-state potential-energy surface of the ion is at about the same level as the potential energy of the asymptotic CH2CH(ã 4A″)+O(3P) fragments. In addition the Franck-Condon factors should not be favorable because of a drastic change in the geometry of the ion.

Betaine Phosphate (CH3)3N+CH2COO-.H3PO4 Modification Using D2O

International Nuclear Information System (INIS)

Saryati; Ridwan; Deswita; Sugiantoro, Sugik

2002-01-01

Betaine fosfate (CH 3 ) 3 N + CH 2 COO - .H 3 PO 4 modification by using D 2 O has been studied. This modification was carried out by slowly evaporation the saturated Betaine phosphat in the D 2 O solution in the dry box at 40 o C, until the dry crystal were formed. Based on the NMR data, can be concluded that the exchange process with D has been runed well and Betaine phosphate-D (CH 3 ) 3 N + CH 2 COO - .H 3 PO 4 has been resulted. From the X-ray diffraction pattern data can be concluded that there are a deference in the crystal structure between Betaine phosphate and Betaine phosphate modification result. From the Differential Scanning Colorimeter (DSC) diagram at the range temperature from 30 o C to 250 o C, can be shown that the Betaine phosphate-H has two endothermic transition phase, at 99 o C with a very little adsorbed calor and at 221.50 o C with -26.75 cal/g. Modified Betaine phosphate has also two endothermic transition phase, at 99.86 o C with -1.94 cal/g and at 171.01 o C with -3.48 cal/g. It can be conclosed that the D atom substitution on the H atoms in Betaine phosphate, to change the crystal and the endothermic fase temperature and energy

Insertion and C-H Bond Activation of Unsaturated Substrates by Bis(benzamidinato)yttrium Alkyl, [PhC(NSiMe3)2]2YR (R = CH2Ph·THF, CH(SiMe3)2), and Hydrido, {[PhC(NSiMe3)2]2Y(μ-H)}2, Compounds

NARCIS (Netherlands)

Duchateau, Robbert; Wee, Cornelis T. van; Teuben, Jan H.

1996-01-01

The reactivity of benzamidinate-stabilized yttrium complexes [PhC(NSiMe3)2]2YR (R = CH2Ph·THF, CH(SiMe3)2) and {[PhC(NSiMe3)2]2Y(μ-H)}2 has been investigated. The complexes are thermally stable showing no sign of decomposition, ligand or solvent metalation, or H/D exchange after hours at 100 °C in

Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X2Σ+), with Unsaturated Hydrocarbons

Science.gov (United States)

Balucani, N.; Asvany, O.; Huang, L. C. L.; Lee, Y. T.; Kaiser, R. I.; Osamura, Y.; Bettinger, H. F.

2000-12-01

Crossed molecular beam experiments of cyano radicals, CN(X2Σ+, ν=0), in their electronic and vibrational ground state reacting with unsaturated hydrocarbons acetylene, C2H2(X1Σ+g), ethylene, C2H4(X1Ag), methylacetylene, CH3CCH(X1A1), allene, H2CCCH2(X1A1), dimethylacetylene, CH3CCCH3(X1A1'), and benzene, C6H6 (X1A1g), were performed at relative collision energies between 13.3 and 36.4 kJ mol-1 to unravel the formation of unsaturated nitriles in the outflows of late-type AGB carbon stars and molecular clouds. In all reactions, the CN radical was found to attack the π electron density of the hydrocarbon molecule with the radical center located at the carbon atom; the formation of an initial addition complex is a prevalent pathway on all the involved potential energy surfaces. A subsequent carbon-hydrogen bond rupture yields the nitriles cyanoacetylene, HCCCN (X1Σ+), vinylcyanide, C2H3CN (X1A'), 1-methylcyanoacetylene, CH3CCCN (X1A1), cyanoallene, H2CCCH(CN) (X1A'), 3-methylcyanoacetylene, HCCCH2CN(X1A'), 1,1-cyanomethylallene, H2CCC(CN)(CH3) (X1A'), and cyanobenzene, C6H5CN (X1A1). In case of acetylene and ethylene, a second reaction channel involves a [1, 2]-H atom shift in the initial HCCHCN and H2CCH2CN collision complexes prior to a hydrogen atom release to form cyanoacetylene, HCCCN (X1Σ+), and vinylcyanide, C2H3CN (X1A'). Since all these radical-neutral reactions show no entrance barriers, have exit barriers well below the energy of the reactant molecules, and are exothermic, the explicit identification of this CN versus H atom exchange pathway under single collision conditions makes this reaction class a compelling candidate to synthesize unsaturated nitriles in interstellar environments holding temperatures as low as 10 K. This general concept makes it even feasible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in the interstellar medium. Here HCCCN, C2H3CN, and CH3CCCN have been already observed

Photocatalytic Activity in CH3CN Related to the Surface Properties of TiO2 Powders Prepared by Sol-Gel Method

Directory of Open Access Journals (Sweden)

Marta Bettoni

2009-01-01

Full Text Available Some TiO2 powders, prepared from titanium(IVtetraisopropoxide by the sol-gel method and thermally treated between 100 and 1000∘C, have been characterized by X-ray powder diffraction and by nitrogen adsorption and desorption at 77 K to calculate the BET-specific surface area, from which the micropore volume and the external surface area can be derived. The photocatalytic activity (ka of the above powders has been evaluated considering the TiO2-sensitized photo-oxidation of 4-methoxybenzyl alcohol in CH3CN as the test reaction. The decrease of ka have been related to the decrease of the BET surface area, the micropore volume, and the external surface area of the TiO2 powders, but a satisfactory linear correlation is observed only for the last superficial parameter.

H12CN and H13CN excitation analysis in the circumstellar outflow of R Sculptoris

Science.gov (United States)

Saberi, M.; Maercker, M.; De Beck, E.; Vlemmings, W. H. T.; Olofsson, H.; Danilovich, T.

2017-03-01

Context. The 12CO/13CO isotopologue ratio in the circumstellar envelope (CSE) of asymptotic giant branch (AGB) stars has been extensively used as the tracer of the photospheric 12C/13C ratio. However, spatially-resolved ALMA observations of R Scl, a carbon rich AGB star, have shown that the 12CO/13CO ratio is not consistent over the entire CSE. Hence, it can not necessarily be used as a tracer of the 12C/13C ratio. The most likely hypothesis to explain the observed discrepancy between the 12CO/13CO and 12C/13C ratios is CO isotopologue selective photodissociation by UV radiation. Unlike the CO isotopologue ratio, the HCN isotopologue ratio is not affected by UV radiation. Therefore, HCN isotopologue ratios can be used as the tracer of the atomic C ratio in UV irradiated regions. Aims: We aim to present ALMA observations of H13CN(4-3) and APEX observations of H12CN(2-1), H13CN(2-1, 3-2) towards R Scl. These new data, combined with previously published observations, are used to determine abundances, ratio, and the sizes of line-emitting regions of the aforementioned HCN isotopologues. Methods: We have performed a detailed non-LTE excitation analysis of circumstellar H12CN(J = 1-0, 2-1, 3-2, 4-3) and H13CN(J = 2-1, 3-2, 4-3) line emission around R Scl using a radiative transfer code based on the accelerated lambda iteration (ALI) method. The spatial extent of the molecular distribution for both isotopologues is constrained based on the spatially resolved H13CN(4-3) ALMA observations. Results: We find fractional abundances of H12CN/H2 = (5.0 ± 2.0) × 10-5 and H13CN/H2 = (1.9 ± 0.4) × 10-6 in the inner wind (r ≤ (2.0 ± 0.25) ×1015 cm) of R Scl. The derived circumstellar isotopologue ratio of H12CN/H13CN = 26.3 ± 11.9 is consistent with the photospheric ratio of 12C/13C 19 ± 6. Conclusions: We show that the circumstellar H12CN/H13CN ratio traces the photospheric 12C/13C ratio. Hence, contrary to the 12CO/13CO ratio, the H12CN/H13CN ratio is not affected by UV

Additional Value of CH4 Measurement in a Combined 13C/H2 Lactose Malabsorption Breath Test: A Retrospective Analysis

Science.gov (United States)

Houben, Els; De Preter, Vicky; Billen, Jaak; Van Ranst, Marc; Verbeke, Kristin

2015-01-01

The lactose hydrogen breath test is a commonly used, non-invasive method for the detection of lactose malabsorption and is based on an abnormal increase in breath hydrogen (H2) excretion after an oral dose of lactose. We use a combined 13C/H2 lactose breath test that measures breath 13CO2 as a measure of lactose digestion in addition to H2 and that has a better sensitivity and specificity than the standard test. The present retrospective study evaluated the results of 1051 13C/H2 lactose breath tests to assess the impact on the diagnostic accuracy of measuring breath CH4 in addition to H2 and 13CO2. Based on the 13C/H2 breath test, 314 patients were diagnosed with lactase deficiency, 138 with lactose malabsorption or small bowel bacterial overgrowth (SIBO), and 599 with normal lactose digestion. Additional measurement of CH4 further improved the accuracy of the test as 16% subjects with normal lactose digestion and no H2-excretion were found to excrete CH4. These subjects should have been classified as subjects with lactose malabsorption or SIBO. In conclusion, measuring CH4-concentrations has an added value to the 13C/H2 breath test to identify methanogenic subjects with lactose malabsorption or SIBO. PMID:26371034

Insertion and C-H bond activation of unsaturated substrates by bis(benzamidinato)yttrium alkyl, [PhC(NSiMe(3))(2)](2)YR (R=CH(2)Ph center dot THF,CH(SiMe(3))(2)), and hydride, {[PhC(NSiMe(3))(2)]Y-2(mu-H)}(2), compounds

NARCIS (Netherlands)

Duchateau, R; vanWee, CT; Teuben, JH

1996-01-01

The reactivity of benzamidinate-stabilized yttrium complexes [PhC(NSiMe(3))(2)](2)YR (R = CH(2)Ph . THF, CH(SiMe(3))(2) and {[PhC(NSiMe(3))(2)]Y-2(mu-H)}(2) have been investigated. The complexes are thermally stable showing no sign of decomposition, ligand or solvent metalation or H/D exchange after

CH-TRU Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2005-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-10-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

Organic chemistry of NH3 and HCN induced by an atmospheric abnormal glow discharge in N2-CH4 mixtures

OpenAIRE

2010-01-01

Abstract The formation of the chemical products produced in an atmospheric glow discharge fed by a N2-CH4 gas mixture has been studied using Fourier Transform InfraRed (FTIR) and Optical Emission Spectrometry (OES). The measurements were carried out in a flowing regime at ambient temperature and pressure with CH4 concentrations ranging from 0.5% to 2%. In the recorded emission spectra the lines of the second positive system CN system and the first negative s...

High-resolution sub-Doppler infrared spectroscopy of atmospherically relevant Criegee precursor CH2I radicals: CH2 stretch vibrations and "charge-sloshing" dynamics

Science.gov (United States)

Kortyna, A.; Lesko, D. M. B.; Nesbitt, D. J.

2018-05-01

The combination of a pulsed supersonic slit-discharge source and single-mode difference frequency direct absorption infrared spectroscopy permit first high resolution infrared study of the iodomethyl (CH2I) radical, with the CH2I radical species generated in a slit jet Ne/He discharge and cooled to 16 K in the supersonic expansion. Dual laser beam detection and collisional collimation in the slit expansion yield sub-Doppler linewidths (60 MHz), an absolute frequency calibration of 13 MHz, and absorbance sensitivities within a factor of two of the shot-noise limit. Fully rovibrationally resolved direct absorption spectra of the CH2 symmetric stretch mode (ν2) are obtained and fitted to a Watson asymmetric top Hamiltonian with electron spin-rotation coupling, providing precision rotational constants and spin-rotation tensor elements for the vibrationally excited state. Analysis of the asymmetric top rotational constants confirms a vibrationally averaged planar geometry in both the ground- and first-excited vibrational levels. Sub-Doppler resolution permits additional nuclear spin hyperfine structures to be observed, with splittings in excellent agreement with microwave measurements on the ground state. Spectroscopic data on CH2I facilitate systematic comparison with previous studies of halogen-substituted methyl radicals, with the periodic trends strongly correlated with the electronegativity of the halogen atom. Interestingly, we do not observe any asymmetric CH2 stretch transitions, despite S/N ≈ 25:1 on strongest lines in the corresponding symmetric CH2 stretch manifold. This dramatic reversal of the more typical 3:1 antisymmetric/symmetric CH2 stretch intensity ratio signals a vibrational transition moment poorly described by simple "bond-dipole" models. Instead, the data suggest that this anomalous intensity ratio arises from "charge sloshing" dynamics in the highly polar carbon-iodine bond, as supported by ab initio electron differential density plots and

Methanesulfonates of high-valent metals. Syntheses and structural features of MoO{sub 2}(CH{sub 3}SO{sub 3}){sub 2}, UO{sub 2}(CH{sub 3}SO{sub 3}){sub 2}, ReO{sub 3}(CH{sub 3}SO{sub 3}), VO(CH{sub 3}SO{sub 3}){sub 2}, and V{sub 2}O{sub 3}(CH{sub 3}SO{sub 3}){sub 4} and their thermal decomposition under N{sub 2} and O{sub 2} atmosphere

Energy Technology Data Exchange (ETDEWEB)

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S. [Carl von Ossietzky University of Oldenburg, Institute of Pure and Applied Chemistry (Germany)

2011-11-04

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO{sub 3}, UO{sub 2}(CH{sub 3}COO){sub 2}.2 H{sub 2}O, Re{sub 2}O{sub 7}(H{sub 2}O){sub 2}, and V{sub 2}O{sub 5} with CH{sub 3}SO{sub 3}H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO{sub 2}(CH{sub 3}SO{sub 3}){sub 2} (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm{sup 3}, Z=8) contains [MoO{sub 2}] moieties connected by [CH{sub 3}SO{sub 3}] ions to form layers parallel to (100). UO{sub 2}(CH{sub 3}SO{sub 3}){sub 2} (P2{sub 1}/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1) {sup circle}, V=1.8937(3) nm{sup 3}, Z=8) consists of linear UO{sub 2}{sup 2+} ions coordinated by five [CH{sub 3}SO{sub 3}] ions, forming a layer structure. VO(CH{sub 3}SO{sub 3}){sub 2} (P2{sub 1}/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1) {sup circle}, V=0.8290(2) nm{sup 3}, Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO{sub 3}(CH{sub 3}SO{sub 3}) (P anti 1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2) {sup circle}, V=1.1523(4) nm{sup 3}, Z=8) a chain structure exhibiting infinite O-[ReO{sub 2}]-O-[ReO{sub 2}]-O chains is formed. Each [ReO{sub 2}]-O-[ReO{sub 2}] unit is coordinated by two bidentate [CH{sub 3}SO{sub 3}] ions. V{sub 2}O{sub 3}(CH{sub 3}SO{sub 3}){sub 4} (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm{sup 3}, Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH{sub 3}SO{sub 3}] ligands. Additional methanesulfonate ions connect the [V{sub 2}O{sub 3}] groups along [001]. Thermal decomposition of the compounds was monitored under N{sub 2} and O{sub 2} atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N{sub 2} the decomposition proceeds

Analysis of the laser photoelectron spectrum of CH-2

International Nuclear Information System (INIS)

Bunker, P.R.; Sears, T.J.

1985-01-01

We have simulated the photoelectron spectrum of CH - 2 using the model described previously [Sears and Bunker, J. Chem. Phys. 79, 5265 (1983)]. The optimization of the fit of the simulated spectrum to the recently observed spectrum of Lineberger and co-workers [J. Chem. Phys. 81, 1048 (1984) and preceding paper] has enabled us to determine the rotation-bending energy levels of triplet CH 2 over an energy range of more than 1 eV. It has also enabled us to determine that the rotational temperature of the CH - 2 in the experiment is 220 K and that, for v 2 = 1, the vibrational temperature is 680 K. For CH - 2 we determine that a/sub e/ = 103 0 and that ν 2 = 1230 cm -1 . The singlet--triplet splitting in methylene is determined to be 3150 +- 30 cm -1 (0.3905 +- 0.004 eV, 9.01 +- 0.09 kcal/mol) from the photoelectron spectrum, in excellent agreement with the more accurate value previously obtained from LMR spectroscopy [McKellar et al., J. Chem. Phys. 79, 5251 (1983)] of 3165 +- 20 cm -1 (0.3924 +- 0.0025 eV, 9.05 +- 0.06 kcal/mol), and the electron affinity of triplet CH 2 is determined to be 0.652 +- 0.006 eV

Cavity ring down spectroscopy of CH, CH2, HCO, and H2CO in a premixed flat flame at both atmospheric and sub-atmospheric pressure

NARCIS (Netherlands)

Evertsen, R.; Staicu, A.D.; Oijen, van J.A.; Dam, N.J.; Goey, de L.P.H.; Meulen, ter J.J.; Cheauveau, C.; Vovelle, C.

2003-01-01

Density distributions of CH, CH2, HCO and H2CO have been measured in a premixed CH4/air flat flame by Cavity Ring Down Spectroscopy (CRDS). At atmospheric pressure problems are encountered due to the narrow spatial distribution of these species. Rotational flame Temperatures have been derived from

Kinetics of the Br2-CH3CHO Photochemical Chain Reaction

Science.gov (United States)

Nicovich, J. M.; Shackelford, C. J.; Wine, P. H.

1997-01-01

Time-resolved resonance fluorescence spectroscopy was employed in conjunction with laser flash photolysis of Br2 to study the kinetics of the two elementary steps in the photochemical chain reaction nBr2 + nCH3CHO + hv yields nCH3CBrO + nHBr. In the temperature range 255-400 K, the rate coefficient for the reaction Br((sup 2)P(sub 3/2)) + CH3CHO yields CH3CO + HBr is given by the Arrhenius expression k(sub 6)(T) = (1.51 +/- 0.20) x 10(exp -11) exp(-(364 +/- 41)/T)cu cm/(molecule.s). At 298 K, the reaction CH3CO + Br2 yields CH3CBrO + Br proceeds at a near gas kinetic rate, k(sub 7)(298 K) = (1.08 +/- 0.38) x 10(exp -10)cu cm/(molecule.s).

Detection of transient infrared absorption of SO3 and 1,3,2-dioxathietane-2,2-dioxide [cyc-(CH2)O(SO2)O] in the reaction CH2OO+SO2

Science.gov (United States)

Wang, Yi-Ying; Dash, Manas Ranjan; Chung, Chao-Yu; Lee, Yuan-Pern

2018-02-01

We recorded time-resolved infrared absorption spectra of transient species produced on irradiation at 308 nm of a flowing mixture of CH2I2/O2/N2/SO2 at 298 K. Bands of CH2OO were observed initially upon irradiation; their decrease in intensity was accompanied by the appearance of an intense band at 1391.5 cm-1 that is associated with the degenerate SO-stretching mode of SO3, two major bands of HCHO at 1502 and 1745 cm-1, and five new bands near >1340, 1225, 1100, 940, and 880 cm-1. The band near 1340 cm-1 was interfered by absorption of SO2 and SO3, so its band maximum might be greater than 1340 cm-1. SO3 in its internally excited states was produced initially and became thermalized at a later period. The rotational contour of the band of thermalized SO3 agrees satisfactorily with the reported spectrum of SO3. These five new bands are tentatively assigned to an intermediate 1,3,2-dioxathietane-2,2-dioxide [cyc-(CH2)O(SO2)O] according to comparison with anharmonic vibrational wavenumbers and relative IR intensities predicted for this intermediate. Observation of a small amount of cyc-(CH2)O(SO2)O is consistent with the expected reaction according to the potential energy scheme predicted previously. SO3+HCHO are the major products of the title reaction. The other predicted product channel HCOOH+SO2 was unobserved and its branching ratio was estimated to be <5%.

Kinetic and theoretical studies on the protonation of [Ni(2-SC6H4N){PhP(CH2CH2PPh2)2}]+: nitrogen versus sulfur as the protonation site.

Science.gov (United States)

Petrou, Athinoula L; Koutselos, Andreas D; Wahab, Hilal S; Clegg, William; Harrington, Ross W; Henderson, Richard A

2011-02-07

The complexes [Ni(4-Spy)(triphos)]BPh(4) and [Ni(2-Spy)(triphos)]BPh(4) {triphos = PhP(CH(2)CH(2)PPh(2))(2), 4-Spy = 4-pyridinethiolate, 2-Spy = 2-pyridinethiolate} have been prepared and characterized both spectroscopically and using X-ray crystallography. In both complexes the triphos is a tridentate ligand. However, [Ni(4-Spy)(triphos)](+) comprises a 4-coordinate, square-planar nickel with the 4-Spy ligand bound to the nickel through the sulfur while [Ni(2-Spy)(triphos)](+) contains a 5-coordinate, trigonal-bipyramidal nickel with a bidentate 2-Spy ligand bound to the nickel through both sulfur and nitrogen. The kinetics of the reactions of [Ni(4-Spy)(triphos)](+) and [Ni(2-Spy)(triphos)](+) with lutH(+) (lut = 2,6-dimethylpyridine) in MeCN have been studied using stopped-flow spectrophotometry, and the two complexes show very different reactivities. The reaction of [Ni(4-Spy)(triphos)](+) with lutH(+) is complete within the deadtime of the stopped-flow apparatus (2 ms) and corresponds to protonation of the nitrogen. However, upon mixing [Ni(2-Spy)(triphos)](+) and lutH(+) a reaction is observed (on the seconds time scale) to produce an equilibrium mixture. The mechanistic interpretation of the rate law has been aided by the application of MSINDO semiempirical and ADF calculations. The kinetics and calculations are consistent with the reaction between [Ni(2-Spy)(triphos)](+) and lutH(+) involving initial protonation of the sulfur followed by dissociation of the nitrogen and subsequent transfer of the proton from sulfur to nitrogen. The factors affecting the position of protonation and the coupling of the coordination state of the 2-pyridinethiolate ligand to the site of protonation are discussed.

