National Library of Energy BETA

Sample records for butyl ether ch

  1. Vapor pressures of methyl tert-butyl ether, ethyl tert-butyl ether, isopropyl tert-butyl ether, tert-amyl methyl ether, and tert-amyl ethyl ether

    SciTech Connect (OSTI)

    Kraehenbuehl, M.A.; Gmehling, J. . Technische Chemie)

    1994-10-01

    The vapor pressures of methyl tert-butyl ether, ethyl tert-butyl ether, isopropyl tert-butyl ether, tert-amyl methyl ether, and tert-amyl ethyl ether were measured by ebulliometry or the static method in the pressure ranges 14--102 and 3--835 kPa (methyl tert-butyl ether), respectively. The data were correlated using the Antoine and Wagner equations. The experimental data of methyl tert-butyl ether and ethyl tert-butyl ether were compared with data available in the literature.

  2. State Restrictions on Methyl Tertiary Butyl Ether (released in AEO2006)

    Reports and Publications (EIA)

    2006-01-01

    By the end of 2005, 25 states had barred, or passed laws banning, any more than trace levels of methyl tertiary butyl ether (MTBE) in their gasoline supplies, and legislation to ban MTBE was pending in 4 others. Some state laws address only MTBE; others also address ethers such as ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether (TAME). Annual Energy Outlook 2006 assumes that all state MTBE bans prohibit the use of all ethers for gasoline blending.

  3. Enhanced diisobutene production in the presence of methyl tertiary butyl ether

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A. (Bellaire, TX)

    1983-01-01

    In the liquid phase reaction of isobutene in the presence of resin cation exchange resins with itself in a C.sub.4 hydrocarbon stream to form dimers, the formation of higher polymers, oligomers, and co-dimer by-products is suppressed by the presence of 0.0001 to 1 mole per mole of isobutene of methyl tertiary butyl ether.

  4. Enhanced diisobutene production in the presence of methyl tertiary butyl ether

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1983-03-01

    In the liquid phase reaction of isobutene in the presence of resin cation exchange resins with itself in a C[sub 4] hydrocarbon stream to form dimers, the formation of higher polymers, oligomers, and co-dimer by-products is suppressed by the presence of 0.0001 to 1 mole per mole of isobutene of methyl tertiary butyl ether. 1 fig.

  5. Methyl tert-butyl ether and ethyl tert-butyl ether: A comparison of properties, synthesis techniques, and operating conditions

    SciTech Connect (OSTI)

    Sneesby, M.G.; Tade, M.O.; Datta, R.

    1996-12-31

    MTBE is currently the most industrially significant oxygenate but some of the properties of ETBE and the EPA ethanol mandate suggest that ETBE could become a viable competitor. Similar synthesis techniques are used for both ethers but the phase behaviour of the ETBE system requires slightly different operating conditions and creates some alternatives for product recovery. The process control strategy for both systems must address some unusual challenges. 9 refs., 1 tab.

  6. Thermodynamic properties and ideal-gas enthalpies of formation for butyl vinyl ether, 1,2-dimethoxyethane, methyl glycolate, bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, di-tert-butyl ether, and hexane-1,6-diol

    SciTech Connect (OSTI)

    Steele, W.V.; Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.; Smith, N.K.

    1996-11-01

    Ideal-gas enthalpies of formation of butyl vinyl ether, 1,2-dimethoxyethane, methyl glycolate, bicyclo-[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, di-tert-butyl ether, and hexane-1,6-diol are reported. Enthalpies of fusion were determined for bicyclo[2.2.1]hept-2-ene and trans-azobenzene. Two-phase (solid + vapor) or (liquid + vapor) heat capacities were determined from 300 K to the critical region or earlier decomposition temperature for each compound studied. Liquid-phase densities along the saturation line were measured for bicyclo[2.2.1]hept-2-ene. For butyl vinyl ether and 1,2-dimethoxyethane, critical temperatures and critical densities were determined from the dsc results and corresponding critical pressures derived from the fitting procedures. Fitting procedures were used to derive critical temperatures, critical pressures, and critical densities for bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, and di-tert-butyl ether. Group-additivity parameters or ring-correction terms useful in the application of the Benson group-contribution correlations were derived.

  7. Manipulation of the HIF–Vegf pathway rescues methyl tert-butyl ether (MTBE)-induced vascular lesions

    SciTech Connect (OSTI)

    Bonventre, Josephine A.; Kung, Tiffany S.; White, Lori A.; Cooper, Keith R.