Reaction of ether and thioether functionalised 1-alkenes with the cationic permethylzirconocene olefin polymerisation catalyst [(eta(5)-C5Me5)(2)ZrMe](+). Molecular structure of the insertion product [(eta(5)-C5Me5)(2)ZrCH2CH(Me)CH2OEt](+)

NARCIS (Netherlands)

Bijpost, Erik A; Zuideveld, Martin A.; Meetsma, Auke; Teuben, Jan H

1998-01-01

Reaction of [(η5-C5Me5)2ZrMe][MeB(C6F5)3] (1) with (thio)ether functionalised alkenes: 3-ethoxy-1-propene and 3-(methylthio)-1-propene gives stable insertion products [(η5-C5Me5)2ZrCH2CH(Me)CH2XR][MeB(C6F5)3] (2: X = O, R = Et; 3: X = S, R = Me) in which the (thio)ether function is intramolecularly

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

Science.gov (United States)

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

1999-01-01

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

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

Science.gov (United States)

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

1999-01-01

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

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2007-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2006-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2005-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2004-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

International Nuclear Information System (INIS)

2008-01-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes 'shipping categories' that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the 'General Case,' which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for 'Close-Proximity Shipments' (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for 'Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-09-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-05-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-02-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-06-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-06-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-01-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codesand corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-12-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2006-01-18

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2004-10-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-03-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-09-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2004-12-01

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-11-20

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-12-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-01-30

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2005-08-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

CH-TRU Waste Content Codes (CH-TRUCON)

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2007-06-15

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C₄F₉CH₂CH₂OH)

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Nielsen, Ole John; Hurley, M. D.

2005-01-01

Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C4F9CH2CH2OH, 4:2 FTOH) in the presence of NOx in 700 Torr of N-2/O-2 diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy...

Study on the covalence of Cu and chemical bonding in an inorganic fullerene-like molecule, [CuCl]20[Cp*FeP5]12[Cu-(CH3CN)2+Cl-]5, by a density functional approach

Institute of Scientific and Technical Information of China (English)

WANG; Bingwu; XU; Guangxian; CHEN; Zhida

2004-01-01

The electronic structure and chemical bonding in a recently synthesized inorganic fullerene-like molecule, {[CuCl]20[Cp*FeP5]12 [Cu(CH3CN)+2Cl-]5}, has been studied by a density functional approach. Geometrical optimization of the three basic structural units of the molecule is performed with Amsterdam Density Functional Program. The results are in agreement with the experiment. Localized MO's obtained by Boys-Foster method give a clear picture of the chemical bonding in this molecule. The reason why CuCl can react with Cp*FeP5 in solvent CH3CN to form the fullerene-like molecule is explained in terms of the soft-hard Lewis acid base theory and a new concept of covalence.

Chloroacetone photodissociation at 193 nm and the subsequent dynamics of the CH3C(O)CH2 radical—an intermediate formed in the OH + allene reaction en route to CH3 + ketene

Science.gov (United States)

Alligood, Bridget W.; FitzPatrick, Benjamin L.; Szpunar, David E.; Butler, Laurie J.

2011-02-01

We use a combination of crossed laser-molecular beam experiments and velocity map imaging experiments to investigate the primary photofission channels of chloroacetone at 193 nm; we also probe the dissociation dynamics of the nascent CH3C(O)CH2 radicals formed from C-Cl bond fission. In addition to the C-Cl bond fission primary photodissociation channel, the data evidence another photodissociation channel of the precursor, C-C bond fission to produce CH3CO and CH2Cl. The CH3C(O)CH2 radical formed from C-Cl bond fission is one of the intermediates in the OH + allene reaction en route to CH3 + ketene. The 193 nm photodissociation laser allows us to produce these CH3C(O)CH2 radicals with enough internal energy to span the dissociation barrier leading to the CH3 + ketene asymptote. Therefore, some of the vibrationally excited CH3C(O)CH2 radicals undergo subsequent dissociation to CH3 + ketene products; we are able to measure the velocities of these products using both the imaging and scattering apparatuses. The results rule out the presence of a significant contribution from a C-C bond photofission channel that produces CH3 and COCH2Cl fragments. The CH3C(O)CH2 radicals are formed with a considerable amount of energy partitioned into rotation; we use an impulsive model to explicitly characterize the internal energy distribution. The data are better fit by using the C-Cl bond fission transition state on the S1 surface of chloroacetone as the geometry at which the impulsive force acts, not the Franck-Condon geometry. Our data suggest that, even under atmospheric conditions, the reaction of OH with allene could produce a small branching to CH3 + ketene products, rather than solely producing inelastically stabilized adducts. This additional channel offers a different pathway for the OH-initiated oxidation of such unsaturated volatile organic compounds, those containing a C=C=C moiety, than is currently included in atmospheric models.

Magnesium replacement in formaldehyde: Theoretical rovibrational analysis of X ∼ 3B1 MgCH2

Science.gov (United States)

Bassett, Matthew K.; Fortenberry, Ryan C.

2018-02-01

A full, anharmonic set of fundamental vibrational frequencies as well as spectrosocpic constants are provided at high-level for X ∼ 3B1 MgCH2 for the first time. The present data are in line with previous computational and Ar-matrix results, but the anharmonic data show that two brightest frequencies, ν4 and ν5 , are nearly coincident with one another at 560 cm-1. Hence, this area is the best spectral region to search for signatures of this molecule. The rotational constants are also provided indicating a near-prolate rotational progression which should aid in microwave/millimeter-wave analysis of this molecule. Magnesium is known to be a significant component of the Earth, and molecules containing it may be more common in the interstellar medium/circumstellar media than previously thought. More spectral characterization of such molecules like MgCH2 should be undertaken, and this work is a step in that direction.

Densities, viscosities, and refractive indexes for {C2H5CO2(CH2)2CH3+C6H13OH+C6H6} at T=308.15 K

International Nuclear Information System (INIS)

Casas, Herminio; Garcia-Garabal, Sandra; Segade, Luisa; Cabeza, Oscar.; Franjo, Carlos; Jimenez, Eulogio

2003-01-01

In this work we present densities, kinematic viscosities, and refractive indexes of the ternary system {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 13 OH+C 6 H 6 } and the corresponding binary mixtures {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 6 }, {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 13 OH}, and {C 6 H 13 OH+C 6 H 6 }. All data have been measured at T=308.15 K and atmospheric pressure over the whole composition range. The excess molar volumes, dynamic viscosity deviations, and changes of the refractive index on mixing were calculated from experimental measurements. The results for binary mixtures were fitted to a polynomial relationship to estimate the coefficients and standard deviations. The Cibulka equation has been used to correlate the experimental values of ternary mixtures. Also, the experimental values obtained for the ternary mixture were used to test the empirical methods of Kohler, Jacob and Fitzner, Colinet, Tsao and Smith, Toop, Scatchard et al., and Hillert. These methods predict excess properties of the ternary mixtures from those of the involved binary mixtures. The results obtained for dynamic viscosities of the binary mixtures were used to test the semi-empirical relations of Grunberg-Nissan, McAllister, Auslaender, and Teja-Rice. Finally, the experimental refractive indexes were compared with the predicted results for the Lorentz-Lorenz, Gladstone-Dale, Wiener, Heller, and Arago-Biot equations. In all cases, we give the standard deviation between the experimental data and that calculated with the above named relations

Kinetics of the R + HBr {r_reversible} RH + Br (CH{sub 3}CHBr, CHBr{sub 2} or CDBr{sub 2}) equilibrium. Thermochemistry of the CH{sub 3}CHBr and CHBr{sub 2} radicals

Energy Technology Data Exchange (ETDEWEB)

Seetula, Jorma A. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014 University of Helsinki, Helsinki (Finland)], E-mail: j.seetula@kolumbus.fi; Eskola, Arkke J. [Laboratory of Physical Chemistry, P.O. Box 55 (A.I. Virtasen aukio 1), FIN-00014 University of Helsinki, Helsinki (Finland)

2008-07-03

The kinetics of the reaction of the CH{sub 3}CHBr, CHBr{sub 2} or CDBr{sub 2} radicals, R, with HBr have been investigated in a temperature-controlled tubular reactor coupled to a photoionization mass spectrometer. The CH{sub 3}CHBr (or CHBr{sub 2} or CDBr{sub 2}) radical was produced homogeneously in the reactor by a pulsed 248 nm exciplex laser photolysis of CH{sub 3}CHBr{sub 2} (or CHBr{sub 3} or CDBr{sub 3}). The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature. The reactions were studied separately from 253 to 344 K (CH{sub 3}CHBr + HBr) and from 288 to 477 K (CHBr{sub 2} + HBr) and in these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1{sigma} + Student's t values, units in cm{sup 3} molecule{sup -1} s{sup -1}, no error limits for the third reaction): k(CH{sub 3}CHBr + HBr) = (1.7 {+-} 1.2) x 10{sup -13} exp[+ (5.1 {+-} 1.9) kJ mol{sup -1}/RT], k(CHBr{sub 2} + HBr) = (2.5 {+-} 1.2) x 10{sup -13} exp[-(4.04 {+-} 1.14) kJ mol{sup -1}/RT] and k(CDBr{sub 2} + HBr) = 1.6 x 10{sup -13} exp(-2.1 kJ mol{sup -1}/RT). The energy barriers of the reverse reactions were taken from the literature. The enthalpy of formation values of the CH{sub 3}CHBr and CHBr{sub 2} radicals and an experimental entropy value at 298 K for the CH{sub 3}CHBr radical were obtained using a second-law method. The result for the entropy value for the CH{sub 3}CHBr radical is 305 {+-} 9 J K{sup -1} mol{sup -1}. The results for the enthalpy of formation values at 298 K are (in kJ mol{sup -1}): 133.4 {+-} 3.4 (CH{sub 3}CHBr) and 199.1 {+-} 2.7 (CHBr{sub 2}), and for {alpha}-C-H bond dissociation energies of analogous compounds are (in kJ mol{sup -1}): 415.0 {+-} 2.7 (CH{sub 3}CH{sub 2}Br) and 412.6 {+-} 2.7 (CH{sub 2}Br{sub 2}), respectively.

Radiative association of CH3(+) and H2

International Nuclear Information System (INIS)

Bates, D.R.

1985-01-01

The temperature variation of the rate coefficient for k(1) for CH3(+) + H2 yields CH5(+) + hv is computed treating the para and ortho forms of H2 separately, taking account of nuclear spin and using an accurate theory of the kinetics of association. The results are made absolute with the aid of the measurement at 13 K by Barlow et al. (1984). By combining this measurement with the CH5(+) vibrational frequencies obtained by Pople (1984) from a quantal study, it is deduced that the probability of the stabilizing radiative transition is 5400/s. The rate coefficients k(1) (T, para) and k(1) (T, ortho) are given at 13 K, 30 K, and 80 K. 23 references

SURVEY OBSERVATIONS OF A POSSIBLE GLYCINE PRECURSOR, METHANIMINE (CH{sub 2}NH)

Energy Technology Data Exchange (ETDEWEB)

Suzuki, Taiki; Ohishi, Masatoshi; Hirota, Tomoya; Saito, Masao [Department of Astronomy, the Graduate University for Advanced Studies (SOKENDAI), Osawa 2-21-1, Mitaka, Tokyo 181-8588 (Japan); Majumdar, Liton; Wakelam, Valentine, E-mail: taiki.suzuki@nao.ac.jp [Univ. Bordeaux, LAB, UMR 5804, F-33270, Floirac (France)

2016-07-01

We conducted survey observations of a glycine precursor, methanimine, or methylenimine (CH{sub 2}NH), with the Nobeyama Radio Observatory 45 m telescope and the Sub-Millimeter Radio telescope toward 12 high-mass and two low-mass star-forming regions in order to increase the number of known CH{sub 2}NH sources and to better understand the characteristics of CH{sub 2}NH sources. As a result of our survey, CH{sub 2}NH was detected in eight sources, including four new sources. The estimated fractional abundances were ∼10{sup −8} in Orion KL and G10.47+0.03, while they were ∼10{sup −9} toward the other sources. Our hydrogen recombination line and past studies suggest that CH{sub 2}NH-rich sources have less (this mean not so evolved) evolved H ii regions. The lower destruction rates from UV flux from the central star would contribute to the high CH{sub 2}NH abundances toward CH{sub 2}NH-rich sources. Our gas-grain chemical simulations suggest that CH{sub 2}NH is mostly formed in the gas phase by neutral–neutral reactions, rather than being the product of thermal evaporation from dust surfaces.

Electronic and electrochemical properties of platinum(II) and platinum-mercury-carboxylato complexes containing 2-Me2NCH2C6H4, 2,6-(Me2NCH2)2C6H3- and 2-Me2NC6H4CH2 - ligands

NARCIS (Netherlands)

Koten, G. van; Ploeg, A.F.M.J. van der; Schmitz, J.E.J.; Linden, J.G.M. van der

1982-01-01

The organoplatinum(II) compounds [{2, 6-(Me{2}NCH{2}){2}C{6}H{3}}PtBr] and cis-[(C-N){2}Pt] (C-N = 2-Me{2}NCH{2}C{6}H{4}, 2-Me{2}NC{6}H{4}CH{2}) can be chemically irreversibly oxidized in the potential range 1.00 to 1.35 V vs. an Ag/AgCl electrode, whereas the organoplatinum@?mercury complexes

Enzyme-controlled nitrogen-atom transfer enables regiodivergent C-H amination.

Science.gov (United States)

Hyster, Todd K; Farwell, Christopher C; Buller, Andrew R; McIntosh, John A; Arnold, Frances H

2014-11-05

We recently demonstrated that variants of cytochrome P450BM3 (CYP102A1) catalyze the insertion of nitrogen species into benzylic C-H bonds to form new C-N bonds. An outstanding challenge in the field of C-H amination is catalyst-controlled regioselectivity. Here, we report two engineered variants of P450BM3 that provide divergent regioselectivity for C-H amination-one favoring amination of benzylic C-H bonds and the other favoring homo-benzylic C-H bonds. The two variants provide nearly identical kinetic isotope effect values (2.8-3.0), suggesting that C-H abstraction is rate-limiting. The 2.66-Å crystal structure of the most active enzyme suggests that the engineered active site can preorganize the substrate for reactivity. We hypothesize that the enzyme controls regioselectivity through localization of a single C-H bond close to the iron nitrenoid.

Transient infrared absorption of t-CH3C(O)OO, c-CH3C(O)OO, and α-lactone recorded in gaseous reactions of CH3CO and O2

Science.gov (United States)

Chen, Sun-Yang; Lee, Yuan-Pern

2010-03-01

A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient species produced in gaseous reactions of CH3CO and O2; IR absorption spectra of CH3C(O)OO and α-lactone were observed. Absorption bands with origins at 1851±1, 1372±2, 1169±6, and 1102±3 cm-1 are attributed to t-CH3C(O)OO, and those at 1862±3, 1142±4, and 1078±6 cm-1 are assigned to c-CH3C(O)OO. A weak band near 1960 cm-1 is assigned to α-lactone, cyc-CH2C(O)O, a coproduct of OH. These observed rotational contours agree satisfactorily with simulated bands based on predicted rotational parameters and dipole derivatives, and observed vibrational wavenumbers agree with harmonic vibrational wavenumbers predicted with B3LYP/aug-cc-pVDZ density-functional theory. The observed relative intensities indicate that t-CH3C(O)OO is more stable than c-CH3C(O)OO by 3±2 kJ mol-1. Based on these observations, the branching ratio for the OH+α-lactone channel of the CH3CO+O2 reaction is estimated to be 0.04±0.01 under 100 Torr of O2 at 298 K. A simple kinetic model is employed to account for the decay of CH3C(O)OO.

Transient infrared absorption of t-CH3C(O)OO, c-CH3C(O)OO, and alpha-lactone recorded in gaseous reactions of CH3CO and O2.

Science.gov (United States)

Chen, Sun-Yang; Lee, Yuan-Pern

2010-03-21

A step-scan Fourier-transform infrared spectrometer coupled with a multipass absorption cell was utilized to monitor the transient species produced in gaseous reactions of CH(3)CO and O(2); IR absorption spectra of CH(3)C(O)OO and alpha-lactone were observed. Absorption bands with origins at 1851+/-1, 1372+/-2, 1169+/-6, and 1102+/-3 cm(-1) are attributed to t-CH(3)C(O)OO, and those at 1862+/-3, 1142+/-4, and 1078+/-6 cm(-1) are assigned to c-CH(3)C(O)OO. A weak band near 1960 cm(-1) is assigned to alpha-lactone, cyc-CH(2)C(=O)O, a coproduct of OH. These observed rotational contours agree satisfactorily with simulated bands based on predicted rotational parameters and dipole derivatives, and observed vibrational wavenumbers agree with harmonic vibrational wavenumbers predicted with B3LYP/aug-cc-pVDZ density-functional theory. The observed relative intensities indicate that t-CH(3)C(O)OO is more stable than c-CH(3)C(O)OO by 3+/-2 kJ mol(-1). Based on these observations, the branching ratio for the OH+alpha-lactone channel of the CH(3)CO+O(2) reaction is estimated to be 0.04+/-0.01 under 100 Torr of O(2) at 298 K. A simple kinetic model is employed to account for the decay of CH(3)C(O)OO.

Selective photocatalytic reduction of CO{sub 2} by H{sub 2}O/H{sub 2} to CH{sub 4} and CH{sub 3}OH over Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} nanocatalyst

Energy Technology Data Exchange (ETDEWEB)

Tahir, Muhammad, E-mail: mtahir@cheme.utm.my [Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, UTM, Johor Bahru, Johor (Malaysia); Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, Punjab (Pakistan); Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar [Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310, UTM, Johor Bahru, Johor (Malaysia)

2016-12-15

Highlights: • Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} nanocatalysts tested for CO{sub 2} photoreduction with H{sub 2}O/H{sub 2}. • Production of CH{sub 4} and CH{sub 3}OH depends on reductants type and metal-loading to TiO{sub 2}. • CH{sub 4} production over Cu-In/TiO{sub 2} was 1.5 fold more than In/TiO{sub 2} and 5 times the TiO{sub 2}. • The Cu-promoted CH{sub 3}OH production while In gave more CH{sub 4} with water vapors. • The H{sub 2} reductant gave negative effect for CH{sub 4} but enhanced CH{sub 3}OH production. - Abstract: Photocatalytic CO{sub 2} reduction by H{sub 2}O and/or H{sub 2} reductant to selective fuels over Cu-promoted In{sub 2}O{sub 3}/TiO{sub 2} photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N{sub 2} adsorption-desorption, UV–vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO{sub 2}, oxidized as Cu{sup 2+} and In{sup 3+}, promoted efficient separation of photo-generated electron/hole pairs (e{sup −}/h{sup +}). The results indicate that the reduction rate of CO{sub 2} by H{sub 2}O to CH{sub 4} approached to 181 μmol g{sup −1} h{sup −1} using 0.5% Cu-3% In{sub 2}O{sub 3}/TiO{sub 2} catalyst, a 1.53 fold higher than the production rate over the 3% In{sub 2}O{sub 3}/TiO{sub 2} and 5 times the amount produced over the pure TiO{sub 2}. In addition, Cu was found to promote efficient production of CH{sub 3}OH and yield rate reached to 68 μmol g{sup −1} h{sup −1} over 1% Cu-3% In{sub 2}O{sub 3}/TiO{sub 2} catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H{sub 2} reductant was less favorable for CH{sub 4} production, yet a significant amount of CH{sub 4} and CH{sub 3}OH were obtained using a mixture of H{sub 2}O/H{sub 2} reductant. Therefore, Cu-loaded In{sub 2}O{sub 3}/TiO{sub 2} catalyst has shown to be capable for

Enhanced selective photocatalytic reduction of CO2 to CH4 over plasmonic Au modified g-C3N4 photocatalyst under UV-vis light irradiation

Science.gov (United States)

Li, Hailong; Gao, Yan; Xiong, Zhuo; Liao, Chen; Shih, Kaimin

2018-05-01

A series of Au-g-C3N4 (Au-CN) catalysts were prepared through a NaBH4-reduction method using g-C3N4 (CN) from pyrolysis of urea as precursor. The catalysts' surface area, crystal structure, surface morphology, chemical state, functional group composition and optical properties were characterized by X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, ultraviolet visible (UV-vis) diffuse reflectance spectra, fourier transform infrared, photoluminescence and transient photocurrent analysis. The carbon dioxide (CO2) photoreduction activities under ultraviolet visible (UV-vis) light irradiation were significantly enhanced when gold (Au) was loaded on the surface of CN. 2Au-CN catalyst with Au to CN mole ratio of 2% showed the best catalytic activity. After 2 h UV-vis light irradiation, the methane (CH4) yield over the 2Au-CN catalyst was 9.1 times higher than that over the pure CN. The CH4 selectivity also greatly improved for the 2Au-CN compared to the CN. The deposited Au nanoparticles facilitated the separation of electron-hole pairs on the CN surface. Moreover, the surface plasmon resonance effect of Au further promoted the generation of hot electrons and visible light absorption. Therefore, Au loading significantly improved CO2 photoreduction performance of CN under UV-vis light irradiation.

CO2/CH4 Separation via Polymeric Blend Membrane

Directory of Open Access Journals (Sweden)

H. Sanaeepur

2013-01-01

Full Text Available CO2/CH4 gas separation is a very important applicatable process in upgrading the natural gas and landfil gas recovery. In this work, to investigate the membrane separation process performance, the gas permeation results andCO2/CH4 separation characteristics of different prepared membranes (via blending different molecular weights of polyethylene glycol (PEG as a modifier with acrylonitrile-butadiene-styrene (ABS as a backbone structure have been studied. Furthermore, SEM analysis was carried out for morphological investigations. The effect of PEG content on gas transport properties on the selected sample was also studied. The effect of pressure on CO2 permeation was examined and showed that at the pressure beyond 4 bar, permeability is not affected by pressure. The results showed that more or less in all cases, incorporation of PEG molecules without any significant increase in CH4 permeability increases the CO2/CH4 selectivity. From the view point of gas separation applications the resultant data are within commercial attractive range

Mechanistic and kinetic study of the CH3CO+O2 reaction

Science.gov (United States)

Hou, Hua; Li, Aixiao; Hu, Hongyi; Li, Yuzhen; Li, Hui; Wang, Baoshan

2005-06-01

Potential-energy surface of the CH3CO+O2 reaction has been calculated by ab initio quantum chemistry methods. The geometries were optimized using the second-order Moller-Plesset theory (MP2) with the 6-311G(d,p) basis set and the coupled-cluster theory with single and double excitations (CCSD) with the correlation consistent polarized valence double zeta (cc-pVDZ) basis set. The relative energies were calculated using the Gaussian-3 second-order Moller-Plesset theory with the CCSD/cc-pVDZ geometries. Multireference self-consistent-field and MP2 methods were also employed using the 6-311G(d,p) and 6-311++G(3df,2p) basis sets. Both addition/elimination and direct abstraction mechanisms have been investigated. It was revealed that acetylperoxy radical [CH3C(O)OO] is the initial adduct and the formation of OH and α-lactone [CH2CO2(A'1)] is the only energetically accessible decomposition channel. The other channels, e.g., abstraction, HO2+CH2CO, O +CH3CO2, CO +CH3O2, and CO2+CH3O, are negligible. Multichannel Rice-Ramsperger-Kassel-Marcus theory and transition state theory (E-resolved) were employed to calculate the overall and individual rate coefficients and the temperature and pressure dependences. Fairly good agreement between theory and experiments has been obtained without any adjustable parameters. It was concluded that at pressures below 3 Torr, OH and CH2CO2(A'1) are the major nascent products of the oxidation of acetyl radials, although CH2CO2(A'1) might either undergo unimolecular decomposition to form the final products of CH2O+CO or react with OH and Cl to generate H2O and HCl. The acetylperoxy radicals formed by collisional stabilization are the major products at the elevated pressures. In atmosphere, the yield of acetylperoxy is nearly unity and the contribution of OH is only marginal.

Valence shell threshold photoelectron spectroscopy of the CHxCN (x = 0-2) and CNC radicals.

Science.gov (United States)

Garcia, Gustavo A; Krüger, Julia; Gans, Bérenger; Falvo, Cyril; Coudert, Laurent H; Loison, Jean-Christophe

2017-07-07

We present the photoelectron spectroscopy of four radical species, CH x CN (x = 0-2) and CNC, formed in a microwave discharge flow-tube reactor by consecutive H abstractions from CH 3 CN (CH x CN + F → CH x-1 CN + HF (x = 1-3)). The spectra were obtained combining tunable vacuum ultraviolet synchrotron radiation with double imaging electron/ion coincidence techniques, which yielded mass-selected threshold photoelectron spectra. The results obtained for H 2 CCN complement existing ones while for the other radicals the data represent the first observation of their (single-photon) ionizing transitions. In the case of H 2 CCN, Franck-Condon calculations have been performed in order to assign the vibrational structure of the X + 1 A 1 ←X 2 B 1 ionizing transition. A similar treatment for the HCCN, CCN, and CNC radicals appeared to be more complicated mainly because a Renner-Teller effect strongly affects the vibrational levels of the ground electronic state of the HCCN + , CCN, and CNC species. Nevertheless, the first adiabatic ionization energies of these radicals are reported and compared to our ab initio calculated values, leading to new values for enthalpies of formation (Δ f H 298 0 (HCCN + (X 2 A ' ))=1517±12kJmol -1 ,Δ f H 298 0 (CCN(X 2 Π))=682±13kJmol -1 , and Δ f H 298 0 (CNC(X 2 Πg))=676±12kJmol -1 ), which are of fundamental importance for astrochemistry.

Synthesis and thermolysis of Cp*(C5Me4CH2)TiR complexes

NARCIS (Netherlands)

Luinstra, GA; Brinkmann, PHP; Teuben, JH; Luinstra, Gerrit A.

1997-01-01

Substitution of the chloride in Cp*FvTiCl with MR (Fv = C5Me4CH2; R = Me, CH2SiMe3, CH2CMe3, CH = CH2, M = Li; R = CH2Ph, M = K; R = C3H5, M = MgCl; R = Ph, M = Na . NaCl) gives Cp*FvTiR. NMR spectroscopic evidence points towards a series of structurally related compounds with a bent-sandwich

Silicon nitride and silicon etching by CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams

Energy Technology Data Exchange (ETDEWEB)

Kaler, Sanbir S.; Lou, Qiaowei; Donnelly, Vincent M., E-mail: vmdonnelly@uh.edu; Economou, Demetre J., E-mail: economou@uh.edu [Department of Chemical and Biomolecular Engineering, Plasma Processing Laboratory, University of Houston, Houston, Texas 77204 (United States)

2016-07-15

Silicon nitride (SiN, where Si:N ≠ 1:1) films low pressure-chemical vapor deposited on Si substrates, Si films on Ge on Si substrates, and p-Si samples were exposed to plasma beams emanating from CH{sub 3}F/O{sub 2} or CH{sub 3}F/CO{sub 2} inductively coupled plasmas. Conditions within the plasma beam source were maintained at power of 300 W (1.9 W/cm{sup 3}), pressure of 10 mTorr, and total gas flow rate of 10 sccm. X-ray photoelectron spectroscopy was used to determine the thicknesses of Si/Ge in addition to hydrofluorocarbon polymer films formed at low %O{sub 2} or %CO{sub 2} addition on p-Si and SiN. Polymer film thickness decreased sharply as a function of increasing %O{sub 2} or %CO{sub 2} addition and dropped to monolayer thickness above the transition point (∼48% O{sub 2} or ∼75% CO{sub 2}) at which the polymer etchants (O and F) number densities in the plasma increased abruptly. The C(1s) spectra for the polymer films deposited on p-Si substrates appeared similar to those on SiN. Spectroscopic ellipsometry was used to measure the thickness of SiN films etched using the CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams. SiN etching rates peaked near 50% O{sub 2} addition and 73% CO{sub 2} addition. Faster etching rates were measured in CH{sub 3}F/CO{sub 2} than CH{sub 3}F/O{sub 2} plasmas above 70% O{sub 2} or CO{sub 2} addition. The etching of Si stopped after a loss of ∼3 nm, regardless of beam exposure time and %O{sub 2} or %CO{sub 2} addition, apparently due to plasma assisted oxidation of Si. An additional GeO{sub x}F{sub y} peak was observed at 32.5 eV in the Ge(3d) region, suggesting deep penetration of F into Si, under the conditions investigated.

Rare gas dependence of vibration--vibration energy transfer processes: A diagnostic technique. Applications to CH2D2 and CH3F

International Nuclear Information System (INIS)

Apkarian, V.A.; Weitz, E.

1979-01-01

The rare gas dependence of V--V rates can be used as a diagnostic technique to identify different mechanisms of vibrational energy transfer and determine the rate constants for individual kinetic steps. The method is especially useful for the identification and measurement of rates of resonant vibrational energy transfer processes. Analytical and numerical solutions of pertinent model equations are presented and their range of applicability is discussed. The technique is applied to CH 2 D 2 and CH 3 F. In CH 2 D 2 results of studies on ν 9 , [ν 1 , ν 6 ] and states in the 2000 cm -1 region are presented where the application of the technique has made it possible to identify the pathways leading to population of these states and to assign rate constants to some of the steps involved. In CH 3 F, by studying the Ar dependence of the V--V rates of the [ν 2 , ν 5 ] and [ν 1 , ν 4 ] states it has been possible to construct a complete map of energy transfer pathways which can explain all experimental observations for this system, to date. The general applicability of the technique and its potential application to other systems is also considered

Are CH2O measurements in the marine boundary layer suitable for testing the current understanding of CH4 photooxidation?: A model study

Science.gov (United States)

Wagner, V.; von Glasow, R.; Fischer, H.; Crutzen, P. J.

2002-02-01

On the basis of a data set collected during the Indian Ocean Experiment (INDOEX) campaign 1999, we investigated the formaldehyde (CH2O) budget in the southern Indian Ocean (SIO). With a photochemical box model we simulated the contribution of methane and nonmethane volatile organic compounds to the CH2O budget. To identify the reactions and model constraints that introduce the largest uncertainties in the modeled CH2O concentration, we carried out a local sensitivity analysis. Furthermore, a Monte Carlo method was used to assess the global error of the model predictions. According to this analysis the 2σ uncertainty in the modeled CH2O concentration is 49%. The deviation between observed (200 +/- 70 parts per trillion by volume (pptv) (2σ)) and modeled (224 +/- 110 pptv (2σ)) daily mean CH2O concentration is 12%. However, the combined errors of model and measurement are such that deviations as large as 65% are not significant at the 2σ level. Beyond the ``standard'' photochemistry we analyzed the impact of halogen and aerosol chemistry on the CH2O concentration and investigated the vertical distribution of CH2O in the marine boundary layer (MBL). Calculations with the Model of Chemistry Considering Aerosols indicate that, based on the current understanding, halogen chemistry and aerosol chemistry have no significant impact on the CH2O concentration under conditions encountered in the SIO. However, a detailed investigation including meteorological effects such as precipitation scavenging and convection reveals an uncertainty in state-of-the-art model predictions for CH2O in the MBL that is too large for a meaningful test of the current understanding of CH4 photooxidation.

Atmospheric chemistry of CH3CHF2 (HFC-152a)

DEFF Research Database (Denmark)

Taketani, Fumikazu; Nakayama, Tomoki; Takahashi, Kenshi

2005-01-01

Smog chamber/Fourier transform infrared (FTIR) and laser-induced fluorescence (LIF) spectroscopic techniques were used to study the atmospheric degradation of CH3CHF2. The kinetics and products of the Cl(2P(3/2)) (denoted Cl) atom- and the OH radical-initiated oxidation of CH3CHF2 in 700 Torr of ...

Kinetics of the reactions H+C2H4->C2H5, H+C2H5->2CH3 and CH3+C2H5->products studies by pulse radiolysis combined with infrared diode laser spectroscopy

DEFF Research Database (Denmark)

Sillesen, A.; Ratajczak, E.; Pagsberg, P.

1993-01-01

Formation of methyl radicals via the consecutive reactions H+C2H4+M-->C2H5+M (1) and H+C2H5-->CH3+CH3 (2a) was initiated by pulse radiolysis of 10-100 mbar H-2 in the presence of ethylene. The kinetics of CH3 Were studied by monitoring the transient infrared absorption at the Q(3, 3) line of the ...

Kinetics of the reaction of CH3O2 radicals with NO2

DEFF Research Database (Denmark)

Wallington, T.J.; Nielsen, O.J.; Sehested, K.

1999-01-01

The kinetics of the gas-phase reaction of CH3O2 radicals with NO2 were studied at 295 K in 0.5-14 arm of SF6 diluent using pulse radiolysis combined with time-resolved UV-VIS spectroscopy. Rate data were obtained by following the loss of CH3O2 using a monitoring wavelength of 260 nm. The results...

4-(2-Tetrathiafulvalenyl-ethenyl)pyridine (TTF-CH=CH-Py) radical cation salts containing poly(beta-diketonate) rare earth complexes: synthesis, crystal structure, photoluminescent and magnetic properties.

Science.gov (United States)

Pointillart, Fabrice; Maury, Olivier; Le Gal, Yann; Golhen, Stéphane; Cador, Olivier; Ouahab, Lahcène

2009-08-03

The reactions between the redox-active 4-(2-tetrathiafulvalenyl-ethenyl)pyridine ligand (TTF-CH=CH-Py) and the tris(1,1,1,5,5,5-hexafluoroacetylacetonate)Ln(III) (Ln = La and Nd) lead to the formation of compounds with the formulas {[La(hfac)(5)][(TTF-CH=CH-Py(*+))](2)} (1), {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2) (2), and {[Nd(hfac)(4)(H(2)O)][(TTF-CH=CH-Py(*+))]}(2)(H(2)O)(C(6)H(14))(0.5) (3) (hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate anion). These compounds have been characterized by single-crystal X-ray diffraction, optical, and magnetic measurements. Compounds 1, 2, and 3 crystallize in the monoclinic C2/c, triclinic P1, and monoclinic P2(1)/c space groups, respectively. La(III) adopts a tetradecahedral geometry, while Nd(III) stands in a distorted capped square antiprism one. In 1, the inorganic network is formed by the [La(hfac)(5)](2-) dianionic complexes, while it is formed by a pseudo-dimeric dianionic unit of formula {[Nd(hfac)(4)(H(2)O)](2)}(2-) in 2 and 3. In all crystal structures, the organic network is constituted by the TTF-CH=CH-Py(*+) radical cations. The inorganic and organic networks interact through intermolecular contacts between the pyridine moieties of the TTF-CH=CH-Py(*+) radical cations and the Ln(III) ions. The luminescence properties of the Nd(III) ions (9400 cm(-1)) and fluorescence band of the TTF-CH=CH-Py(*+) radical cations (10200 cm(-1)) have been observed and studied for compound 2. Complexes 2 and 3 are paramagnetic because of Nd(III) ions. Compound 2 is a paramagnetic luminescent TTF-radical-cation-based material. Resistivity measurements have also been performed on these materials.

Mechanisms and rates of proton transfer to coordinated carboxydithioates: studies on [Ni(S2CR){PhP(CH2CH2PPh2)2}](+) (R = Me, Et, Bu(n) or Ph).

Science.gov (United States)

Alwaaly, Ahmed; Clegg, William; Henderson, Richard A; Probert, Michael R; Waddell, Paul G

2015-02-21

The complexes [Ni(S2CR)(triphos)]BPh4 (R = Me, Et, Bu(n) or Ph; triphos = PhP{CH2CH2PPh2}2) have been prepared and characterised. X-ray crystallography (for R = Et, Ph, C6H4Me-4, C6H4OMe-4 and C6H4Cl-4) shows that the geometry of the five-coordinate nickel in the cation is best described as distorted trigonal bipyramidal, containing a bidentate carboxydithioate ligand with the two sulfur atoms spanning axial and equatorial sites, the other axial site being occupied by the central phosphorus of triphos. The reactions of [Ni(S2CR)(triphos)](+) with mixtures of HCl and Cl(-) in MeCN to form equilibrium solutions containing [Ni(SH(S)CR)(triphos)](2+) have been studied using stopped-flow spectrophotometry. The kinetics show that proton transfer is slower than the diffusion-controlled limit and involves at least two coupled equilibria. The first step involves the rapid association between [Ni(S2CR)(triphos)](+) and HCl to form the hydrogen-bonded precursor, {[Ni(S2CR)(triphos)](+)HCl} (K) and this is followed by the intramolecular proton transfer (k) to produce [Ni(SH(S)CR)(triphos)](2+). In the reaction of [Ni(S2CMe)(triphos)](+) the rate law is consistent with the carboxydithioate ligand undergoing chelate ring-opening after protonation. It seems likely that chelate ring-opening occurs for all [Ni(S2CR)(triphos)](+), but only with [Ni(S2CMe)(triphos)](+) is the protonation step sufficiently fast that chelate ring-opening is rate-limiting. With all other systems, proton transfer is rate-limiting. DFT calculations indicate that protonation can occur at either sulfur atom, but only protonation at the equatorial sulfur results in chelate ring-opening. The ways in which protonation of either sulfur atom complicates the analyses and interpretation of the kinetics are discussed.

Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials

DEFF Research Database (Denmark)

Andersen, Mads Peter Sulbæk; Hurley, MD; Wallington, TJ

2004-01-01

Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH3O(CF2CF2O)(n)CH3 (n = 1-3) in 720 +/- 20 Torr of air at 296 +/- 3 K. Relative rate techniques were used to measure k(Cl + CH3O(CF2CF2O)(n)CH3) (3.7 +/- 10.7) x 10(-13) and k......(OH + CH3O(CF2CF2O)(n)CH3) = (2.9 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) leading to an estimated atmospheric lifetime of 2 years for CH3O(CF2CF2O),CH3. The Cl initiated oxidation of CH3O(CF2CF2O),CH3 in air diluent gives CH3O(CF2CF2O)(n)C(O)H in a yield which is indistinguishable from 100 Further...... oxidation leads to the diformate, H(O)CO(CF2CF2O)(n)C(O)H. A rate constant of k(Cl + CH3O(CF2CF2O)(n)CHO) = (1.81 +/- 0.36) x 10(-13) cm(3) molecule(-1) s-1 was determined. Quantitative infrared spectra for CH3O(CF2CF2O)(n)CH3 (n = 1-3) were recorded and used to estimate halocarbon global warming potentials...

Transport Mechanisms for CO2-CH4 Exchange and Safe CO2 Storage in Hydrate-Bearing Sandstone

Directory of Open Access Journals (Sweden)

Knut Arne Birkedal

2015-05-01

Full Text Available CO2 injection in hydrate-bearing sediments induces methane (CH4 production while benefitting from CO2 storage, as demonstrated in both core and field scale studies. CH4 hydrates have been formed repeatedly in partially water saturated Bentheim sandstones. Magnetic Resonance Imaging (MRI and CH4 consumption from pump logs have been used to verify final CH4 hydrate saturation. Gas Chromatography (GC in combination with a Mass Flow Meter was used to quantify CH4 recovery during CO2 injection. The overall aim has been to study the impact of CO2 in fractured and non-fractured samples to determine the performance of CO2-induced CH4 hydrate production. Previous efforts focused on diffusion-driven exchange from a fracture volume. This approach was limited by gas dilution, where free and produced CH4 reduced the CO2 concentration and subsequent driving force for both diffusion and exchange. This limitation was targeted by performing experiments where CO2 was injected continuously into the spacer volume to maintain a high driving force. To evaluate the effect of diffusion length multi-fractured core samples were used, which demonstrated that length was not the dominating effect on core scale. An additional set of experiments is presented on non-fractured samples, where diffusion-limited transportation was assisted by continuous CO2 injection and CH4 displacement. Loss of permeability was addressed through binary gas (N2/CO2 injection, which regained injectivity and sustained CO2-CH4 exchange.

Synthesis of Fe3O4@SiO2@OSi(CH2)3NHRN(CH2PPh2)2PdCl2 type nanocomposite complexes: Highly efficient and magnetically-recoverable catalysts in vitamin K3 synthesis.

Science.gov (United States)

Uruş, Serhan

2016-12-15

The synthesis of aminomethylphosphine-metal complexes have opened a new perspective to the catalytic applications of organic compounds. Magnetic Fe3O4 nano-core was synthesized using the closed quartz tube with Teflon cover and microwaved 200°C for 1h with power controlled instrument set to max. 600W. Novel nano-composite supported; Fe3O4@SiO2(CH2)3NHArN(CH2PPh2)2 and Fe3O4@SiO2(CH2)3N(CH2PPh2)2 type bis(diphenylphosphinomethyl)amino ligands and their Pd(II) complexes have been synthesized and characterized with FT-IR, SEM, EDX, TEM, UV-Visible, XRD and TG/DTA techniques. All the complexes were used as heterogeneous catalysts in the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1, 4-naphthoquinone (vitamin K3, menadione, 2MNQ) in the presence of hydrogen peroxide and acetic acid. Selectivity reached about 55-60% with a conversion of 90-96% using the nano-magnetite supported aminomethylphosphine-Pd(II) complexes. The complexes were very active in three times in the catalytic recycling experiments in five catalytic cycles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Diazadienes in chemistry of lanthanides: latest view on old ligands. Synthesis, structure and properties of complexes {[(R)CNC6H3Pr2i]2}Lu(THF)2(μ-Cl)2Li(THF2 (R=CH3, CH2)

International Nuclear Information System (INIS)

Makhrova, T.V.; Fukin, G.K.; Cherkasov, A.V.; Trifonov, A.A.