    2013-12-15

    Methyl tert-butyl ether (MTBE) has been shown to be specifically anti-angiogenic in piscine and mammalian model systems at concentrations that appear non-toxic in other organ systems. The mechanism by which MTBE targets developing vascular structures is unknown. A global transcriptome analysis of zebrafish embryos developmentally exposed to 0.00625–5 mM MTBE suggested that hypoxia inducible factor (HIF)-regulated pathways were affected. HIF-driven angiogenesis via vascular endothelial growth factor (vegf) is essential to the developing vasculature of an embryo. Three rescue studies were designed to rescue MTBE-induced vascular lesions: pooled blood in the common cardinal vein (CCV), cranial hemorrhages (CH), and abnormal intersegmental vessels (ISV), and test the hypothesis that MTBE toxicity was HIF–Vegf dependent. First, zebrafish vegf-a over-expression via plasmid injection, resulted in significantly fewer CH and ISV lesions, 46 and 35% respectively, in embryos exposed to 10 mM MTBE. Then HIF degradation was inhibited in two ways. Chemical rescue by N-oxaloylglycine significantly reduced CCV and CH lesions by 30 and 32% in 10 mM exposed embryos, and ISV lesions were reduced 24% in 5 mM exposed zebrafish. Finally, a morpholino designed to knock-down ubiquitin associated von Hippel–Lindau protein, significantly reduced CCV lesions by 35% in 10 mM exposed embryos. In addition, expression of some angiogenesis related genes altered by MTBE exposure were rescued. These studies demonstrated that MTBE vascular toxicity is mediated by a down regulation of HIF–Vegf driven angiogenesis. The selective toxicity of MTBE toward developing vasculature makes it a potentially useful chemical in the designing of new drugs or in elucidating roles for specific angiogenic proteins in future studies of vascular development. - Highlights: • Global gene expression of MTBE exposed zebrafish suggested altered HIF1 signaling. • Over expression of zebrafish vegf-a rescues MTBE

  8. Exposure to methyl tert-butyl ether, benzene, and total hydrocarbons at the Singapore-Malaysia causeway immigration checkpoint

    SciTech Connect (OSTI)

    Tan, C.; Ong, H.Y.; Kok, P.W.

    1996-12-31

    The primary aim of this study was to determine the extent and levels of exposure to volatile organic compounds (VOCs) from automobile emissions in a group of immigration officers at a busy cross-border checkpoint. A majority (80%) of the workers monitored were exposed to benzene at levels between 0.01 and 0.5 ppm, with only 1.2% exceeding the current Occupational Safety and Health Administration occupational exposure limit of 1 ppm. The geometric mean (GM) concentrations of 8-hr time-weighted average exposure were 0.03 ppm, 0.9 ppm, and 2.46 ppm for methyl-tert-butyl ether (MTBE), benzene, and total hydrocarbons (THC), respectively. The highest time-weighted average concentrations measured were 1.05 ppm for MTBE, 2.01 ppm for benzene, and 34 ppm for THC. It was found that motorbikes emitted a more significant amount of pollutants compared with motor cars. On average, officers at the motorcycle booths were exposed to four to five times higher levels of VOCs (GMs of 0.07 ppm, 0.23 ppm, and 4.7 ppm for MTBE, benzene, and THC) than their counterparts at the motor car booths (GMs of 0.01 ppm, 0.05 ppm, and 1.5 ppm). The airborne concentrations of all three pollutants correlated with the flow of vehicle traffic. Close correlations were also noted for the concentrations in ambient air for the three pollutants measured. Benzene and MTBE had a correlation coefficient of 0.97. The overall findings showed that the concentrations of various VOCs were closely related to the traffic density, suggesting that they were from a common source, such as exhaust emissions from the vehicles. The results also indicated that although benzene, MTBE, and THC are known to be volatile, a significant amount could still be detected in the ambient environment, thus contributing to our exposure to these compounds. 4 refs., 6 figs.

  9. Cytotoxic and DNA-damaging effects of methyl tert-butyl ether and its metabolites on HL-60 cells in vitro

    SciTech Connect (OSTI)

    Tang, G.H.; Shen, Y.; Shen, H.M.