2008-01-01

Reaction of dianion derivative [DADLi 2 ] (DAD -1,4-bis(2,6-diisopropylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene) prepared in situ by the reduction of corresponding DAD by the excess of metal lithium in THF with anhydrous LuCl 3 (1:1) results in the formation of the metal cyclic complex {[(R)CNC 6 H 3 Pr 2 i ] 2 }Lu(THF) 2 (μ-Cl) 2 Li(THF) 2 (1) containing the fragment N-C(Me)=C(Me)-N. DAD Treatment by two equivalents BuLi in the mixture ether-hexane (20 Deg C) results in the activation of the C-H bond of methyl substitutes at imine carbon. By the reaction of dilithium derivative [DAD - 2 H Li 2 ] formed in situ with LuCl 3 in THF the complex {[(CH 2 )CNC 6 H 3 Pr 2 i ] 2 }Lu(THF) 2 (μ-Cl) 2 Li(THF) 2 (2) with diamide ligand N-C(=CH 2 )-C(=CH 2 )-N was prepared. Structures of 1 and 2 complexes have been established by X-ray structure analysis [ru

Replacement of CH4 in the hydrate by use of liquid CO2

International Nuclear Information System (INIS)

Ota, Masaki; Morohashi, Kenji; Abe, Yuki; Watanabe, Masaru; Smith, Richard Lee Jr.; Inomata, Hiroshi

2005-01-01

The dynamics of CH 4 replacement in the CH 4 hydrate with saturated liquid CO 2 at 273.2 K was measured with a high pressure optical cell. The results showed that CH 4 in the hydrate gradually moved to the liquid CO 2 phase while CO 2 in the liquid phase penetrated into the hydrate from the quantitative analysis. The decomposing process of the CH 4 hydrate during the replacement was analyzed with in situ Raman spectroscopy, which allowed us to distinguish the cage structure of the CH 4 hydrate and discuss the microscopic view of the replacement in the hydrate. It was found that the decomposition of the medium cage (M-cage) in the CH 4 hydrate proceeded faster than that of the small cage (S-cage). The observed rate difference could be related to the stability of the S-cage in the CH 4 hydrate or the re-formation tendency of CH 4 and water molecules in the S-cage after decomposing the hydrate structure, whereas the guest molecule exchange of CH 4 with CO 2 could occur in the M-cage. Based on the experimental data, we developed a kinetic model for calculation of the CH 4 remaining in the hydrate considering the decomposition rate difference between the M-cage and S-cage in the CH 4 hydrate. The results indicate that the driving force could be the fugacity difference between the fluid phase and the hydrate phase for the replacement process

RELATIONSHIP BETWEEN ATMOSPHERIC CO_2 AND CH_4 CONCENTRATIONS AT SYOWA STATION, ANTARCTICA

OpenAIRE

アオキ, シュウジ; ナカザワ, タカキヨ; ムラヤマ, ショウヘイ; シミズ, アキラ; ハヤシ, マサヒコ; イワイ, クニモト; Shuhji, AOKI; Takakiyo, NAKAZAWA; Shohei, MURAYAMA; Akira, SHIMIZU; Masahiko, HAYASHI; Kunimoto, IWAI

1994-01-01

Precise measurements of the atmospheric CO_2 and CH_4 concentrations have been continued at Syowa Station since 1984 and 1987,respectively. Measured concentrations show secular increase, together with seasonal cycle and irregular variations. Negative correlation is clearly seen between the secular trends of the CO_2 and CH_4 concentrations. The increase rates of CO_2 and CH_4 show oscillations with periods of 2.3 to 2.8 years. The phases of the average seasonal cycles of CO_2 and CH_4 coincid...

Fluxes of CH4 and N2O in aspen stands grown under ambient and twice-ambient CO2

DEFF Research Database (Denmark)

Ambus, P.; Robertson, G.P.

1999-01-01

Elevated atmospheric CO2 has the potential to change below-ground nutrient cycling and thereby alter the soil-atmosphere exchange of biogenic trace gases. We measured fluxes of CH4 and N2O in trembling aspen (Populus tremuloides Michx.) stands grown in open-top chambers under ambient and twice......-ambient CO2 concentrations crossed with `high' and low soil-N conditions. Flux measurements with small static chambers indicated net CH4 oxidation in the open-top chambers. Across dates, CH4 oxidation activity was significantly (P CO2 (8.7 mu g CH4-C m(-2) h(-1)) than...... with elevated CO2 (6.5 mu g CH4-C m(-2) h(-1)) in the low N soil. Likewise, across dates and soil N treatments CH4 was oxidized more rapidly (P CO2 (9.5 mu g CH4-C m(-2) h(-1)) than in chambers with elevated CO2 (8.8 mu g CH4-C m(-2) h(-1)). Methane oxidation in soils incubated...

Determination of the rate coefficients of the CH{sub 4} + O{sub 2} → HO{sub 2}+CH{sub 3} and HCO+O{sub 2} → HO{sub 2} + CO reactions at high temperatures

Energy Technology Data Exchange (ETDEWEB)

Ryu, Si Ok [School of Chemical Engineering, Yeungnam University, Gyeongsan (Korea, Republic of); Shin, Kuan Soo [Dept. of Chemistry, Soongsil University, Seoul (Korea, Republic of); Hwang, Soon Muk [Science Applications International Corp oration, 3000 Aerospace Park way, Brook Park, Ohio (United States)

2017-02-15

Rate coefficients of the title reactions, R1 (CH{sub 4} + O{sub 2} → HO{sub 2}+CH{sub 3}) and R{sub 2} (HCO+O{sub 2} → HO{sub 2} + CO) were obtained over T = 1610 ⁓ 1810 K and T = 200 ⁓ 1760 K, respectively, and at ρ = 7.1 μmol/cm{sup 3}. A lean CH{sub 4}/O{sub 2}/Ar mixture (0.1% CH{sub 4}, ϕ = 0.02) was heated behind reflected shock waves and the temporal OH absorption profiles were measured using a laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the experimental profiles via optimization of k1 and k2 values in the reaction simulation. The rate coefficient expressions derived are k{sub 1} = 1.46 × 10{sup 14} exp (−26 210 K/T) cm{sup 3}/mol/s, T = 1610 ⁓ 1810 K and k{sub 2} = 1.9 × 10{sup 12} T{sup 0.1{sup 6}} exp (−245 K/T) cm{sup 3}/mol/s, T = 200 ⁓ 1760 K.

Quantum chemical spectral characterization of CH2NH2+ for remote sensing of Titan's atmosphere

Science.gov (United States)

Thackston, Russell; Fortenberry, Ryan C.

2018-01-01

Cassini has shown that CH2NH2+ is likely present in relatively high abundance in Titan's upper atmosphere. Relatively little is known about this molecule even though it contains the same number of electrons as ethylene, a molecule of significance to Titan's chemistry. Any studies on CH2NH2+ with application to Titan or its atmospheric chemistry will have to be done remotely at this point with the end of the fruitful Cassini mission. Consequently, trusted quantum chemical techniques are utilized here to produce the rotational, vibrational, and rovibrational spectroscopic constants for CH2NH2+ for the first time. The methodology produces a tightly fit potential energy surface here that is well-behaved indicating a strong credence in the accuracy for the produced values. Most notably, the 884.1 cm-1 NH2 out-of-plane bend is the brightest of the vibrational frequencies reported here for CH2NH2+ , and an observed and unattributed feature in this spectral region has been documented but never assigned to a molecular carrier. Follow-up IR or radio observations making use of the 540 GHz to 660 GHz range with the 0.45 D molecular dipole moment will have to be undertaken in order to confirm this or any attribution, but the data provided in this work will greatly assist in any such studies related to CH2NH2+.

Simulation and optical spectroscopy of a DC discharge in a CH4/H2/N2 mixture during deposition of nanostructured carbon films

Science.gov (United States)

Mironovich, K. V.; Mankelevich, Yu. A.; Voloshin, D. G.; Dagesyan, S. A.; Krivchenko, V. A.

2017-08-01

Two-dimensional numerical simulations of a dc discharge in a CH4/H2/N2 mixture in the regime of deposition of nanostructured carbon films are carried out with account of the cathode electron beam effects. The distributions of the gas temperature and species number densities are calculated, and the main plasmachemical kinetic processes governing the distribution of methyl radicals above the substrate are analyzed. It is shown that the number density of methyl radicals above the substrate is several orders of magnitude higher than the number densities of other hydrocarbon radicals, which indicates that the former play a dominant role in the growth of nanostructured carbon films. The model is verified by comparing the measured optical emission profiles of the H( n ≡ 3), C 2 * , CH*, and CN* species and the calculated number densities of excited species, as well as the measured and calculated values of the discharge voltage and heat fluxes onto the electrodes and reactor walls. The key role of ion-electron recombination and dissociative excitation of H2, C2H2, CH4, and HCN molecules in the generation of emitting species (first of all, in the cold regions adjacent to the electrodes) is revealed.

Chemical reaction surface vibrational frequencies evaluated in curvilinear internal coordinates: Application to H + CH(4) H(2) + CH(3).

Science.gov (United States)

Banks, Simon T; Clary, David C

2009-01-14

We consider the general problem of vibrational analysis at nonglobally optimized points on a reduced dimensional reaction surface. We discuss the importance of the use of curvilinear internal coordinates to describe molecular motion and derive a curvilinear projection operator to remove the contribution of nonzero gradients from the Hessian matrix. Our projection scheme is tested in the context of a two-dimensional quantum scattering calculation for the reaction H + CH(4) --> H(2) + CH(3) and its reverse H(2) + CH(3) --> H + CH(4). Using zero-point energies calculated via rectilinear and curvilinear projections we construct two two-dimensional, adiabatically corrected, ab initio reaction surfaces for this system. It is shown that the use of curvilinear coordinates removes unphysical imaginary frequencies observed with rectilinear projection and leads to significantly improved thermal rate constants for both the forward and reverse reactions.

Ultrasonic irradiation-promoted one-pot synthesis of CH3NH3PbBr3 quantum dots without using flammable CH3NH2 precursor

Science.gov (United States)

Jiang, Han; Wang, Chunlei; Lv, Changgui; Xu, Shuhong; Zhu, Li; Zhang, Ruohu; Cui, Yiping

2017-02-01

At present, the CH3NH3PbBr3 quantum dots (QDs) reported in the literature usually contain two synthesis steps: the initial preparation of CH3NH3Br via the reaction of flammable CH3NH2 and HBr, together with the subsequent formation of CH3NH3PbBr3 QDs. To avoid the use of dangerous CH3NH2, this work develops a novel one-pot method for synthesizing CH3NH3PbBr3 QDs using safe and commercially available reactants (CH3NH3Cl, KBr and PbCl2). It is found that ultrasonic treatment plays a key role during the synthesis of CH3NH3PbBr3 QDs. Without ultrasonic irradiation, it is not possible to synthesize CH3NH3PbBr3 QDs under heating or vigorous stirring. Aliquots of samples taken at different ultrasonic irradiation time intervals show a time-dependent redshift in the emission wavelength. This suggests the formation of CH3NH3PbCl3 QDs first, followed by the formation of CH3NH3PbBr3 QDs through ultrasonically promoted halide exchange. Moreover, mixed CH3NH3PbCl x Br3-x QDs with a tunable emission wavelength can also be prepared through this one-pot method by controlling the ultrasonic irradiation time. In comparison to the previous two-step method, the current one-pot method is simpler, less time-consuming and does not use flammable CH3NH2. The as-prepared CH3NH3PbBr3 QDs show a comparable photoluminescence (PL) quantum yield (QY) to that of the literature. What is more, the ultrasonic time-controlled emission wavelength of CH3NH3PbCl x Br3-x QDs also provides an alternative way of tuning QD emission to the traditional way of controlling the halide ratios.

Exploring mechanisms of a tropospheric archetype: CH{sub 3}O{sub 2} + NO

Energy Technology Data Exchange (ETDEWEB)

Launder, Andrew M.; Agarwal, Jay; Schaefer, Henry F., E-mail: ccq@uga.edu [Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602 (United States)

2015-12-21

Methylperoxy radical (CH{sub 3}O{sub 2}) and nitric oxide (NO) contribute to the propagation of photochemical smog in the troposphere via the production of methoxy radical (CH{sub 3}O) and nitrogen dioxide (NO{sub 2}). This reaction system also furnishes trace quantities of methyl nitrate (CH{sub 3}ONO{sub 2}), a sink for reactive NO{sub x} species. Here, the CH{sub 3}O{sub 2} + NO reaction is examined with highly reliable coupled-cluster methods. Specifically, equilibrium geometries for the reactants, products, intermediates, and transition states of the ground-state potential energy surface are characterized. Relative reaction enthalpies at 0 K (ΔH{sub 0K}) are reported; these values are comprised of electronic energies extrapolated to the complete basis set limit of CCSDT(Q) and zero-point vibrational energies computed at CCSD(T)/cc-pVTZ. A two-part mechanism involving CH{sub 3}O and NO{sub 2} production followed by radical recombination to CH{sub 3}ONO{sub 2} is determined to be the primary channel for formation of CH{sub 3}ONO{sub 2} under tropospheric conditions. Constrained optimizations of the reaction paths at CCSD(T)/cc-pVTZ suggest that the homolytic bond dissociations involved in this reaction path are barrierless.

CO2 Reforming of CH4 by Atmospheric Pressure Abnormal Glow Plasma

International Nuclear Information System (INIS)

Chen Qi; Dai Wei; Tao Xumei; Yu Hui; Dai Xiaoyan; Yin Yongxiang

2006-01-01

A novel plasma atmospheric pressure abnormal glow discharge was used to investigate synthesis gas production from reforming methane and carbon dioxide. Special attentions were paid to the discharge characteristics and CH 4 , CO 2 conversion, H 2 , CO selectivity, and ratio of H 2 /CO varied with the changing of discharging power, the total flux, and the ratio of CH 4 /CO 2 . Experiments were performed in wider operation variables, the discharging power of 240 to 600 W, the CH 4 /CO 2 of 0.2 to 1.0 and the total flux of 140 to 500 mL/min. The experiments showed that the conversion of CH 4 and CO 2 was up to 91.9% and 83.2%, the selectivity of CO and H 2 was also up to 80% and 90% and H 2 /CO mole ratio was 0.2 to 1.2, respectively. A brief analysis for discharge characteristics and the experimental results were given

Cationic polyhydrido cluster complexes. Crystal and molecular structures of (Ir3(Ph2P(CH2)3PPh2)3(H)7(CO))2+ and (Ir3(Ph2P(CH2)2(2-py))3(H)7)2+

International Nuclear Information System (INIS)

Hsienhau Wang; Casalnuovo, A.L.; Johnson, B.J.; Mueting, A.M.; Pignolet, L.H.

1988-01-01

Two new cationic polyhydrido cluster complexes of iridium have been synthesized and characterized by single-crystal x-ray diffraction and by ir and 1 H and 31 P NMR spectroscopy (Ir 3 (dppp) 3 (H) 7 (CO)) 2+ (2) and (Ir3 (PN) 3 (H) 7)2+ (5), where dppp = 1,3-bis(diphenylphosphino)propane and PN = 1-(2-pyridyl)-2-(diphenylphosphino)ethane, were synthesized by the reaction of CO with (Ir 3 (dppp) 3 (H) 7 ) 2+ (1) in CH 2 Cl 2 solution and H 2 with (Ir(PN)(COD)) + (4) in CH 3 OH solution, respectively. Crystal structures for both compounds is reported. The hydride positions were not located in the crystal structure analyses but were deduced from structural and 1 H NMR data. The molecular structure of 2 consists of a bilateral triangle of three iridium atoms with a carbonyl at the vertex and a chelating dppp ligand on each iridium atom. 1 H NMR data with use of acetone-d 6 as solvent showed that 2 possesses four doubly bridging hydrides and three terminal hydrides, yielding C 1 symmetry. The molecular structure of 5 consists of an approximately equilateral triangle of three iridium atoms (average Ir-Ir distance 2.746 (1) angstrom) with one PN ligand chelated to each iridium atom. 1 H NMR analysis, with use of CD 2 Cl 2 as solvent, showed that 5 has one triply bridging hydride and six terminal hydrides, giving C 3 symmetry. (Ir 3 (dppp) 3 (H) 7 (CH 3 C 6 H 4 NC)) 2+ (3) a complex structurally analogous to 2, was synthesized from 1 and p-tolyl isocyanide in CH 2 Cl 2 solution and characterized by ir and 1 H and 31 P NMR spectroscopy. 44 refs., 3 figs., 3 tabs

Microbial CH4 and N2O consumption in acidic wetlands

Directory of Open Access Journals (Sweden)

Steffen eKolb

2012-03-01

Full Text Available Acidic wetlands are global sources of the atmospheric greenhouse gases methane (CH4, and nitrous oxide (N2O. Consumption of both atmospheric gases has been observed in various acidic wetlands, but information on the microbial mechanisms underlying these phenomena is scarce. A substantial amount of CH4 is consumed in sub soil by aerobic methanotrophs at anoxic–oxic interfaces (e.g., tissues of Sphagnum mosses, rhizosphere of vascular plant roots. Methylocystis-related species are likely candidates that are involved in the consumption of atmospheric CH4 in acidic wetlands. Oxygen availability regulates the activity of methanotrophs of acidic wetlands. Other parameters impacting on the methanotroph-mediated CH4 consumption have not been systematically evaluated. N2O is produced and consumed by microbial denitrification, thus rendering acidic wetlands as temporary sources or sinks for N2O. Denitrifier communities in such ecosystems are diverse, and largely uncultured and/or new, and environmental factors that control their consumption activity are unresolved. Analyses of the composition of N2O reductase genes in acidic wetlands suggest that acid-tolerant Proteobacteria have the potential to mediate N2O consumption in such soils. Thus, the fragmented current state of knowledge raises open questions concerning methanotrophs and dentrifiers that consume atmospheric CH4 and N2O in acidic wetlands.

Modeling Plasma-based CO2 and CH4 Conversion in Mixtures with N2, O2 and H2O: the Bigger Plasma Chemistry Picture

KAUST Repository

Wang, Weizong; Snoeckx, Ramses; Zhang, Xuming; Cha, Min; Bogaerts, Annemie

2018-01-01

performed regarding the single component gases, i.e. CO2 splitting and CH4 reforming, as well as for two component mixtures, i.e. dry reforming of methane (CO2/CH4), partial oxidation of methane (CH4/O2), artificial photosynthesis (CO2/H2O), CO2

Catalysis of the reduction of Tl+ and of CH2Cl2 by colloidal silver in aqueous solution

International Nuclear Information System (INIS)

Henglein, A.

1979-01-01

(CH 3 ) 2 COH radicals (1-hydroxy-1-methylethyl) do not reduce Tl + or CH 2 Cl 2 in homogeneous aqueous solution. In the presence of 2.5 x 10 -4 g atom/L of colloidal silver, Tl + is reduced to yield colloidal thallium, and CH 2 Cl 2 to yield Cl - plus CH 3 Cl. These reactions occur in competition with the silver-catalyzed reduction of water. Tl + is reduced in a one-electron transfer reaction and CH 2 Cl 2 in a two-electron transfer process. The effects are understood in terms of the colloidal particles acting as a pool for electrons that is continuously charged by the organic radicals and discharged by water or dissolved substrates. The specific rate for the CH 2 Cl 2 reduction at the silver pool is 4.3 x 10 3 times greater than that of the water reduction. Electrochemical considerations are carried out to estimate a stationary potential of -0.62 V (vs the standard hydrogen electrode) for the electron pool and to discuss the energetics of the observed reactions and the possible role of adsorbed hydrogen atoms. Colloidal silver and organic radicals were radiolytically produced. 7 figures

Catalysis of the reduction of Tl+ and of CH2Cl2 by colloidal silver in aqueous solution

International Nuclear Information System (INIS)

Henglein, A.

1979-01-01

(CH 3 ) 2 COH radicals (1-hydroxy-1-methylethyl) do not reduce Tl + or CH 2 CL 2 in homogeneous aqueous solution. In the presence of 2.5 x 10 -4 g atom/L of colloidal silver, Tl + is reduced to yield colloidal thallium, and CH 2 Cl 2 to yield Cl - plus CH 3 Cl. These reactions occur in competition with the silver-catalyzed reduction of water. Tl + is reduced in a one-electron transfer reaction and CH 2 Cl 2 in a two-electron transfer process. The effects are understood in terms of the colloidal particles acting as a pool for electrons that is continuously charged by the organic radicals and discharged by water or dissolved substrates. The specific rate for the CH 2 Cl 2 reduction at the silver pool is 4.3 x 10 3 times greater than that of the water reduction. Electrochemical considerations are carried out to estimate a stationary potential of -0.62 V (vs the standard hydrogen electrode) for the electron pool and to discuss the energetics of the observed reactions and tha materials handling point of view, are being determined

Kinetics of the gas-phase reactions of chlorine atoms with CH2F2, CH3CCl3 and CF3CFH2 over the temperature range 253 – 551 K

DEFF Research Database (Denmark)

Nilsson, Elna Johanna Kristina; Johnson, Matthew Stanley; Nielsen, Ole John

2009-01-01

Relative rate techniques were used to study the title reactions in 930–1200 mbar of N2 diluent. The reaction rate coefficients measured in the present work are summarized by the expressions k(Cl+CH2F2) = 1.19×10-17 T 2 exp(-1023/T ) cm3 molecule-1 s-1 (253– 553 K), k(Cl+CH3CCl3) = 2.41×10-12 exp(...

Micellar induced regioselectivity in the two-step consecutive reaction of SO3(2-) with Br-(CH2CH2)n-Br (n=2-5).

Science.gov (United States)

Currie, Fredrik; Jarvoll, Patrik; Holmberg, Krister; Romsted, Laurence S; Gunaseelan, Krishnan

2007-08-15

High field (800 MHz) (1)H NMR was used to monitor the two-step consecutive reaction of excess SO(3)(2-) with symmetrical bifunctional alpha,omega-dibromoalkanes with butane (DBB), hexane (DBH), octane (DBO), and decane (DBD) chains in CTAB micelles at 25 degrees C. The first-order rate constant for the first substitution step for DBB and DBH is about 5 times faster than for the second, but the kinetics for DBO and DBD were not cleanly first-order. After 40 min, the solution contained about 80% of the intermediate bromoalkanesulfonate from DBB and DBH and the remainder is alkanedisulfonate and unreacted starting material. The same reactions were carried out in homogeneous MeOH/D(2)O solutions at 50 degrees C. The rate constants for all four alpha,omega-dibromoalkanes were first-order throughout the time course of the reaction and the same within +/-10%. However, because micellar solutions are organized on the nanoscale and bring together lipophilic and hydrophilic reactants into a small reaction volume at the micellar interface, they speed this substitution reaction considerably compared to reaction in MeOH/D(2)O. The CTAB micelles also induce a significant regioselectivity in product formation by speeding the first step of the consecutive reaction more than the second. The results are consistent with the bromoalkanesulfonate intermediates having a radial orientation within the micelles with the -CH(2)SO(3)(-) group in the interfacial region and the -CH(2)Br group directed into the micellar core such that the concentration of -CH(2)Br groups in the reactive zone, i.e., the micellar interface, is significantly reduced. These results provide the first example of self-assembled surfactant system altering the relative rates of the reaction steps of a consecutive reaction and, in doing so, enhancing monosubstitution of a symmetrically disubstituted species.

The reaction of Cs{sub 2}[Tc(NO)F{sub 5}] with BF{sub 3} in acetonitrile. Formation and structure of [{Tc(NO)(CH_3CN)_4}{sub 2}(μ-F)](BF{sub 4}){sub 3}

Energy Technology Data Exchange (ETDEWEB)

Balasekaran, Samundeeswari Mariappan [Institute of Chemistry and Biochemistry, Freie Universitaet Berlin (Germany); Department of Chemistry, University of Nevada, Las Vegas, NV (United States); Hagenbach, Adelheid; Spandl, Johann; Abram, Ulrich [Institute of Chemistry and Biochemistry, Freie Universitaet Berlin (Germany)

2017-10-04

The deep blue, paramagnetic Cs{sub 2}[Tc{sup II}(NO)F{sub 5}] is formed during reactions of pertechnetate, acetohydroxamic acid, and CsF in aqueous HF. A reaction of Cs{sub 2}[Tc(NO)F{sub 5}] with BF{sub 3}.MeOH in acetonitrile gives yellow blocks of the fluorido-bridged dimer [{Tc"I(NO)(CH_3CN)_4}{sub 2}F](BF{sub 4}){sub 3}. The compound is stable as solid and in acetonitrile solutions. The complex cation contains a bent μ-F{sup -} ligand and two linear nitrosyl groups. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Mechanistic study of the gas-phase reaction of CH₂FO₂ radicals with HO₂

DEFF Research Database (Denmark)

Wallington, T.J.; Hurley, M.D.; Schneider, W.F.

1994-01-01

.71 +/- 0.11 were established. Quoted errors are 2 standard deviations together with our estimate of systematic uncertainties. This result is discussed with respect to previous literature data and to computer models of atmospheric chemistry. As part of this work, the reactivity of Cl atoms towards CH2FCl...... and CH2FOOH was investigated; rate constants of k(Cl + CH2FCl) = (1.1 +/- 0.1) X 10(-3) and k(Cl + CH2FOOH) = (1.5 +/- 0.5) X 10(-3) cm(3) molecule(-1) s(-1) were determined....

CHEMICAL DIAGNOSTICS OF THE MASSIVE STAR CLUSTER-FORMING CLOUD G33.92+0.11. I. {sup 13}CS, CH{sub 3}OH, CH{sub 3}N, OCS, H{sub 2}S, SO{sub 2}, and SiO

Energy Technology Data Exchange (ETDEWEB)

Minh, Young Chol [Korea Astronomy and Space Science Institute, 776 Daedeok-daero, Yuseong, Daejeon 34055 (Korea, Republic of); Liu, Hauyu Baobab [Institute of Astronomy and Astrophysics, Academia Sinica, P.O. Box 23-141, Taipei 10617, Taiwan (China); Galvań-Madrid, Roberto [Centro de Radioastronoma y Astrofísica, UNAM, A.P. 3-72, Xangari, Morelia 58089 (Mexico)

2016-06-20

Large chemical diversity was found in the gas clumps associated with the massive star cluster-forming G33.92+0.11 region with sub-arcsecond angular resolution (0.″6–0.″8) observations with ALMA. The most prominent gas clumps are associated with the dust emission peaks A1, A2, and A5. The close correlation between CH{sub 3}OH and OCS in the emission distributions strongly suggests that these species share a common origin of hot core grain mantle evaporation. The latest generation of star clusters are forming in the A5 clump, as indicated by multiple SiO outflows and its rich hot core chemistry. We also found a narrow SiO emission associated with the outflows, which may trace a cooled component of the outflows. Part of the chemical complexity may have resulted from the accreting gas from the ambient clouds, especially in the northern part of A1 and the southern part of A2. The chemical diversity found in this region is believed to mainly result from the different chemical evolutionary timescales of massive star formation. In particular, the abundance ratio between CH{sub 3}OH and CH{sub 3}CN may be a good chemical clock for the early phase of star formation.

[CH(3)(CH(2))(11)NH(3)]SnI(3): a hybrid semiconductor with MoO(3)-type tin(II) iodide layers.

Science.gov (United States)

Xu, Zhengtao; Mitzi, David B

2003-10-20

The organic-inorganic hybrid [CH(3)(CH(2))(11)NH(3)]SnI(3) presents a lamellar structure with a Sn-I framework isotypic to that of MoO(3). The SnI(3)(-) layer consists of edge and corner-sharing SnI(6) octahedra in which one of the six Sn-I bonds is distinctly elongated (e.g., 3.62 A), indicating lone-pair stereoactivity for the Sn(II) atom. The overall electronic character remains comparable with that of the well-studied SnI(4)(2)(-)-based perovskite semiconductors, such as [CH(3)(CH(2))(11)NH(3)](2)SnI(4), with a red-shifted and broadened exciton peak associated with the band gap, apparently due to the increased dimensionality of the Sn-I framework. The title compound offers, aside from the hybrid perovskites, a new type of solution-processable Sn-I network for potential applications in semiconductive devices.

Thermodynamic stability and guest distribution of CH4/N2/CO2 mixed hydrates for methane hydrate production using N2/CO2 injection

International Nuclear Information System (INIS)

Lim, Dongwook; Ro, Hyeyoon; Seo, Yongwon; Seo, Young-ju; Lee, Joo Yong; Kim, Se-Joon; Lee, Jaehyoung; Lee, Huen

2017-01-01

Highlights: • We examine the thermodynamic stability and guest distribution of CH 4 /N 2 /CO 2 mixed hydrates. • Phase equilibria of the CH 4 /N 2 /CO 2 mixed hydrates were measured to determine the thermodynamic stability. • The N 2 /CO 2 ratio of the hydrate phase is almost constant despite the enrichment of CO 2 in the hydrate phase. • 13 C NMR results indicate the preferential occupation of N 2 and CO 2 in the small and large cages of sI hydrates, respectively. - Abstract: In this study, thermodynamic stability and cage occupation behavior in the CH 4 – CO 2 replacement, which occurs in natural gas hydrate reservoirs by injecting flue gas, were investigated with a primary focus on phase equilibria and composition analysis. The phase equilibria of CH 4 /N 2 /CO 2 mixed hydrates with various compositions were measured to determine the thermodynamic stability of gas hydrate deposits replaced by N 2 /CO 2 gas mixtures. The fractional experimental pressure differences (Δp/p) with respect to the CSMGem predictions were found to range from −0.11 to −0.02. The composition analysis for various feed gas mixtures with a fixed N 2 /CO 2 ratio (4.0) shows that CO 2 is enriched in the hydrate phase, and the N 2 /CO 2 ratio in the hydrate phase is independent of the feed CH 4 fractions. Moreover, 13 C NMR measurements indicate that N 2 molecules preferentially occupy the small 5 12 cages of sI hydrates while the CO 2 molecules preferentially occupy the large 5 12 6 2 cages, resulting in an almost constant area ratio of CH 4 molecules in the large to small cages of the CH 4 /N 2 /CO 2 mixed hydrates. The overall experimental results provide a better understanding of stability conditions and guest distributions in natural gas hydrate deposits during CH 4 – flue gas replacement.

Určení hodnoty věcných břemen stavby na cizím pozemku a přechodu nebo přejezdu přes pozemek jiného vlastníka

OpenAIRE

Kuhrová, Kristýna

2011-01-01

Diplomová práce je zaměřena na problematiku věcných břemen z hlediska činnosti znalce. V první části práce je proveden rozbor platné právní úpravy věcných břemen, jejich členění, příčiny možného vzniku, změn a zániku. Dále následuje obecný popis metodiky oceňování věcných břemen, vymezení jednotlivých druhů cen a účelů oceňování věcných břemen. V návrhové části je teoretický rozbor aplikován na dva konkrétní případy věcných břemen, a to věcného břemene přechodu přes pozemek jiného vlastníka a...

Synthesis and structure of PbBipy2(1-B10H9S(CH3)2)2

International Nuclear Information System (INIS)

Orlova, A.M.; Sivaev, I.B.; Lagun, V.L.; Katser, S.B.; Solntsev, K.A.; Kuznetsov, N.T.

1993-01-01

Lead complex with B 10 H 9 S(CH 3 ) 2 - anion and 2,2'-bipyridine was synthesized and characterized. According to the data of X-ray diffraction analysis the crystals belong to monoclinic crystal system, sp. gr. P2 1 /a: a = 9.940(4), b 31.568(4), c = 13.458(2) A, β = 111.09(2) deg, V = 3940(2) A 3 , Z = 4. The structure consists of monomer units PbBipy 2 (1-B 10 H 9 S(CH 3 ) 2 ) 2 . The Pb-B distances are within 3.24-3.55 A. 15 refs., 1 fig., 2 tabs

Ab Initio Theoretical Studies on the Kinetics of Hydrogen Abstraction Type Reactions of Hydroxyl Radicals with CH3CCl2F and CH3CClF2

Science.gov (United States)

Saheb, Vahid; Maleki, Samira

2018-03-01

The hydrogen abstraction reactions from CH3Cl2F (R-141b) and CH3CClF2 (R-142b) by OH radicals are studied theoretically by semi-classical transition state theory. The stationary points for the reactions are located by using KMLYP density functional method along with 6-311++G(2 d,2 p) basis set and MP2 method along with 6-311+G( d, p) basis set. Single-point energy calculations are performed by the CBS-Q and G4 combination methods on the geometries optimized at the KMLYP/6-311++G(2 d,2 p) level of theory. Vibrational anharmonicity coefficients, x ij , which are needed for semi-classical transition state theory calculations, are computed at the KMLYP/6-311++G(2 d,2 p) and MP2/6-311+G( d, p) levels of theory. The computed barrier heights are slightly sensitive to the quantum-chemical method. Thermal rate coefficients are computed over the temperature range from 200 to 2000 K and they are shown to be in accordance with available experimental data. On the basis of the computed rate coefficients, the tropospheric lifetime of the CH3CCl2F and CH3CClF2 are estimated to be about 6.5 and 12.0 years, respectively.

Silver(I) complexes of the weakly coordinating solvents SO(2) and CH(2)Cl(2): crystal structures, bonding, and energetics of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)].

Science.gov (United States)

Decken, Andreas; Knapp, Carsten; Nikiforov, Grigori B; Passmore, Jack; Rautiainen, J Mikko; Wang, Xinping; Zeng, Xiaoqing

2009-06-22

Pushing the limits of coordination chemistry: The most weakly coordinated silver complexes of the very weakly coordinating solvents dichloromethane and liquid sulfur dioxide were prepared. Special techniques at low temperatures and the use of weakly coordinating anions allowed structural characterization of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(Cl(2)CH(2))(2)][SbF(6)] (see figure). An investigation of the bonding shows that these complexes are mainly stabilized by electrostatic monopole-dipole interactions.The synthetically useful solvent-free silver(I) salt Ag[Al(pftb)(4)] (pftb=--OC(CF(3))(3)) was prepared by metathesis reaction of Li[Al(pftb)(4)] with Ag[SbF(6)] in liquid SO(2). The solvated complexes [Ag(OSO)][Al(pftb)(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)] were prepared and isolated by special techniques at low temperatures and structurally characterized by single-crystal X-ray diffraction. The SO(2) complexes provide the first examples of coordination of the very weak Lewis base SO(2) to silver(I). The SO(2) molecule in [Ag(OSO)][Al(pftb)(4)] is eta(1)-O coordinated to Ag(+), while the SO(2) ligands in [Ag(OSO)(2/2)][SbF(6)] bridge two Ag(+) ions in an eta(2)-O,O' (trans,trans) manner. [Ag(CH(2)Cl(2))(2)][SbF(6)] contains [Ag(CH(2)Cl(2))(2)](+) ions linked through [SbF(6)](-) ions to give a polymeric structure. The solid-state silver(I) ion affinities (SIA) of SO(2) and CH(2)Cl(2), based on bond lengths and corresponding valence units in the corresponding complexes and tensimetric titrations of Ag[Al(pftb)(4)] and Ag[SbF(6)] with SO(2) vapor, show that SO(2) is a weaker ligand to Ag(+) than the commonly used weakly coordinating solvent CH(2)Cl(2) and indicated that binding strength of SO(2) to silver(I) in the silver(I) salts increases with increasing size of the corresponding counteranion ([Al(pftb)(4)](-)>[SbF(6)](-)). The experimental findings are in good agreement with theoretical gas-phase ligand

ChR2 transgenic animals in peripheral sensory system: Sensing light as various sensations.

Science.gov (United States)

Ji, Zhi-Gang; Wang, Hongxia

2016-04-01

Since the introduction of Channelrhodopsin-2 (ChR2) to neuroscience, optogenetics technology was developed, making it possible to activate specific neurons or circuits with spatial and temporal precision. Various ChR2 transgenic animal models have been generated and are playing important roles in revealing the mechanisms of neural activities, mapping neural circuits, controlling the behaviors of animals as well as exploring new strategy for treating the neurological diseases in both central and peripheral nervous system. An animal including humans senses environments through Aristotle's five senses (sight, hearing, smell, taste and touch). Usually, each sense is associated with a kind of sensory organ (eyes, ears, nose, tongue and skin). Is it possible that one could hear light, smell light, taste light and touch light? When ChR2 is targeted to different peripheral sensory neurons by viral vectors or generating ChR2 transgenic animals, the animals can sense the light as various sensations such as hearing, touch, pain, smell and taste. In this review, we focus on ChR2 transgenic animals in the peripheral nervous system. Firstly the working principle of ChR2 as an optogenetic actuator is simply described. Then the current transgenic animal lines where ChR2 was expressed in peripheral sensory neurons are presented and the findings obtained by these animal models are reviewed. Copyright © 2016 Elsevier Inc. All rights reserved.

Effect of solvent on cocrystallization of Es2+ with SrCl2

International Nuclear Information System (INIS)

Mikheev, N.B.; Veleshko, I.E.; Kulyukhin, S.A.

1994-01-01

Complexation of Es 2+ with tetraphenylborate (BPh 4 - ) in acetonitrile (CH 3 CN) and tetrahydrofuran (THF) is studied by cocrystallization. The dependence of the cocrystallization coefficients of Es 2+ on [LiBPh 4 ] demonstrated that in THF, in contrast with CH 3 CN, Es 2+ is not complexed by BPh 4 . The stability constants β 1 and β 2 of the Es 2+ -BPh 4 complexes are 6.6 and 16.0, respectively, in CH 3 CN

Variable temperature ion trap studies of CH4+ + H2, HD and D2: negative temperature dependence and significant isotope effect

International Nuclear Information System (INIS)

Asvany, O.; Savic, I.; Schlemmer, S.; Gerlich, D.

2004-01-01

Reactions of methane cations, CH 4 + , with H 2 , HD and D 2 have been studied in a variable temperature 22-pole ion trap from room temperature down to 15 K. The formation of CH 5 + in collisions with H 2 is slow at 300 K, but it becomes faster by at least one order of magnitude when the temperature is lowered to 15 K. This behavior is tentatively explained with a longer complex lifetime at low temperatures. However, since tunneling is most probably not responsible for product formation, other dynamical or statistical restrictions must be responsible for the negative temperature dependence. In collisions of CH 4 + with HD, the CH 5 + product ion (68% at 15 K) prevails over CH 4 D + (32%). Reaction of CH 4 + with D 2 is found to be much slower than with H 2 or HD. The rate coefficient for converting CH 4 + into CH 3 D + by H-D exchange has been determined to be smaller than 10 -12 cm 3 /s, indicating that scrambling in the CH 6 + complex is very unlikely

Synthesis, Resistivity, and Thermal Properties of the Cubic Perovskite NH 2CH=NH 2SnI 3and Related Systems

Science.gov (United States)

Mitzi, D. B.; Liang, K.

1997-12-01

Combining concentrated hydriodic acid solutions of tin(II) iodide and formamidine acetate in an inert atmosphere results in the precipitation of a new conducting organic-inorganic compound, NH 2CH=NH 2SnI 3, which at room temperature adopts a cubic perovskite structure. The lattice constant for NH 2CH=NH 2SnI 3is found to be a=6.316(1) Å, which is approximately 1.2% larger than that for the isostructural compound CH 3NH 3SnI 3. The electrical resistivity of a pressed pellet of the new compound exhibits semimetallic temperature dependence from 10 to 300 K, with evidence of a structural transition at approximately 75 K. NH 2CH=NH 2SnI 3begins to slowly decompose in an inert atmosphere at temperatures as low as 200°C, with bulk decomposition/melting occurring above 300°C. The properties of the formamidinium-based perovskite are compared with those of the related cubic (at room temperature) perovskite CH 3NH 3SnI 3and the mixed-cation system (CH 3NH 3) 1- x(NH 2CH=NH 2) xSnI 3.

Modeling Plasma-based CO2 and CH4 Conversion in Mixtures with N2, O2 and H2O: the Bigger Plasma Chemistry Picture

KAUST Repository

Wang, Weizong

2018-01-18

Due to the unique properties of plasma technology, its use in gas conversion applications is gaining significant interest around the globe. Plasma-based CO2 and CH4 conversion have become major research areas. Many investigations have already been performed regarding the single component gases, i.e. CO2 splitting and CH4 reforming, as well as for two component mixtures, i.e. dry reforming of methane (CO2/CH4), partial oxidation of methane (CH4/O2), artificial photosynthesis (CO2/H2O), CO2 hydrogenation (CO2/H2), and even first steps towards the influence of N2 impurities have been taken, i.e. CO2/N2 and CH4/N2. In this feature article we briefly discuss the advances made in literature for these different steps from a plasma chemistry modeling point of view. Subsequently, we present a comprehensive plasma chemistry set, combining the knowledge gathered in this field so far, and supported with extensive experimental data. This set can be used for chemical kinetics plasma modeling for all possible combinations of CO2, CH4, N2, O2 and H2O, to investigate the bigger picture of the underlying plasmachemical pathways for these mixtures in a dielectric barrier discharge plasma. This is extremely valuable for the optimization of existing plasma-based CO2 conversion and CH4 reforming processes, as well as for investigating the influence of N2, O2 and H2O on these processes, and even to support plasma-based multi-reforming processes.

Pionic X-ray intensities from C, CH2 and CD2

International Nuclear Information System (INIS)

Daniel, H.; Seki, R.

1980-01-01

The relative intensities of the carbon Lsub(α) and Lsub(β) pionic X-ray lines from graphite, polyethylene, and deuterated polyethylene have been measured. No differences between CH 2 and CD 2 were observed, but differences were found between graphite and the two polyethylene targets. (orig.)

Electron pairing analysis of the Fischer-type chromium-carbene complexes (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH )

Energy Technology Data Exchange (ETDEWEB)

Poater, Jordi; Cases, Montserrat; Fradera, Xavier; Duran, Miquel; Sola, Miquel

2003-10-15

The electron-pair density distributions of a series of 25 Fischer carbene complexes of the type (CO){sub 5}Cr=C(X)R (X=H, OH, OCH{sub 3}, NH{sub 2}, NHCH{sub 3} and R=H, CH{sub 3}, CH=CH{sub 2}, Ph, C-CH) are analyzed using the Atoms in Molecules theory. Localization and delocalization indices are used to characterize the electron pairing taking place in the Cr=C---X moiety in these complexes. Electron delocalization between the Cr and C atoms and between the C atom and the X group are related to the {pi}-donor strength of the X group and the degree of back-donation between the chromium pentacarbonyl and the carbene fragments. The results obtained with the Atoms in Molecules theory complement those obtained in a previous study by means of energy and charge decomposition analyses. Electron delocalization between the Cr atom and the X group is consistent with the hypothesis of a weak 3-center 4-electron bonding interaction in the Cr=C-X group of atoms. Except for X=H, {delta}(Cr,X) increases with the decrease of the {pi}-donor character of the X group.

Experimental measurements of vapor-liquid equilibria of the H2O + CO2 + CH4 ternary system

Science.gov (United States)

Qin, J.; Rosenbauer, R.J.; Duan, Zhenhao

2008-01-01

Reported are the experimental measurements on vapor-liquid equilibria in the H2O + CO2 + CH4 ternary system at temperatures from (324 to 375) K and pressures from (10 to 50) MPa. The results indicate that the CH4 solubility in the ternary mixture is about 10 % to 40 % more than that calculated by interpolation from the Henry's law constants of the binary system, H2O + CH4, and the solubility of CO2 is 6 % to 20 % more than what is calculated by the interpolation from the Henry's law constants of the binary mixture, H 2O + CO2. ?? 2008 American Chemical Society.

The effect of CO2, H2O and SO2 on the kinetics of NO reduction by CH4 over La2O3

International Nuclear Information System (INIS)

Toops, Todd J.; Walters, Arden B.; Vannice, M.A.