    1996-12-31

    Methyl tert-butyl ether (MTBE) is a widely used oxygenate in unleaded gasoline; however, few studies have been conducted on the toxicity of this compound. This study evaluates the cytotoxic and DNA-damaging effects of MTBE and its metabolites in a human haemopoietic cell line, HL-60. The metabolites of MTBE studied include tertiary butyl alcohol (TBA), {alpha}-hydroxyisobutyric acid (HIBA), and formaldehyde. Comet assay is used to assess DNA damage, and the cytotoxicity is investigated by lactate dehydrogenease (LDH) release. The results show no significant cytotoxic effects of MTBE, TBA, and HIBA over a concentration ranging from 1 to 30 mM. Formaldehyde, in contrast, causes a substantial LDH release at a concentration of 5 {mu}M. Hydrogen peroxide, a known oxidative agent, at concentrations ranging from 10 to 100 {mu}M, produces a significant dose-related increase in DNA damage, whereas a much higher concentration of MTBE (1 to 30 mM) is required to produce a similar observation. The genotoxic effects of TBA and HIBA appear to be identical to that of MTBE. Conversely, DNA damage is observed for formaldehyde at a relatively low concentration range (5 to 100 {mu}M). These findings suggest that MTBE and its metabolites, except formaldehyde, have relatively low cytotoxic and genotoxic effects. 16 refs., 4 figs.

  10. {gamma}-aminobutyric acid{sub A} (GABA{sub A}) receptor regulates ERK1/2 phosphorylation in rat hippocampus in high doses of Methyl Tert-Butyl Ether (MTBE)-induced impairment of spatial memory

    SciTech Connect (OSTI)

    Zheng Gang; Zhang Wenbin; Zhang Yun; Chen Yaoming; Liu Mingchao; Yao Ting; Yang Yanxia; Zhao Fang; Li Jingxia; Huang Chuanshu; Luo Wenjing Chen Jingyuan

    2009-04-15

    Experimental and occupational exposure to Methyl Tert-Butyl Ether (MTBE) has been reported to induce neurotoxicological and neurobehavioral effects, such as headache, nausea, dizziness, and disorientation, etc. However, the molecular mechanisms involved in MTBE-induced neurotoxicity are still not well understood. In the present study, we investigated the effects of MTBE on spatial memory and the expression and function of GABA{sub A} receptor in the hippocampus. Our results demonstrated that intraventricular injection of MTBE impaired the performance of the rats in a Morris water maze task, and significantly increased the expression of GABA{sub A} receptor {alpha}1 subunit in the hippocampus. The phosphorylation of ERK1/2 decreased after the MTBE injection. Furthermore, the decreased ability of learning and the reduction of phosphorylated ERK1/2 level of the MTBE-treated rats was partly reversed by bicuculline injected 30 min before the training. These results suggested that MTBE exposure could result in impaired spatial memory. GABA{sub A} receptor may play an important role in the MTBE-induced impairment of learning and memory by regulating the phosphorylation of ERK in the hippocampus.

  11. HIGH-RESOLUTION EXPANDED VERY LARGE ARRAY IMAGE OF DIMETHYL ETHER (CH{sub 3}){sub 2}O IN ORION-KL

    SciTech Connect (OSTI)

    Favre, C.; Wootten, H. A.; Remijan, A. J.; Brouillet, N.; Despois, D.; Baudry, A.; Wilson, T. L. E-mail: brouillet@obs.u-bordeaux1.fr E-mail: baudry@obs.u-bordeaux1.fr E-mail: aremijan@nrao.edu

    2011-09-20

    We report the first subarcsecond (0.''65 x 0.''51) image of the dimethyl ether molecule, (CH{sub 3}){sub 2}O, toward the Orion Kleinmann-Low nebula. The observations were carried at 43.4 GHz with the Expanded Very Large Array (EVLA). The distribution of the lower energy transition 6{sub 1,5}-6{sub 0,6}, EE (E {sub u} = 21 K) mapped in this study is in excellent agreement with the published dimethyl ether emission maps imaged with a lower resolution. The main emission peaks are observed toward the Compact Ridge and Hot Core southwest components, at the northern parts of the Compact Ridge and in an intermediate position between the Compact Ridge and the Hot Core. A notable result is that the distribution of dimethyl ether is very similar to that of another important larger O-bearing species, the methyl formate (HCOOCH{sub 3}), imaged at a lower resolution. Our study shows that higher spectral resolution (WIDAR correlator) and increased spectral coverage provided by the EVLA offer new possibilities for imaging complex molecular species. The sensitivity improvement and the other EVLA improvements make this instrument well suited for high sensitivity, high angular resolution, and molecular line imaging.