2002-01-01

The effect of CO 2 , H 2 O and SO 2 on the kinetics of NO reduction by CH 4 over unsupported La 2 O 3 has been examined between 773 and 973K in the presence of O 2 in the feed. La 2 O 3 can maintain a stable, high specific activity (mol/(sm 2 )) for NO reduction with high concentrations of CO 2 and H 2 O in the feed; however, either of these two products reversibly inhibits the activity by about one-half in the presence of excess O 2 . The catalyst is poisoned by SO 2 at these temperatures and an oxysulfate phase is formed, but partial regeneration can be achieved at 1023K. CO 2 in the feed causes the formation of lanthanum oxycarbonate, which reverts to La 2 O 3 when CO 2 is removed, but no bulk La oxyhydroxide is detected after quenching with H 2 O in the feed. The influence of CO 2 and H 2 O on kinetic behavior can be described by assuming they compete with reactants for adsorption on surface sites, including them in the site balance equation, and using the rate expression proposed previously for NO reduction by CH 4 in excess O 2 . With O 2 in the feed, integral conversions of CH 4 and O 2 frequently occurred due to the direct combustion of CH 4 by O 2 , although NO conversions remained differential; thus, an integral reactor model was chosen to analyze the data which utilized a recently determined rate equation for CH 4 combustion on La 2 O 3 in conjunction with a previously proposed model for NO reduction by CH 4 . The following rate expression described the rate of N 2 formation: N 2 T = ' NO P NO P CH 4 P O 2 0.5 / 1 + K NO P NO + K CH 4 P CH 4 + K O 2 0.5 P O 2 0.5 + K CO 2 P CO 2 + K H 2 O P H 2 O 2 . It gave a good fit to the experimental rate data for NO reduction, as well as providing enthalpies and entropies of adsorption obtained from the fitting parameters that demonstrated thermodynamic consistency and were similar to previous values. The heats of adsorption were altered somewhat when either CO 2 or H 2 O was added to the feed, and the following

Quantum Dynamics Study of the Isotopic Effect on Capture Reactions: HD, D2 + CH3

Science.gov (United States)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

Time-dependent wave-packet-propagation calculations are reported for the isotopic reactions, HD + CH3 and D2 + CH3, in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probabilities for different initial rotational-vibrational states are presented in this study. This study shows that excitations of the HD(D2) enhances the reactivities; whereas the excitations of the CH3 umbrella mode have the opposite effects. This is consistent with the reaction of H2 + CH3. The comparison of these three isotopic reactions also shows the isotopic effects in the initial-state-selected reaction probabilities. The cumulative reaction probabilities (CRP) are obtained by summing over initial-state-selected reaction probabilities. The energy-shift approximation to account for the contribution of degrees of freedom missing in the six dimensionality calculation is employed to obtain approximate full-dimensional CRPs. The rate constant comparison shows H2 + CH3 reaction has the biggest reactivity, then HD + CH3, and D2 + CH3 has the smallest.

Coupled-cluster sum-frequency generation nonlinear susceptibilities of methyl (CH3) and methylene (CH2) groups.

Science.gov (United States)

Tetsassi Feugmo, Conrard Giresse; Liégeois, Vincent; Champagne, Benoît

2017-11-15

The first vibrational sum frequency generation (SFG) spectra based on molecular properties calculated at the coupled cluster singles and doubles (CCSD) level of approximation have been simulated for interfacial model alkyl chains, providing benchmark data for comparisons with approximate methods, including density functional theory (DFT). The approach proceeds in three steps. In the first two steps, the molecular spectral properties are determined: the vibrational normal modes and frequencies and then the derivatives of the dipole moment and of the polarizability with respect to the normal coordinates. These derivatives are evaluated with a numerical differentiation approach, of which the accuracy was monitored using Romberg's procedure. Then, in the last step, a three-layer model is employed to evaluate the macroscopic second-order nonlinear optical responses and thereby the simulated SFG spectra of the alkyl interface. Results emphasize the following facts: (i) the dipole and polarizability derivatives calculated at the DFT level with the B3LYP exchange-correlation functional can differ, with respect to CCSD, by as much as ±10 to 20% and ±20 to 50% for the CH 3 and CH 2 vibrations, respectively; (ii) these differences are enhanced when considering the SFG intensities as well as their variations as a function of the experimental configuration (ppp versus ssp) and as a function of the tilt and rotation angles, defining the orientation of the alkyl chain at the interface; (iii) these differences originate from both the vibrational normal coordinates and the Cartesian derivatives of the dipole moment and polarizability; (iv) freezing the successive fragments of the alkyl chain strongly modifies the SFG spectrum and enables highlighting the delocalization effects between the terminal CH 3 group and its neighboring CH 2 units; and finally (v) going from the free chain to the free methyl model, and further to C 3v constraints on leads to large variations of two ratios

Background CH4 and N2O fluxes in low-input short rotation coppice

Science.gov (United States)

Görres, Carolyn-Monika; Zenone, Terenzio; Ceulemans, Reinhart

2016-04-01

Extensively managed short rotation coppice systems are characterized by low fluxes of CH4 and N2O. However due to the large global warming potential of these trace gases (GWP100: CH4: 34, N2O: 298), such background fluxes can still significantly contribute to offsetting the CO2 uptake of short rotation coppice systems. Recent technological advances in fast-response CH4 and N2O analysers have improved our capability to capture these background fluxes, but their quantification still remains a challenge. As an example, we present here CH4 and N2O fluxes from a short-rotation bioenergy plantation in Belgium. Poplars have been planted in a double-row system on a loamy sand in 2010 and coppiced in the beginning of 2012 and 2014 (two-year rotation system). In 2013 (June - November) and 2014 (April - August), the plantation's CH4 and N2O fluxes were measured in parallel with an eddy covariance tower (EC) and an automated chamber system (AC). The EC had a detection limit of 13.68 and 0.76 μmol m-2 h-1 for CH4 and N2O, respectively. The median detection limit of the AC was 0.38 and 0.08 μmol m-2 h-1 for CH4 and N2O, respectively. The EC picked up a few high CH4 emission events with daily averages >100 μmol m-2 h-1, but a large proportion of the measured fluxes were within the EC's detection limit. The same was true for the EC-derived N2O fluxes where the daily average flux was often close to the detection limit. Sporadically, some negative (uptake) fluxes of N2O were observed. On the basis of the EC data, no clear link was found between CH4 and N2O fluxes and environmental variables. The problem with fluxes within the EC detection limit is that a significant amount of the values can show the opposite sign, thus "mirroring" the true flux. Subsequently, environmental controls of background trace gas fluxes might be disguised in the analysis. As a next step, it will be tested if potential environmental drivers of background CH4 and N2O fluxes at the plantation can be

Large CO2 and CH4 release from a flooded formerly drained fen

Science.gov (United States)

Sachs, T.; Franz, D.; Koebsch, F.; Larmanou, E.; Augustin, J.

2016-12-01

Drained peatlands are usually strong carbon dioxide (CO2) sources. In Germany, up to 4.5 % of the national CO2 emissions are estimated to be released from agriculturally used peatlands and for some peatland-rich northern states, such as Mecklenburg-Western Pomerania, this share increases to about 20%. Reducing this CO2 source and restoring the peatlands' natural carbon sink is one objective of large-scale nature protection and restoration measures, in which 37.000 ha of drained and degraded peatlands in Mecklenburg-Western Pomerania are slated for rewetting. It is well known, however, that in the initial phase of rewetting, a reduction of the CO2 source strength is usually accompanied by an increase in CH4 emissions. Thus, whether and when the intended effects of rewetting with regard to greenhouse gases are achieved, depends on the balance of CO2 and CH4 fluxes and on the duration of the initial CH4 emission phase. In 2013, a new Fluxnet site went online at a flooded formerly drained river valley fen site near Zarnekow, NE Germany (DE-Zrk), to investigate the combined CO2 and CH4 dynamics at such a heavily degraded and rewetted peatland. The site is dominated by open water with submerged and floating vegetation and surrounding Typha latifolia.Nine year after rewetting, we found large CH4 emissions of 53 g CH4 m-2 a-1 from the open water area, which are 4-fold higher than from the surrounding vegetation zone (13 g CH4 m-2 a-1). Surprisingly, both the open water and the vegetated area were net CO2 sources of 158 and 750 g CO2 m-2 a-1, respectively. Unusual meteorological conditions with a warm and dry summer and a mild winter might have facilitated high respiration rates, particularly from temporally non-inundated organic mud in the vegetation zone.

Unveiling the chemistry of interstellar CH. Spectroscopy of the 2 THz N = 2 ← 1 ground state line

Science.gov (United States)

Wiesemeyer, H.; Güsten, R.; Menten, K. M.; Durán, C. A.; Csengeri, T.; Jacob, A. M.; Simon, R.; Stutzki, J.; Wyrowski, F.

2018-04-01

Context. The methylidyne radical CH is commonly used as a proxy for molecular hydrogen in the cold, neutral phase of the interstellar medium. The optical spectroscopy of CH is limited by interstellar extinction, whereas far-infrared observations provide an integral view through the Galaxy. While the HF ground state absorption, another H2 proxy in diffuse gas, frequently suffers from saturation, CH remains transparent both in spiral-arm crossings and high-mass star forming regions, turning this light hydride into a universal surrogate for H2. However, in slow shocks and in regions dissipating turbulence its abundance is expected to be enhanced by an endothermic production path, and the idea of a "canonical" CH abundance needs to be addressed. Aim. The N = 2 ← 1 ground state transition of CH at λ149 μm has become accessible to high-resolution spectroscopy thanks to the German Receiver for Astronomy at Terahertz Frequencies (GREAT) aboard the Stratospheric Observatory for Infrared Astronomy (SOFIA). Its unsaturated absorption and the absence of emission from the star forming regions makes it an ideal candidate for the determination of column densities with a minimum of assumptions. Here we present an analysis of four sightlines towards distant Galactic star forming regions, whose hot cores emit a strong far-infrared dust continuum serving as background signal. Moreover, if combined with the sub-millimeter line of CH at λ560 μm , environments forming massive stars can be analyzed. For this we present a case study on the "proto-Trapezium" cluster W3 IRS5. Methods: While we confirm the global correlation between the column densities of HF and those of CH, both in arm and interarm regions, clear signposts of an over-abundance of CH are observed towards lower densities. However, a significant correlation between the column densities of CH and HF remains. A characterization of the hot cores in the W3 IRS5 proto-cluster and its envelope demonstrates that the sub

Vacuum ultraviolet photoabsorption spectroscopy of CH2Cl2 and CD2Cl2 in the energy region 50,000-95,000 cm-1

Science.gov (United States)

Mandal, Anuvab; Singh, Param Jeet; Shastri, Aparna; Jagatap, B. N.

2014-12-01

A consolidated study of the VUV absorption spectra of CH2Cl2 and CD2Cl2 in the 50,000-95,000 cm-1 region using synchrotron radiation is presented. Rydberg series and vibronic analysis are carried out and supported by quantum chemical calculations. The broad absorption band of CH2Cl2 in the region 50,000-60,000 cm-1 is attributed to the valence states 11B2, 11B1 and 11A1. Most of the bands in the 60,000-95,000 cm-1 region are fitted to Rydberg series of ns, np and nd type converging to the first four ionization potentials 11.320, 11.357, 12.152 and 12.271 eV of CH2Cl2 arising from excitation of an electron from one of the four outermost Cl non-bonding orbitals (2b1, 3b2, 1a2 and 4a1). Vertical excited states of CH2Cl2 calculated using TDDFT are correlated with experimentally observed electronic states based on the symmetries of the initial and final MOs involved in a transition. A few Rydberg transitions viz. 2b1→5s, 4p, 5p, 6p; 3b2→4p, 5p; 1a2→4p are accompanied by vibronic features. Observed vibronic bands are assigned mainly to the CCl symmetric stretch (ν3‧) mode with smaller contributions from the CH symmetric stretch (ν1‧), CH2 bend (ν2‧) and CH2 wag (ν8‧) modes. Assignments are corroborated by comparison with the VUV absorption spectrum of the deuterated isotopologue CD2Cl2, reported here for the first time. The high underlying intensities seen in several sub-regions are explained by valence or valence-Rydberg mixed type transitions predicted with high oscillator strengths by the TDDFT calculations.

Imaging the Dynamics of CH2BrI Photodissociation in the Near Ultraviolet Region.

Science.gov (United States)

Pan, Changen; Zhang, Yi; Lee, Joseph D; Kidwell, Nathanael M

2018-04-19

The photodissociation dynamics of jet-cooled CH 2 BrI were investigated in the near-ultraviolet (UV) region from 280-310 nm using velocity map imaging. We report the translational and internal energy distributions of the CH 2 Br radical and ground state I ( 2 P 3/2 ) or spin-orbit excited I ( 2 P 1/2 ) fragments determined by velocity map imaging of the ionized iodine fragments following 2 + 1 resonance-enhanced multiphoton ionization of the nascent neutral iodine products. The velocity distributions indicate that most of the available energy is partitioned into the internal energy of the CH 2 Br radical with only modest translational excitation imparted to the cofragments, which is consistent with a simple impulsive model. Furthermore, from extrapolation of the velocity distribution results, the first determination of the C-I bond dissociation energy of CH 2 BrI is presented in this work to be D 0 = 16 790 ± 590 cm -1 . The ion images appear anisotropic, indicative of a prompt dissociation, and the derived anisotropy parameters are consistently positive. Additionally, the angular distributions report on the electronic excited state dynamics, which validate recent works characterizing the electronic states responsible for the first absorption band of CH 2 BrI. In the current work, photolysis of CH 2 BrI on the red edge of the absorption spectrum reveals an additional channel producing I ( 2 P 3/2 ) fragments.

Facile And Reversible Co Insertion Into The Ir-ch3 Bond Of [ir4(ch3)(co)8(μ4- η3-ph2pccph)(μ-pph2)

OpenAIRE

Vargas M.D.; Pereira R.M.S.; Braga D.; Grepioni F.

1993-01-01

Reaction of [Ir4H(CO)10(mu-PPh2)) with BuLi, Ph2PC=CPh and then Mel gives [Ir4(CH3)(CO)8(mu4-eta3-Ph2PCCPh)(mu-PPh2)], which undergoes a reversible two-step CO insertion under extremely mild conditions to yield Ir4{(CH3C(O)}(CO)8-(mu4:eta3-Ph2PCCPh)(mu-PPh2)] as the final product; the structures of both species have been established by X-ray diffraction studies.

NMR Spectroscopic Characterization of Methylcobalt(III) Compounds with Classical Ligands. Crystal Structures of [Co(NH(3))(5)(CH(3))]S(2)O(6), trans-[Co(en)(2)(NH(3))(CH(3))]S(2)O(6) (en = 1,2-Ethanediamine), and [Co(NH(3))(6)]-mer,trans-[Co(NO(2))(3)(NH(

DEFF Research Database (Denmark)

Kofod, Pauli; Harris, Pernille; Larsen, Sine

1997-01-01

magnetic resonance spectroscopy and by absorption spectroscopy. Single-crystal X-ray structure determinations at 122.0(5) K were performed on [Co(NH(3))(5)(CH(3))]S(2)O(6) (1), trans-[Co(en)(2)(NH(3))(CH(3))]S(2)O(6) (2), and [Co(NH(3))(6)]-mer,trans-[Co(NO(2))(3)(NH(3))(2)(CH(3))](2)-trans-[Co(NO(2...

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures.

Science.gov (United States)

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-09-26

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H 2 ) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H 2 /CH 4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311-500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H 2 /CH 4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H 2 /CH 4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400-500 °C, the H 2 /CH 4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H 2 /CH 4 ratios cannot reliably discriminate abiotic from biotic methane.

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures

Science.gov (United States)

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-09-01

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311-500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400-500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane.

Atmospheric chemistry of dimethyl sulfide. Kinetics of the CH3SCH2O2 + NO2 reaction in the gas phase at 296 K

DEFF Research Database (Denmark)

Nielsen, O.J.; Sehested, J.; Wallington, T.J.

1995-01-01

The pulse radiolysis of SF6/CH3SCH3/O-2/NO2 gas mixtures was used to generate CH3SCH2O2 radicals in the presence of NO2. By monitoring the rate of NO2 decay using its absorption at 400 nm, rate constants for the reaction of CH3SCH2O2 radicals with NO2 were measured to be (9.2 +/- 0.9) x 10...

Biogeochemical controls on microbial CH4 and CO2 production in Arctic polygon tundra

Science.gov (United States)

Zheng, J.

2016-12-01

Accurately simulating methane (CH4) and carbon dioxide (CO2) emissions from high latitude soils is critically important for reducing uncertainties in soil carbon-climate feedback predictions. The signature polygonal ground of Arctic tundra generates high level of heterogeneity in soil thermal regime, hydrology and oxygen availability, which limits the application of current land surface models with simple moisture response functions. We synthesized CH4 and CO2 production measurements from soil microcosm experiments across a wet-to dry permafrost degradation gradient from low-centered (LCP) to flat-centered (FCP), and high-centered polygons (HCP) to evaluate the relative importance of biogeochemical processes and their response to warming. More degraded polygon (HCP) showed much less carbon loss as CO2 or CH4, while the total CO2 production from FCP is comparable to that from LCP. Maximum CH4 production from the active layer of LCP was nearly 10 times that of permafrost and FCP. Multivariate analyses identifies gravimetric water content and organic carbon content as key predictors for CH4 production, and iron reduction as a key regulator of pH. The synthesized data are used to validate the geochemical model PHREEQC with extended anaerobic organic substrate turnover, fermentation, iron reduction, and methanogenesis reactions. Sensitivity analyses demonstrate that better representations of anaerobic processes and their pH dependency could significantly improve estimates of CH4 and CO2 production. The synthesized data suggest local decreases in CH4 production along the polygon degradation gradient, which is consistent with previous surface flux measurements. Methane oxidation occurring through the soil column of degraded polygons contributes to their low CH4 emissions as well.

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

Soil-atmospheric exchange of CO2, CH4, and N2O in three subtropical forest ecosystems in southern China

Science.gov (United States)

Tang, X.; Liu, S.; Zhou, G.; Zhang, Dongxiao; Zhou, C.

2006-01-01

The magnitude, temporal, and spatial patterns of soil-atmospheric greenhouse gas (hereafter referred to as GHG) exchanges in forests near the Tropic of Cancer are still highly uncertain. To contribute towards an improvement of actual estimates, soil-atmospheric CO2, CH4, and N2O fluxes were measured in three successional subtropical forests at the Dinghushan Nature Reserve (hereafter referred to as DNR) in southern China. Soils in DNR forests behaved as N2O sources and CH4 sinks. Annual mean CO2, N2O, and CH4 fluxes (mean ?? SD) were 7.7 ?? 4.6MgCO2-Cha-1 yr-1, 3.2 ?? 1.2 kg N2ONha-1 yr-1, and 3.4 ?? 0.9 kgCH4-Cha-1 yr-1, respectively. The climate was warm and wet from April through September 2003 (the hot-humid season) and became cool and dry from October 2003 through March 2004 (the cool-dry season). The seasonality of soil CO2 emission coincided with the seasonal climate pattern, with high CO2 emission rates in the hot-humid season and low rates in the cool-dry season. In contrast, seasonal patterns of CH4 and N2O fluxes were not clear, although higher CH4 uptake rates were often observed in the cool-dry season and higher N2O emission rates were often observed in the hot-humid season. GHG fluxes measured at these three sites showed a clear increasing trend with the progressive succession. If this trend is representative at the regional scale, CO2 and N2O emissions and CH4 uptake in southern China may increase in the future in light of the projected change in forest age structure. Removal of surface litter reduced soil CO2 effluxes by 17-44% in the three forests but had no significant effect on CH4 absorption and N2O emission rates. This suggests that microbial CH4 uptake and N2O production was mainly related to the mineral soil rather than in the surface litter layer. ?? 2006 Blackwell Publishing Ltd.

CO2 adsorption-assisted CH4 desorption on carbon models of coal surface: A DFT study

Science.gov (United States)

Xu, He; Chu, Wei; Huang, Xia; Sun, Wenjing; Jiang, Chengfa; Liu, Zhongqing

2016-07-01

Injection of CO2 into coal is known to improve the yields of coal-bed methane gas. However, the technology of CO2 injection-enhanced coal-bed methane (CO2-ECBM) recovery is still in its infancy with an unclear mechanism. Density functional theory (DFT) calculations were performed to elucidate the mechanism of CO2 adsorption-assisted CH4 desorption (AAD). To simulate coal surfaces, different six-ring aromatic clusters (2 × 2, 3 × 3, 4 × 4, 5 × 5, 6 × 6, and 7 × 7) were used as simplified graphene (Gr) carbon models. The adsorption and desorption of CH4 and/or CO2 on these carbon models were assessed. The results showed that a six-ring aromatic cluster model (4 × 4) can simulate the coal surface with limited approximation. The adsorption of CO2 onto these carbon models was more stable than that in the case of CH4. Further, the adsorption energies of single CH4 and CO2 in the more stable site were -15.58 and -18.16 kJ/mol, respectively. When two molecules (CO2 and CH4) interact with the surface, CO2 compels CH4 to adsorb onto the less stable site, with a resulting significant decrease in the adsorption energy of CH4 onto the surface of the carbon model with pre-adsorbed CO2. The Mulliken charges and electrostatic potentials of CH4 and CO2 adsorbed onto the surface of the carbon model were compared to determine their respective adsorption activities and changes. At the molecular level, our results showed that the adsorption of the injected CO2 promoted the desorption of CH4, the underlying mechanism of CO2-ECBM.

The relationships between termite mound CH4/CO2 emissions and internal concentration ratios are species specific

Directory of Open Access Journals (Sweden)

H. Jamali

2013-04-01

Full Text Available We investigated the relative importance of CH4 and CO2 fluxes from soil and termite mounds at four different sites in the tropical savannas of northern Australia near Darwin and assessed different methods to indirectly predict CH4 fluxes based on CO2 fluxes and internal gas concentrations. The annual flux from termite mounds and surrounding soil was dominated by CO2 with large variations among sites. On a carbon dioxide equivalent (CO2-e basis, annual CH4 flux estimates from termite mounds were 5- to 46-fold smaller than the concurrent annual CO2 flux estimates. Differences between annual soil CO2 and soil CH4 (CO2-e fluxes were even greater, soil CO2 fluxes being almost three orders of magnitude greater than soil CH4 (CO2-e fluxes at site. The contribution of CH4 and CO2 emissions from termite mounds to the total CH4 and CO2 emissions from termite mounds and soil in CO2-e was less than 1%. There were significant relationships between mound CH4 flux and mound CO2 flux, enabling the prediction of CH4 flux from measured CO2 flux; however, these relationships were clearly termite species specific. We also observed significant relationships between mound flux and gas concentration inside mound, for both CH4 and CO2, and for all termite species, thereby enabling the prediction of flux from measured mound internal gas concentration. However, these relationships were also termite species specific. Using the relationship between mound internal gas concentration and flux from one species to predict mound fluxes from other termite species (as has been done in the past would result in errors of more than 5-fold for mound CH4 flux and 3-fold for mound CO2 flux. This study highlights that CO2 fluxes from termite mounds are generally more than one order of magnitude greater than CH4 fluxes. There are species-specific relationships between CH4 and CO2 fluxes from a mound, and between the inside mound concentration of a gas and the mound flux emission of the

The relationships between termite mound CH4/CO2 emissions and internal concentration ratios are species specific

Science.gov (United States)

Jamali, H.; Livesley, S. J.; Hutley, L. B.; Fest, B.; Arndt, S. K.