  12. Determination of Methyl tert-Butyl Ether and tert-Butyl Alcohol...

    Office of Scientific and Technical Information (OSTI)

    ... Authors: Oh, Keun-Chan ; Stringfellow, William T. Publication Date: 2003-10-02 OSTI Identifier: 820662 Report Number(s): LBNL--53866 R&D Project: G41101; TRN: US200405%%70 DOE ...

  13. Radiation chemistry of alternative fuel oxygenates -- Substituted ethers

    SciTech Connect (OSTI)

    Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

    1999-11-15

    The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE).

  14. Crown ethers in graphene

    SciTech Connect (OSTI)

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I; Gallego, Nidia C; Pantelides, Sokrates T.; Pennycook, Stephen J; Moyer, Bruce A; Chisholm, Matthew F

    2014-01-01

    Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basic structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.

  15. Tropospheric oxidation mechanism of dimethyl ether and methyl formate

    SciTech Connect (OSTI)

    Good, D.A.; Francisco, J.S.

    2000-02-17

    The oxidation mechanism of dimethyl ether is investigated using ab initio methods. The structure and energetics of reactants, products, and transition structures are determined for all pathways involved in the oxidation mechanism. The detailed pathways leading to the experimentally observed products of dimethyl ether oxidation are presented. The energetics of over 50 species and transition structures involved in the oxidation process are calculated with G2 and G2(MP2) energies. The principal pathway following the initial attack of dimethyl ether (CH{sub 3}OCH{sub 3}) by the OH radical is the formation of the methoxymethyl radical (CH{sub 2}OCH{sub 3}). Oxidation steps lead to the formation of methyl formate, which is consistent with the experimentally observed products. Oxidation pathways of methyl formate are also considered.

  16. Reaction Pathways and Energetics of Etheric C−O Bond Cleavage Catalyzed by Lanthanide Triflates

    SciTech Connect (OSTI)

    Assary, Rajeev S.; Atesin, Abdurrahman C.; Li, Zhi; Curtiss, Larry A.; Marks, Tobin J.

    2013-07-15

    Efficient and selective cleavage of etheric C−O bonds is crucial for converting biomass into platform chemicals and liquid transportation fuels. In this contribution, computational methods at the DFT B3LYP level of theory are employed to understand the efficacy of lanthanide triflate catalysts (Ln(OTf)3, Ln = La, Ce, Sm, Gd, Yb, and Lu) in cleaving etheric C−O bonds. In agreement with experiment, the calculations indicate that the reaction pathway for C−O cleavage occurs via a C−H → O−H proton transfer in concert with weakening of the C−O bond of the coordinated ether substrate to ultimately yield a coordinated alkenol. The activation energy for this process falls as the lanthanide ionic radius decreases, reflecting enhanced metal ion electrophilicity. Details of the reaction mechanism for Yb(OTf)3-catalyzed ring opening are explored in depth, and for 1-methyl-d3-butyl phenyl ether, the computed primary kinetic isotope effect of 2.4 is in excellent agreement with experiment (2.7), confirming that etheric ring-opening pathway involves proton transfer from the methyl group alpha to the etheric oxygen atom, which is activated by the electrophilic lanthanide ion. Calculations of the catalytic pathway using eight different ether substrates indicate that the more rapid cleavage of acyclic versus cyclic ethers is largely due to entropic effects, with the former C−O bond scission processes increasing the degrees of freedom/particles as the transition state is approached.

  17. Hydrogen Atom Reactivity toward Aqueous tert-Butyl Alcohol

    SciTech Connect (OSTI)

    Lymar S. V.; Schwarz, H.A.

    2012-02-09

    Through a combination of pulse radiolysis, purification, and analysis techniques, the rate constant for the H + (CH{sub 3}){sub 3}COH {yields} H{sub 2} + {sm_bullet}CH{sub 2}C(CH{sub 3}){sub 2}OH reaction in aqueous solution is definitively determined to be (1.0 {+-} 0.15) x 10{sup 5} M{sup -1} s{sup -1}, which is about half of the tabulated number and 10 times lower than the more recently suggested revision. Our value fits on the Polanyi-type, rate-enthalpy linear correlation ln(k/n) = (0.80 {+-} 0.05){Delta}H + (3.2 {+-} 0.8) that is found for the analogous reactions of other aqueous aliphatic alcohols with n equivalent abstractable H atoms. The existence of such a correlation and its large slope are interpreted as an indication of the mechanistic similarity of the H atom abstraction from {alpha}- and {beta}-carbon atoms in alcohols occurring through the late, product-like transition state. tert-Butyl alcohol is commonly contaminated by much more reactive secondary and primary alcohols (2-propanol, 2-butanol, ethanol, and methanol), whose content can be sufficient for nearly quantitative scavenging of the H atoms, skewing the H atom reactivity pattern, and explaining the disparity of the literature data on the H + (CH{sub 3}){sub 3}COH rate constant. The ubiquitous use of tert-butyl alcohol in pulse radiolysis for investigating H atom reactivity and the results of this work suggest that many other previously reported rate constants for the H atom, particularly the smaller ones, may be in jeopardy.

  18. Alternative Fuels Data Center: Dimethyl Ether

    Alternative Fuels and Advanced Vehicles Data Center [Office of Energy Efficiency and Renewable Energy (EERE)]

    Dimethyl Ether to someone by E-mail Share Alternative Fuels Data Center: Dimethyl Ether on Facebook Tweet about Alternative Fuels Data Center: Dimethyl Ether on Twitter Bookmark Alternative Fuels Data Center: Dimethyl Ether on Google Bookmark Alternative Fuels Data Center: Dimethyl Ether on Delicious Rank Alternative Fuels Data Center: Dimethyl Ether on Digg Find More places to share Alternative Fuels Data Center: Dimethyl Ether on AddThis.com... More in this section... Biobutanol Dimethyl Ether

  19. Butyl Fuel LLC formerly Environmental Energy Inc | Open Energy...

    Open Energy Info (EERE)

    Butyl Fuel LLC formerly Environmental Energy Inc Jump to: navigation, search Name: Butyl Fuel LLC (formerly Environmental Energy Inc) Place: Ohio Zip: 43004 Product:...

  20. Propenyl ether monomers for photopolymerization

    DOE Patents [OSTI]

    Crivello, J.V.

    1996-10-22

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of the above formula together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  1. Propenyl ether monomers for photopolymerization

    DOE Patents [OSTI]

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  2. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A.; Jones, Jr., Edward M.; Hearn, Dennis

    1984-01-01

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150.degree. to 250.degree. F. at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C.sub.3 to C.sub.6 and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom.

  3. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOE Patents [OSTI]

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

    1984-05-08

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150 to 250 F at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C[sub 3] to C[sub 6] and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom. 2 figs.

  4. Atmospheric and combustion chemistry of dimethyl ether

    SciTech Connect (OSTI)

    Nielsen, O.J.; Egsgaard, H.; Larsen, E.; Sehested, J.; Wallington, T.J.

    1997-12-31

    It has been demonstrated that dimethyl ether (DME) is an ideal diesel fuel alternative. DME, CH{sub 3}OCH{sub 3}, combines good fuel properties with low exhaust emissions and low combustion noise. Large scale production of this fuel can take place using a single step catalytic process converting CH{sub 4} to DME. The fate of DME in the atmosphere has previously been studied. The atmospheric degradation is initiated by the reaction with hydroxyl radicals, which is also a common feature of combustion processes. Spectrokinetic investigations and product analysis were used to demonstrate that the intermediate oxy radical, CH{sub 3}OCH{sub 2}O, exhibits a novel reaction pathway of hydrogen atom ejection. The application of tandem mass spectrometry to chemi-ions based on supersonic molecular beam sampling has recently been demonstrated. The highly reactive ionic intermediates are sampled directly from the flame and identified by collision activation mass spectrometry and ion-molecule reactions. The mass spectrum reflects the distribution of the intermediates in the flame. The atmospheric degradation of DME as well as the unique fuel properties of a oxygen containing compound will be discussed.

  5. Ether and ester derivatives of the perborate icosahedron

    DOE Patents [OSTI]

    Hawthorne, M. Frederick; Peymann, Toralf; Maderna, Andreas

    2003-12-16

    New boron icosahedral ethers and esters formed from Cs.sub.2 [closo-B.sub.12 (OH).sub.12 ],; Cs[closo-1-H-1-CB.sub.11 (OH).sub.11 ]; and closo-1,12-H.sub.2 -1,12-C.sub.2 B.sub.10 (OH).sub.10 are disclosed. Also set forth are their preparation by reacting the icosahedral boranes [closo-B.sub.12 H.sub.12 ].sup.2-, [closo-1-CB.sub.11 H.sub.12 ].sup.- and closo-1,12-(CH.sub.2 OH).sub.2 -1,12-C.sub.2 B.sub.10 H.sub.10 with an acid anhdride or acid chloride to form the ester or an alkylating agent to form the ether.