2013-04-01

We investigated the relative importance of CH4 and CO2 fluxes from soil and termite mounds at four different sites in the tropical savannas of northern Australia near Darwin and assessed different methods to indirectly predict CH4 fluxes based on CO2 fluxes and internal gas concentrations. The annual flux from termite mounds and surrounding soil was dominated by CO2 with large variations among sites. On a carbon dioxide equivalent (CO2-e) basis, annual CH4 flux estimates from termite mounds were 5- to 46-fold smaller than the concurrent annual CO2 flux estimates. Differences between annual soil CO2 and soil CH4 (CO2-e) fluxes were even greater, soil CO2 fluxes being almost three orders of magnitude greater than soil CH4 (CO2-e) fluxes at site. The contribution of CH4 and CO2 emissions from termite mounds to the total CH4 and CO2 emissions from termite mounds and soil in CO2-e was less than 1%. There were significant relationships between mound CH4 flux and mound CO2 flux, enabling the prediction of CH4 flux from measured CO2 flux; however, these relationships were clearly termite species specific. We also observed significant relationships between mound flux and gas concentration inside mound, for both CH4 and CO2, and for all termite species, thereby enabling the prediction of flux from measured mound internal gas concentration. However, these relationships were also termite species specific. Using the relationship between mound internal gas concentration and flux from one species to predict mound fluxes from other termite species (as has been done in the past) would result in errors of more than 5-fold for mound CH4 flux and 3-fold for mound CO2 flux. This study highlights that CO2 fluxes from termite mounds are generally more than one order of magnitude greater than CH4 fluxes. There are species-specific relationships between CH4 and CO2 fluxes from a mound, and between the inside mound concentration of a gas and the mound flux emission of the same gas, but

Oxidation mechanisms of CF2Br2 and CH2Br2 induced by air nonthermal plasma.

Science.gov (United States)

Schiorlin, Milko; Marotta, Ester; Dal Molin, Marta; Paradisi, Cristina

2013-01-02

Oxidation mechanisms in air nonthermal plasma (NTP) at room temperature and atmospheric pressure were investigated in a corona reactor energized by +dc, -dc, or +pulsed high voltage.. The two bromomethanes CF(2)Br(2) and CH(2)Br(2) were chosen as model organic pollutants because of their very different reactivities with OH radicals. Thus, they served as useful mechanistic probes: they respond differently to the presence of humidity in the air and give different products. By FT-IR analysis of the postdischarge gas the following products were detected and quantified: CO(2) and CO in the case of CH(2)Br(2), CO(2) and F(2)C ═ O in the case of CF(2)Br(2). F(2)C ═ O is a long-lived oxidation intermediate due to its low reactivity with atmospheric radicals. It is however removed from the NTP processed gas by passage through a water scrubber resulting in hydrolysis to CO(2) and HF. Other noncarbon containing products of the discharge were also monitored by FT-IR analysis, including HNO(3) and N(2)O. Ozone, an important product of air NTP, was never detected in experiments with CF(2)Br(2) and CH(2)Br(2) because of the highly efficient ozone depleting cycles catalyzed by BrOx species formed from the bromomethanes. It is concluded that, regardless of the type of corona applied, CF(2)Br(2) reacts in air NTP via a common intermediate, the CF(2)Br radical. The possible reactions leading to this radical are discussed, including, for -dc activation, charge exchange with O(2)(-), a species detected by APCI mass spectrometry.

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.

A pan-Arctic synthesis of CH4 and CO2 production from anoxic soil incubations

Science.gov (United States)

Treat, C.C.; Natali, Susan M.; Ernakovich, Jessica; Iverson, Colleen M.; Lupasco, Massimo; McGuire, A. David; Norby, Richard J.; Roy Chowdhury, Taniya; Richter, Andreas; Šantrůčková, Hana; Schädel, C.; Schuur, Edward A.G.; Sloan, Victoria L.; Turetsky, Merritt R.; Waldrop, Mark P.

2015-01-01

Permafrost thaw can alter the soil environment through changes in soil moisture, frequently resulting in soil saturation, a shift to anaerobic decomposition, and changes in the plant community. These changes, along with thawing of previously frozen organic material, can alter the form and magnitude of greenhouse gas production from permafrost ecosystems. We synthesized existing methane (CH4) and carbon dioxide (CO2) production measurements from anaerobic incubations of boreal and tundra soils from the geographic permafrost region to evaluate large-scale controls of anaerobic CO2 and CH4 production and compare the relative importance of landscape-level factors (e.g., vegetation type and landscape position), soil properties (e.g., pH, depth, and soil type), and soil environmental conditions (e.g., temperature and relative water table position). We found fivefold higher maximum CH4 production per gram soil carbon from organic soils than mineral soils. Maximum CH4 production from soils in the active layer (ground that thaws and refreezes annually) was nearly four times that of permafrost per gram soil carbon, and CH4 production per gram soil carbon was two times greater from sites without permafrost than sites with permafrost. Maximum CH4 and median anaerobic CO2 production decreased with depth, while CO2:CH4 production increased with depth. Maximum CH4 production was highest in soils with herbaceous vegetation and soils that were either consistently or periodically inundated. This synthesis identifies the need to consider biome, landscape position, and vascular/moss vegetation types when modeling CH4 production in permafrost ecosystems and suggests the need for longer-term anaerobic incubations to fully capture CH4 dynamics. Our results demonstrate that as climate warms in arctic and boreal regions, rates of anaerobic CO2 and CH4 production will increase, not only as a result of increased temperature, but also from shifts in vegetation and increased

Reduced gas seepages in ophiolitic complexes: Evidences for multiple origins of the H2-CH4-N2 gas mixtures

Science.gov (United States)

Vacquand, Christèle; Deville, Eric; Beaumont, Valérie; Guyot, François; Sissmann, Olivier; Pillot, Daniel; Arcilla, Carlo; Prinzhofer, Alain

2018-02-01

This paper proposes a comparative study of reduced gas seepages occurring in ultrabasic to basic rocks outcropping in ophiolitic complexes based on the study of seepages from Oman, the Philippines, Turkey and New Caledonia. This study is based on analyses of the gas chemical composition, noble gases contents, stable isotopes of carbon, hydrogen and nitrogen. These seepages are mostly made of mixtures of three main components which are H2, CH4 and N2 in various proportions. The relative contents of the three main gas components show 4 distinct types of gas mixtures (H2-rich, N2-rich, N2-H2-CH4 and H2-CH4). These types are interpreted as reflecting different zones of gas generation within or below the ophiolitic complexes. In the H2-rich type, associated noble gases display signatures close to the value of air. In addition to the atmospheric component, mantle and crustal contributions are present in the N2-rich, N2-H2-CH4 and H2-CH4 types. H2-bearing gases are either associated with ultra-basic (pH 10-12) spring waters or they seep directly in fracture systems from the ophiolitic rocks. In ophiolitic contexts, ultrabasic rocks provide an adequate environment with available Fe2+ and alkaline conditions that favor H2 production. CH4 is produced either directly by reaction of dissolved CO2 with basic-ultrabasic rocks during the serpentinization process or in a second step by H2-CO2 interaction. H2 is present in the gas when no more carbon is available in the system to generate CH4. The N2-rich type is notably associated with relatively high contents of crustal 4He and in this gas type N2 is interpreted as issued mainly from sediments located below the ophiolitic units.

OH yields from the CH3CO+O-2 reaction using an internal standard\\ud

OpenAIRE

Carr, S.A.; Baeza-Romero, M.T.; Blitz, M.A.; Pilling, M.J.; Heard, D.E.; Seakins, P.W.

2007-01-01

Laser flash photolysis of CH3C(O)OH at 248 nm was used to create equal zero time yields of CH3CO and OH. The absolute OH yield from the CH3CO + O2 (+M) reaction was determined by following the OH temporal profile using the zero time\\ud OH concentration as an internal standard. The OH yield from CH3CO + O2 (+M) was observed to decrease with increasing pressure with an extrapolated zero pressure yield\\ud close to unity (1.1 ± 0.2, quoted uncertainties correspond to 95% confidence limits). The r...

Photosynthates as dominant source of CH4 and CO2 in soil water and CH4 emitted to the atmosphere from paddy fields

Science.gov (United States)

Minoda, Tomomi; Kimura, Mamoto; Wada, Eitaro

1996-09-01

Emission rates of CH4 from paddy soil with and without rice straw applications were measured with pot experiments to estimate the contribution of rice straw to the total CH4 emission during the growth period of rice plants. The CH4 derived from rice straw was calculated to be 44% of the total emission. 13CO2 uptake experiments were also carried out four times from June 30 to September 13, 1994, to estimate the contribution of photosynthesized carbon to CH4 emission. The contribution percentages of photosynthesized carbon to the total CH4 emitted to the atmosphere were 3.8% around June 30, 31% around July 25, 30% around August 19, and 14% around September 13 in the treatment with rice straw applications, and 52% around July 25, 28% around August 19, and 15% around September 13 in the treatment without rice straw applications. They were calculated to be 22% and 29% for the entire growth period in the treatments with and without rice straw applications, respectively. The contribution percentages of photosynthesized carbon to the total CH4 and inorganic carbon (Σ CO2) dissolved in soil water were 1.3%, 30%, 29%, and 34% for dissolved CH4 and 3.0%, 36%, 30% and 28% for dissolved inorganic carbon around June 30, July 25, August l9, and September 13, respectively, in the treatment with rice straw applications. They were 70%, 23%, and 32% for dissolved CH4 and 31%, 16%, and 19% for dissolved inorganic carbon around July 25, August 19, and September 13, respectively, in the treatment without rice straw applications.

Infrared absorption of CH3OSO and CD3OSO radicals produced upon photolysis of CH3OS(O)Cl and CD3OS(O)Cl in p-H2 matrices

International Nuclear Information System (INIS)

Lee, Yu-Fang; Kong, Lin-Jun; Lee, Yuan-Pern

2012-01-01

Irradiation at 239 ± 20 nm of a p-H 2 matrix containing methoxysulfinyl chloride, CH 3 OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to ν 1 , CH 2 antisymmetric stretching), 2999.5 (ν 2 , CH 3 antisymmetric stretching), 2950.4 (ν 3 , CH 3 symmetric stretching), 1465.2 (ν 4 , CH 2 scissoring), 1452.0 (ν 5 , CH 3 deformation), 1417.8 (ν 6 , CH 3 umbrella), 1165.2 (ν 7 , CH 3 wagging), 1152.1 (ν 8 , S=O stretching mixed with CH 3 rocking), 1147.8 (ν 9 , S=O stretching mixed with CH 3 wagging), 989.7 (ν 10 , C-O stretching), and 714.5 cm -1 (ν 11 , S-O stretching) modes of syn-CH 3 OSO. When CD 3 OS(O)Cl in a p-H 2 matrix was used, lines at 2275.9 (ν 1 ), 2251.9 (ν 2 ), 2083.3 (ν 3 ), 1070.3 (ν 4 ), 1056.0 (ν 5 ), 1085.5 (ν 6 ), 1159.7 (ν 7 ), 920.1 (ν 8 ), 889.0 (ν 9 ), 976.9 (ν 10 ), and 688.9 (ν 11 ) cm -1 appeared and are assigned to syn-CD 3 OSO; the mode numbers correspond to those used for syn-CH 3 OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86/aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH 3 OSO near 2991, 2956, 1152, and 994 cm -1 to 11 lines, including those associated with C-O, O-S, and S=O stretching modes. Vibrational wavenumbers of syn-CD 3 OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H 2 such that the Cl atom, produced via UV photodissociation of CH 3 OS(O)Cl in situ, might escape from the original cage to yield isolated CH 3 OSO radicals.

Infrared absorption of CH3OSO and CD3OSO radicals produced upon photolysis of CH3OS(O)Cl and CD3OS(O)Cl in p-H2 matrices.

Science.gov (United States)

Lee, Yu-Fang; Kong, Lin-Jun; Lee, Yuan-Pern

2012-03-28

Irradiation at 239 ± 20 nm of a p-H(2) matrix containing methoxysulfinyl chloride, CH(3)OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to ν(1), CH(2) antisymmetric stretching), 2999.5 (ν(2), CH(3) antisymmetric stretching), 2950.4 (ν(3), CH(3) symmetric stretching), 1465.2 (ν(4), CH(2) scissoring), 1452.0 (ν(5), CH(3) deformation), 1417.8 (ν(6), CH(3) umbrella), 1165.2 (ν(7), CH(3) wagging), 1152.1 (ν(8), S=O stretching mixed with CH(3) rocking), 1147.8 (ν(9), S=O stretching mixed with CH(3) wagging), 989.7 (ν(10), C-O stretching), and 714.5 cm(-1) (ν(11), S-O stretching) modes of syn-CH(3)OSO. When CD(3)OS(O)Cl in a p-H(2) matrix was used, lines at 2275.9 (ν(1)), 2251.9 (ν(2)), 2083.3 (ν(3)), 1070.3 (ν(4)), 1056.0 (ν(5)), 1085.5 (ν(6)), 1159.7 (ν(7)), 920.1 (ν(8)), 889.0 (ν(9)), 976.9 (ν(10)), and 688.9 (ν(11)) cm(-1) appeared and are assigned to syn-CD(3)OSO; the mode numbers correspond to those used for syn-CH(3)OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86∕aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH(3)OSO near 2991, 2956, 1152, and 994 cm(-1) to 11 lines, including those associated with C-O, O-S, and S=O stretching modes. Vibrational wavenumbers of syn-CD(3)OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H(2) such that the Cl atom, produced via UV photodissociation of CH(3)OS(O)Cl in situ, might escape from the original cage to yield isolated CH(3)OSO radicals.

Reaction of singlet-excited 2,3-diazabicyclo[2.2.2]oct-2-ene and tert-butoxyl radicals with aryl-substituted benzofuranones.

Science.gov (United States)

Lundgren, Cecilia Vannesjö; Koner, Apurba L; Tinkl, Michael; Pischel, Uwe; Nau, Werner M

2006-03-03

5,7-Di-tert-butyl-3-aryl-3H-benzofuran-2-ones are lactones with potential antioxidant activity, owing to their abstractable benzylic C-H hydrogens. The fluorescence quenching of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO), an established probe for the hydrogen-donor propensity of chain-breaking antioxidants, was investigated for 16 aryl-substituted benzofuranone derivatives [m,m-(CF3)2, p-CN, m-CN, p-CF3, p-COOCH3, m-CF3, p-Cl, p-F, H, m-CH3, p-CH3, m,p-(CH3)2, p-OCH3, o-CH3, o-CF3, o,m-(CH3)2]. Analysis of the rate data in terms of a linear free energy relationship yielded a reaction constant of rho = +0.35. This implies that n,pi*-excited DBO acts as nucleophilic species. In contrast, hydrogen abstraction of tert-butoxyl radicals from the benzofuranones was accelerated by electron-donating substituents (rho = -0.23), in conformity with the electrophilic character of oxygen-centered alkoxyl radicals. Possible implications for the optimization of the hydrogen-donor propensity of antioxidants through structural variation are discussed.

Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

Science.gov (United States)

Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A

2017-09-19

promote C-H bond formation. Thermochemical insights into the disparate reactivities of these clusters were achieved through hydricity measurements using SEC. We found that only [H-Fe 4 N(CO) 12 ] - and its derivative [H-Fe 4 N(CO) 11 (PPh 3 )] - have hydricities modest enough to avoid H 2 production but strong enough to make formate. [H-Fe 4 C(CO) 12 ] 2- is a stronger hydride donor, theoretically capable of making formate, but due to an overwhelming thermodynamic driving force and the increased electrostatic attraction between the more negative cluster and H + , only H 2 is observed experimentally. This illustrates the fundamental importance of controlling thermochemistry when designing new catalysts selective for C-H bond formation and establishes a hydricity range of 15.5-24.1 or 44-49 kcal mol -1 where C-H bond formation may be favored in water or MeCN, respectively.

Influence of the pressure and power on the non-equilibrium plasma chemistry of C{sub 2}, C{sub 2}H, C{sub 2}H{sub 2}, CH{sub 3} and CH{sub 4} affecting the synthesis of nanodiamond thin films from C{sub 2}H{sub 2} (1%)/H{sub 2}/Ar-rich plasmas

Energy Technology Data Exchange (ETDEWEB)

Gordillo-Vazquez, F J [Instituto de Optica, C.S.I.C., Serrano 121, 28006 Madrid (Spain); Albella, J M [Instituto de Materiales de Madrid, C.S.I.C., Cantoblanco, 28049 Madrid (Spain)

2004-02-01

We have used a kinetic model to investigate the influence of changing the pressure (0.1-0.8 Torr) and power (100-300 W) on the non-equilibrium plasma chemistry of RF (13.56 MHz) produced C{sub 2}H{sub 2} (1%)/H{sub 2}/Ar plasmas of interest for the synthesis of nanodiamond thin films. We found that the concentrations of the species C{sub 2}(X{sup 1}SIGMA{sup +}{sub g}), C{sub 2}(a{sup 3}PI{sub u}) and C{sub 2}H are not sensitive to variations in the power but they exhibit a significant increase when the pressure decreases at high argon content in the plasma. In addition, the concentrations of C{sub 2}H{sub 2}, CH{sub 4} and CH{sub 3} exhibit a slight (case of C{sub 2}H{sub 2}) or negligible (case of CH{sub 3} and CH{sub 4}) power-dependence although they decrease (case of C{sub 2}H{sub 2} and CH{sub 4}) or remain almost constant (case of CH{sub 3}) as the pressure decreases. A reasonable agreement is found when comparing the model predictions with available experimental results. These findings provide a basic understanding of the plasma chemistry of hydrocarbon/Ar-rich plasma environments and, at the same time, can be of interest to optimize the processing conditions of nanodiamond films from medium pressure RF hydrocarbon/Ar-rich plasmas.

Polymorphism Analysis of Ch1 and Ch2 Genes in the Siberian Cat

Directory of Open Access Journals (Sweden)

Stefano Sartore

2017-12-01

Full Text Available Cats are usually spreaders of allergens that are critical for sensitive people; the Siberian cat is a breed supposed to be low level allergenic, according to some breeders’ statements. The sequence of the two genes, namely Ch1 and Ch2, that code for the allergen Fel d 1, the major allergen responsible for outbreaks of allergy symptoms, is not yet known in the Siberian cat, and finding this was the aim of our investigation. Notably, our work is the first survey of the genetic structure of these genes in Siberian cats. The comparison of the sequences of Siberian cats, non-Siberian cats, and sequences present in the National Center for Biotechnology Information database revealed a considerable number of mutations; some of those detected in the Siberian cat, due to their position in exon regions, could affect the Fel d 1 allergenic properties. Therefore, further investigations are recommended to assess if the identified mutations can be responsible for a reduced-allergen synthesis and can be used as markers for selection of low level allergenic cats.

Optimisation of expansion liquefaction processes using mixed refrigerant N_2–CH_4

International Nuclear Information System (INIS)

Ding, He; Sun, Heng; He, Ming

2016-01-01

Highlights: • A refrigerant composition matching method for N_2–CH_4 expansion processes. • Efficiency improvements for propane pre-cooled N_2–CH_4 expansion processes. • The process shows good adaptability to varying natural gas compositions. - Abstract: An expansion process with a pre-cooling system is simulated and optimised by Aspen HYSYS and MATLAB"™. Taking advantage of higher specific refrigeration effect of methane and easily reduced refrigeration temperature of nitrogen, the designed process adopts N_2–CH_4 as a mixed refrigerant. Based on the different thermodynamic properties and sensitivity difference of N_2 and CH_4 over the same heat transfer temperature range, this work proposes a novel method of matching refrigerant composition which aims at single-stage or multi-stage series expansion liquefaction processes with pre-cooling systems. This novel method is applied successfully in propane pre-cooled N_2–CH_4 expansion process, and the unit power consumption is reduced to 7.09 kWh/kmol, which is only 5.35% higher than the global optimised solutions obtained by genetic algorithm. This novel method can fulfil the accomplishments of low energy consumption and high liquefaction rate, and thus decreases the gap between the mixed refrigerant and expansion processes in energy consumption. Furthermore, the high exergy efficiency of the process indicates good adaptability to varying natural gas compositions.

Optical properties of bias-induced CH sub 4 -H sub 2 plasma for diamond film deposition

CERN Document Server

Zhu, X D; Zhou, H Y; Wen, X H; Li, D

2002-01-01

Methane (CH sub 4) and hydrogen (H sub 2) reactive gas mixture has been in situ investigated in a hot filament diamond chemical vapor deposition reactor with a negatively variable biasing voltage applied to the hot filament with respect to the substrate using infrared absorption spectroscopy and optical emission spectroscopy. It is found that CH sub 4 converts increasingly to C sub 2 H sub 2 upon raising the filament temperature in a pure thermal activation state, no optical emission of species is observed. Upon bias application, both CH sub 4 and C sub 2 H sub 2 in infrared (IR) absorption intensity decrease with increasing bias current, even the IR absorption intensity of C sub 2 H sub 2 decreases more rapidly than that of CH sub 4. Meanwhile, the clear emission lines indexed to H, CH, and CH sup + appear in the optical emission spectrum obtained, showing that a large amount of excited radicals are produced in the gas phase after applying bias. It is believed that the further generation of activated radical...

The relationship between termite mound CH4/CO2 emissions and internal concentration ratios are species specific

Science.gov (United States)

Jamali, H.; Livesley, S. J.; Hutley, L. B.; Fest, B.; Arndt, S. K.

2012-12-01

1. We investigated the relative importance of CH4 and CO2 fluxes from soil and termite mounds at four different sites in the tropical savannas of Northern Australia near Darwin and assessed different methods to indirectly predict CH4 fluxes based on CO2 fluxes and internal gas concentrations. 2. The annual flux from termite mounds and surrounding soil was dominated by CO2 with large variations among sites. On a CO2-e basis, annual CH4 flux estimates from termite mounds were 5- to 46-fold smaller than the concurrent annual CO2 flux estimates. Differences between annual soil CO2 and soil CH4 (CO2-e) fluxes were even greater, soil CO2 fluxes being almost three orders of magnitude greater than soil CH4 (CO2-e) fluxes at site. 3. There were significant relationships between mound CH4 flux and mound CO2 flux, enabling the prediction of CH4 flux from measured CO2 flux, however, these relationships were clearly termite species specific. 4. We also observed significant relationships between mound flux and gas concentration inside mound, for both CH4 and CO2, and for all termite species, thereby enabling the prediction of flux from measured mound internal gas concentration. However, these relationships were also termite species specific. Using the relationship between mound internal gas concentration and flux from one species to predict mound fluxes from other termite species (as has been done in past) would result in errors of more than 5-fold for CH4 and 3-fold for CO2. 5. This study highlights that CO2 fluxes from termite mounds are generally more than one order of magnitude greater than CH4 fluxes. There are species-specific relationships between CH4 and CO2 fluxes from a~mound, and between the inside mound concentration of a gas and the mound flux emission of the same gas, but these relationships vary greatly among termite species. Consequently, there is no generic relationship that will allow for the prediction of CH4 fluxes from termite mounds of all species.

Stabilization and reactivity of a terminal phosphidounit on Pt(II). Synthesis and X-ray structure of cationic diphelylphosphine [Pt{C6H3(CH2NMe2)2-2,6}(PHPh2)][CF3SO3] and Diphenyl-phosphido Bridged Pt(II)-Pd(II) Complex [Pt{C6H3(CH2NMe2)2-2,6} (µ-PPh2) Pd(C6H4CH2NMe2-2)(H2O)][BF4] CH2Cl2

NARCIS (Netherlands)

Koten, G. van; Maassarani, F.; Davidson, M.F.; Wehman-Ooyevaar, ICM; Grove, D.M.; Koten, M.A. van; Smeets, W.J.J.; Spek, A.L.

1995-01-01

Reaction of diphenylphosphine with the complexes [Pt(NCN)(H{2}O)]X (NCN = C{6}H{3}(CH{2}NMe{2}){2}-2, 6; X = BF{4} (1a), OSO{2}CF{3} (1b)) leads to substitution of the H{2}O ligand to afford the ionic Pt(II) complexes [Pt(NCN)(PHPh{2})]X (X = BF{4} (2a), OSO{2}CF{3} (2b)). The X-ray structure of the

[(CH3)3NCH2CH2NH3]SnI4: a layered perovskite with quaternary/primary ammonium dications and short interlayer iodine-iodine contacts.

Science.gov (United States)

Xu, Zhengtao; Mitzi, David B; Medeiros, David R

2003-03-10

The organic-inorganic hybrid [(CH(3))(3)NCH(2)CH(2)NH(3)]SnI(4) presents a layered perovskite structure, templated by an organic dication containing both a primary and a quaternary ammonium group. Due to the high charge density and small size of the organic cation, the separation of the perovskite layers is small and short iodine-iodine contacts of 4.19 A are formed between the layers. Optical thin-film measurements on this compound indicate a significant red shift of the exciton peak (630 nm) associated with the band gap, as compared with other SnI(4)(2)(-)-based layered perovskite structures.

TEA CO2 laser-induced reaction of CH3NO2 with CF2HCl: A ...

Indian Academy of Sciences (India)

Unknown

and CH3NO2 molecules as well as UV absorption of CF2 radicals are carried out to elucidate ... nitromethane and H2 under high fluence conditions 10, bright visible ... CF2HCl was monitored by gas chromatography and FTIR spectrometry.

Adsorption of Dissolved Gases (CH4, CO2, H2, Noble Gases) by Water-Saturated Smectite Clay Minerals

Science.gov (United States)

Bourg, I. C.; Gadikota, G.; Dazas, B.

2016-12-01

Adsorption of dissolved gases by water-saturated clay minerals plays important roles in a range of fields. For example, gas adsorption in on clay minerals may significantly impact the formation of CH4 hydrates in fine-grained sediments, the behavior of CH4 in shale, CO2 leakage across caprocks of geologic CO2 sequestration sites, H2 leakage across engineered clay barriers of high-level radioactive waste repositories, and noble gas geochemistry reconstructions of hydrocarbon migration in the subsurface. Despite its importance, the adsorption of gases on clay minerals remains poorly understood. For example, some studies have suggested that clay surfaces promote the formation of CH4 hydrates, whereas others indicate that clay surfaces inhibit the formation of CH4 hydrates. Here, we present molecular dynamics (MD) simulations of the adsorption of a range of gases (CH4, CO2, H2, noble gases) on clay mineral surfaces. Our results indicate that the affinity of dissolved gases for clay mineral surfaces has a non-monotone dependence on the hydrated radius of the gas molecules. This non-monotone dependence arises from a combination of two effects: the polar nature of certain gas molecules (in particular, CO2) and the templating of interfacial water structure by the clay basal surface, which results in the presence of interfacial water "cages" of optimal size for intermediate-size gas molecules (such as Ne or Ar).

CO2 and CH4 exchange by Phragmites australis under different climates

Science.gov (United States)

Serrano Ortiz, Penélope; Chojnickic, Bogdan H.; Sánchez-Cañete, Enrique P.; Kowalska, Natalia; López-Ballesteros, Ana; Fernández, Néstor; Urbaniak, Marek; Olejnik, Janusz; Kowalski, Andrew S.

2015-04-01

The key role of wetlands regarding global warming is the resulting balance between net CO2 assimilation, via photosynthesis, and CO2 and CH4 emissions, given the potential to release stored carbon, because of the high temperature sensitivity of heterotrophic soil respiration and anoxic conditions. However, it is still unknown whether wetlands will convert from long-term carbon sinks to sources as a result of climate change and other anthropogenic effects such as land use changes. Phragmites australis is one of the most common species found in wetlands and is considered the most globally widespread and productive plant species in this type of ecosystem. In this context, the main objective of this study is to analyse the GHG exchange (CO2 and CH4) of two wetlands with Phragmites australis as the dominant species under different climates using the eddy covariance (EC) technique. The first site, Padul, is located in southern Spain, with a sub-humid warm climate, characterised by a mean annual temperature of 16°C and annual precipitation of ca. 470 mm, with a very dry summer. The second site, Rzecin is located in Poland with a mean annual temperature of 8°C, and annual precipitation around 600mm with no dry season. The Padul EC station is equipped with two infrared gas analysers to measure CO2 and CH4 fluxes (LI-7200 and LI-7700 respectively) while the Rzecin EC station has the same CH4 sensor as Padul, but also a sensor measuring both GHG fluxes (DLT-100 Fast Methane Analyser, Los Gatos). In this study, we present: i) the results of a CH4 analyser inter-comparison campaign (LI-7700 vs. Los Gatos), ii) a comparative analysis of the functional behaviour of respiration and photosynthesis in both sites testing relationships between CO2 fluxes measured with the EC technique and meteorological variables such as temperature and direct or diffuse radiation and iii) the CH4 dynamicsat both sites by identifying, when possible, annual, seasonal and diurnal patterns.

Correlations among atmospheric CO[sub 2], CH[sub 4] and CO in the Arctic, March 1989

Energy Technology Data Exchange (ETDEWEB)

Conway, T.J.; Steele, L.P.; Novelli, P.C. (NOAA Climate Monitoring and Diagnostics Lab., Boulder, CO (United States))

1993-12-01

During six aircraft flights conducted as part of the third Arctic Gas and Aerosol Sampling Program (AGASP III, March 1989), 189 air samples were collected throughout the Arctic troposphere and lower stratosphere for analysis of CO[sub 2], CH[sub 4] and CO. The mixing ratios of the three gases varied significantly both horizontally and vertically. Elevated concentrations were found in layers with high anthropogenic aerosol concentrations (Arctic Haze). The mixing ratios of CO[sub 2], CH[sub 4] and CO were highly correlated on all flights. A linear regression of CH[sub 4] vs CO[sub 2] for pooled data from all flights yielded a correlation coefficient (r[sup 2]) of 0.88 and a slope of 13.5 ppb CH[sub 4]/ppm CO[sub 2] (n 186). For CO vs CO[sub 2] a pooled linear regression gave r[sup 2] 0.91 and a slope of 15.8 ppb CO/ppm CO[sub 2] (n 182). Carbon dioxide CH[sub 4] and CO also exhibited mean vertical gradients with slopes of 0.37, -4.4 and -4.2 ppb km[sup -1], respectively. Since the carbon dioxide variations observed in the Arctic atmosphere during winter are due primarily to variations in the emissions and transport of anthropogenic CO[sub 2] from Europe and Asia, the strong correlations that we have found suggest that a similar interpretation applies to CH[sub 4] and CO. Using reliable estimates of CO[sub 2] emissions for the source regions and the measured CH[sub 4]/CO[sub 2] and CO/CO[sub 2] ratios, we estimate a regional European CH[sub 4] source of 47[+-] 6 Tg CH[sub 4] yr[sup -1] that may be associated with fossil fuel combustion. A similar calculation for CO results in an estimated regional CO source of 82[+-]2 Tg CO yr[sup -1]. 31 refs., 7 figs., 4 tabs.

Transport and transformation of soil-derived CO2, CH4 and DOC sustain CO2 supersaturation in small boreal streams.

Science.gov (United States)

Rasilo, Terhi; Hutchins, Ryan H S; Ruiz-González, Clara; Del Giorgio, Paul A

2017-02-01

Streams are typically supersaturated in carbon dioxide (CO 2 ) and methane (CH 4 ), and are recognized as important components of regional carbon (C) emissions in northern landscapes. Whereas there is consensus that in most of the systems the CO 2 emitted by streams represents C fixed in the terrestrial ecosystem, the pathways delivering this C to streams are still not well understood. We assessed the contribution of direct soil CO 2 injection versus the oxidation of soil-derived dissolved organic C (DOC) and CH 4 in supporting CO 2 supersaturation in boreal streams in Québec. We measured the concentrations of CO 2 , CH 4 and DOC in 43 streams and adjacent soil waters during summer base-flow period. A mass balance approach revealed that all three pathways are significant, and that the mineralization of soil-derived DOC and CH 4 accounted for most of the estimated stream CO 2 emissions (average 75% and 10%, respectively), and that these estimated contributions did not change significantly between the studied low order (≤3) streams. Whereas some of these transformations take place in the channel proper, our results suggest that they mainly occur in the hyporheic zones of the streams. Our results further show that stream CH 4 emissions can be fully explained by soil CH 4 inputs. This study confirms that these boreal streams, and in particular their hyporheic zones, are extremely active processors of soil derived DOC and CH 4 , not just vents for soil produced CO 2 . Copyright © 2016 Elsevier B.V. All rights reserved.

Probing the global potential energy minimum of (CH2O)2: THz absorption spectrum of (CH2O)2 in solid neon and para-hydrogen.

Science.gov (United States)

Andersen, J; Voute, A; Mihrin, D; Heimdal, J; Berg, R W; Torsson, M; Wugt Larsen, R

2017-06-28

The true global potential energy minimum configuration of the formaldehyde dimer (CH 2 O) 2 , including the presence of a single or a double weak intermolecular CH⋯O hydrogen bond motif, has been a long-standing subject among both experimentalists and theoreticians as two different energy minima conformations of C s and C 2h symmetry have almost identical energies. The present work demonstrates how the class of large-amplitude hydrogen bond vibrational motion probed in the THz region provides excellent direct spectroscopic observables for these weak intermolecular CH⋯O hydrogen bond motifs. The combination of concentration dependency measurements, observed isotopic spectral shifts associated with H/D substitutions and dedicated annealing procedures, enables the unambiguous assignment of three large-amplitude infrared active hydrogen bond vibrational modes for the non-planar C s configuration of (CH 2 O) 2 embedded in cryogenic neon and enriched para-hydrogen matrices. A (semi)-empirical value for the change of vibrational zero-point energy of 5.5 ± 0.3 kJ mol -1 is proposed for the dimerization process. These THz spectroscopic observations are complemented by CCSD(T)-F12/aug-cc-pV5Z (electronic energies) and MP2/aug-cc-pVQZ (force fields) electronic structure calculations yielding a (semi)-empirical value of 13.7 ± 0.3 kJ mol -1 for the dissociation energy D 0 of this global potential energy minimum.

Studies on the adsorption behavior of CO2-CH4 mixtures using activated carbon

Directory of Open Access Journals (Sweden)

R. B. Rios

2013-12-01

Full Text Available Separation of CO2 from CO2-CH4 mixtures is an important issue in natural gas and biogas purification. The design of such separation processes depends on the knowledge of the behavior of multicomponent adsorption, particularly that of CO2-CH4 mixtures. In this study, we present a series of experimental binary equilibrium isotherms for CO2-CH4 mixtures on an activated carbon at 293 K and compare them with predicted values using the Ideal Adsorption Solution Theory (IAST and the Extended Langmuir (EL model. Even at concentrations of ca. 20% for all binary isotherms, CO2 already presents higher adsorbed amounts with respect to CH4. A maximum selectivity of around 8.7 was observed for a nearly equimolar mixture at 0.1 MPa. The IAST in conjunction with the Toth equation showed slightly better results than IAST using the Langmuir equation and both showed better results than the EL model.

CH-TRU Waste Content Codes

Energy Technology Data Exchange (ETDEWEB)

Washington TRU Solutions LLC

2008-01-16

The CH-TRU Waste Content Codes (CH-TRUCON) document describes the inventory of the U.S. Department of Energy (DOE) CH-TRU waste within the transportation parameters specified by the Contact-Handled Transuranic Waste Authorized Methods for Payload Control (CH-TRAMPAC). The CH-TRAMPAC defines the allowable payload for the Transuranic Package Transporter-II (TRUPACT-II) and HalfPACT packagings. This document is a catalog of TRUPACT-II and HalfPACT authorized contents and a description of the methods utilized to demonstrate compliance with the CH-TRAMPAC. A summary of currently approved content codes by site is presented in Table 1. The CH-TRAMPAC describes "shipping categories" that are assigned to each payload container. Multiple shipping categories may be assigned to a single content code. A summary of approved content codes and corresponding shipping categories is provided in Table 2, which consists of Tables 2A, 2B, and 2C. Table 2A provides a summary of approved content codes and corresponding shipping categories for the "General Case," which reflects the assumption of a 60-day shipping period as described in the CH-TRAMPAC and Appendix 3.4 of the CH-TRU Payload Appendices. For shipments to be completed within an approximately 1,000-mile radius, a shorter shipping period of 20 days is applicable as described in the CH-TRAMPAC and Appendix 3.5 of the CH-TRU Payload Appendices. For shipments to WIPP from Los Alamos National Laboratory (LANL), Nevada Test Site, and Rocky Flats Environmental Technology Site, a 20-day shipping period is applicable. Table 2B provides a summary of approved content codes and corresponding shipping categories for "Close-Proximity Shipments" (20-day shipping period). For shipments implementing the controls specified in the CH-TRAMPAC and Appendix 3.6 of the CH-TRU Payload Appendices, a 10-day shipping period is applicable. Table 2C provides a summary of approved content codes and corresponding shipping categories for "Controlled Shipments

Rate Constant of the Reaction between CH3O2 Radicals and OH Radicals Revisited.

Science.gov (United States)

Assaf, Emmanuel; Song, Bo; Tomas, Alexandre; Schoemaecker, Coralie; Fittschen, Christa

2016-11-17

The reaction between CH 3 O 2 and OH radicals has been studied in a laser photolysis cell using the reaction of F atoms with CH 4 and H 2 O for the simultaneous generation of both radicals, with F atoms generated through 248 nm photolysis of XeF 2 . An experimental setup combining cw-Cavity Ring Down Spectroscopy (cw-CRDS) and high repetition rate laser-induced fluorescence (LIF) to a laser photolysis cell has been used. The absolute concentration of CH 3 O 2 was measured by cw-CRDS, while the relative concentration of OH(v = 0) radicals was determined by LIF. To remove dubiety from the quantification of CH 3 O 2 by cw-CRDS in the near-infrared, its absorption cross section has been determined at 7489.16 cm -1 using two different methods. A rate constant of k 1 = (1.60 ± 0.4) × 10 -10 cm 3 s -1 has been determined at 295 K, nearly a factor of 2 lower than an earlier determination from our group ((2.8 ± 1.4) × 10 -10 cm 3 s -1 ) using CH 3 I photolysis as a precursor. Quenching of electronically excited I atoms (from CH 3 I photolysis) in collision with OH(v = 0) is suspected to be responsible for a bias in the earlier, fast rate constant.

Early Mars serpentinization-derived CH4 reservoirs, H2 induced warming and paleopressure evolution

Science.gov (United States)

Lasue, J.; Chassefiere, E.; Langlais, B.; Quesnel, Y.

2016-12-01

CH4 has been observed on Mars both by remote sensing and in situ during the past 15 years. Early Mars serpentinization is one possible abiotic mechanism that could not only produce methane, but also explain the observed Martian remanent magnetic field. Assuming a cold early Mars, a cryosphere could trap such CH4 as clathrates in stable form at depth. We recently estimated the maximum storage capacity of such clathrate layer to be about 2x1019 to 2x1020 moles of methane. Such reservoirs may be stable or unstable, depending on many factors that are poorly constrained: major and sudden geological events such as the Tharsis bulge formation, the Hellas impact or the martian polar wander, could have destabilized the clathrates early in the history of the planet and released large quantities of gas in the atmosphere. Here we estimate the associated amounts of serpentinization-derived CH4 stored in the cryosphere that have been released to the atmosphere at the end of the Noachian and the beginning of the Hesperian. Due to rapid clathrate dissociation and photochemical conversion of CH4 to H2, these episodes of massive CH4 release may have resulted in transient H2-rich atmospheres, at typical levels of 10-20% in a background 1-2 bar CO2 atmosphere. We propose that the early Mars cryosphere had a sufficient CH4 storage capacity to have maintained H2-rich transient atmospheres during a total time period up to several Myr or tens of Myr, having potentially contributed - by collision-induced heating effect of atmospheric H2 - to the formation of valley networks during the late Noachian and early Hesperian.

Double C-H activation of ethane by metal-free SO2*+ radical cations.

Science.gov (United States)

de Petris, Giulia; Cartoni, Antonella; Troiani, Anna; Barone, Vincenzo; Cimino, Paola; Angelini, Giancarlo; Ursini, Ornella

2010-06-01

The room-temperature C-H activation of ethane by metal-free SO(2)(*+) radical cations has been investigated under different pressure regimes by mass spectrometric techniques. The major reaction channel is the conversion of ethane to ethylene accompanied by the formation of H(2)SO(2)(*+), the radical cation of sulfoxylic acid. The mechanism of the double C-H activation, in the absence of the single activation product HSO(2)(+), is elucidated by kinetic studies and quantum chemical calculations. Under near single-collision conditions the reaction occurs with rate constant k=1.0 x 10(-9) (+/-30%) cm(3) s(-1) molecule(-1), efficiency=90%, kinetic isotope effect k(H)/k(D)=1.1, and partial H/D scrambling. The theoretical analysis shows that the interaction of SO(2)(*+) with ethane through an oxygen atom directly leads to the C-H activation intermediate. The interaction through sulfur leads to an encounter complex that rapidly converts to the same intermediate. The double C-H activation occurs by a reaction path that lies below the reactants and involves intermediates separated by very low energy barriers, which include a complex of the ethyl cation suitable to undergo H/D scrambling. Key issues in the observed reactivity are electron-transfer processes, in which a crucial role is played by geometrical constraints. The work shows how mechanistic details disclosed by the reactions of metal-free electrophiles may contribute to the current understanding of the C-H activation of ethane.

Conductivity, XRD, and FTIR studies of New Mg2+-ion-conducting solid polymer electrolytes: [PEG: Mg(CH3COO)2

International Nuclear Information System (INIS)

Polu, Anji Reddy; Kumar, Ranveer; Causin, Valerio; Neppalli, Ramesh

2011-01-01

Solid polymer electrolytes based on poly (ethylene glycol) (PEG) doped with Mg(CH 3 COO) 2 have been prepared by using the solution-casting method. The X-ray diffraction patterns of PEG with Mg(CH 3 COO) 2 salt indicated a decrease in the degree of crystallinity with increasing concentration of the salt. The complexation of Mg(CH 3 COO) 2 salt with the polymer was confirmed by using Fourier transform infrared spectroscopy (FTIR) studies. The ionic conductivity was measured for the [PEG: Mg(CH 3 COO) 2 ] system in the frequency range 50 Hz - 1 MHz. The addition of Mg salt was found to improve the ionic conductivity significantly. The 15-wt-% Mg(CH 3 COO) 2 -doped system had a maximum conductivity of 1.07 x 10 -6 S/cm at 303 K. The conductance spectrum shows two distinct regions: a dc plateau and a dispersive region. The temperature dependence of the ionic conductivity reveals the conduction mechanism to be an Arrhenius-type thermally activated process.

Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

KAUST Repository

Chen, Yin; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Hamzaoui, Bilel; Emsley, Lyndon; Basset, Jean-Marie

2015-01-01

By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

KAUST Repository

Chen, Yin

2015-01-21

By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

A combustion setup to precisely reference δ13C and δ2H isotope ratios of pure CH4 to produce isotope reference gases of δ13C-CH4 in synthetic air