  6. Features of the spectral dependences of transmittance of organic semiconductors based on tert-butyl substituted lutetium phthalocyanine molecules

    SciTech Connect (OSTI)

    Belogorokhov, I. A.; Tikhonov, E. V.; Dronov, M. A.; Belogorokhova, L. I.; Ryabchikov, Yu. V.; Tomilova, L. G.; Khokhlov, D. R.

    2011-11-15

    Vibronic properties of organic semiconductors based on tert-butyl substituted phthalocyanine lutetium diphthalocyanine molecules are studied by IR and Raman spectroscopy. It is shown that substitution of several carbon atoms in initial phthalocyanine (Pc) ligands with {sup 13}C isotope atoms causes a spectral shift in the main absorption lines attributed to benzene, isoindol, and peripheral C-H groups. A comparison of spectral characteristics showed that the shift can vary from 3 to 1 cm{sup -1}.

  7. Sulfonimide-containing poly(arylene ether)s and poly(arylene ether sulfone)s, methods for producing the same, and uses thereof

    DOE Patents [OSTI]

    Hofmann, Michael A.

    2006-11-14

    The present invention is directed to sulfonimide-containing polymers, specifically sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, and processes for making the sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, for use conductive membranes and fuel cells.

  8. Mechanisms of Selective Cleavage of C-O Bonds in Di-aryl Ethers in Aqueous Phase

    SciTech Connect (OSTI)

    He, Jiayue; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-01-02

    A novel route for cleaving the C-O aryl ether bonds of p-substituted H-, CH3-, and OH- diphenyl ethers has been explored over Ni/SiO2 catalysts at very mild conditions. The C-O bond of diphenyl ether is cleaved by parallel hydrogenolysis and hydrolysis (hydrogenolysis combined with HO* addition) on Ni. The rates as a function of H2 pressure from 0 to 10 MPa indicate that the rate-determining step is the C-O bond cleavage on Ni. H* atoms compete with the organic reactant for adsorption leading to a maximum in the rate with increasing H2 pressure. In contrast to diphenyl ether, hydrogenolysis is the exclusive route for cleaving an ether C-O bond of di-p-tolyl ether to form p-cresol and toluene. 4,4'-dihydroxydiphenyl ether undergoes sequential surface hydrogenolysis, first to phenol and HOC6H4O* (adsorbed), which is then cleaved to phenol (C6H5O* with added H*) and H2O (O* with two added H*) in a second step. Density function theory supports the operation of this pathway. Notably, addition of H* to HOC6H4O* is less favorable than a further hydrogenolytic C-O bond cleavage. The TOFs of three aryl ethers with Ni/SiO2 in water followed the order 4,4'-dihydroxydiphenyl ether (69 h-1) > diphenyl ether (26 h-1) > di-p-tolyl ether (1.3 h-1), in line with the increasing apparent activation energies, ranging from 93 kJ∙mol-1 (4,4'-dihydroxydiphenyl ether) < diphenyl ether (98 kJ∙mol-1) to di-p-tolyl ether (105 kJ∙mol-1). D.M. thanks the support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R

  9. Aza crown ether compounds as anion receptors

    DOE Patents [OSTI]

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  10. Aza crown ether compounds as anion receptors

    DOE Patents [OSTI]

    Lee, H.S.; Yang, X.O.; McBreen, J.

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

  11. Crown ethers in graphene (Journal Article) | DOE PAGES

    Office of Scientific and Technical Information (OSTI)

    Crown ethers in graphene Prev Next Title: Crown ethers in graphene Crown ethers, ... them for many uses that demand higher binding affinity and selectivity9,10. In this ...

  12. Alternative Fuels lDimethyl Ether Rheology and Materials Studies...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Fuels lDimethyl Ether Rheology and Materials Studies Alternative Fuels lDimethyl Ether Rheology and Materials Studies 2004 Diesel Engine Emissions Reduction (DEER) Conference ...

  13. Barrierless proton transfer across weak CH⋯O hydrogen bonds in dimethyl ether dimer

    SciTech Connect (OSTI)

    Yoder, Bruce L. West, Adam H. C.; Signorell, Ruth; Bravaya, Ksenia B.; Bodi, Andras; Sztáray, Bálint

    2015-03-21

    We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME − h{sub 6}){sub n} and (DME − d{sub 6}){sub n}n = 1 and 2, in the 9–14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying C–H⋯O interactions. Results from electronic structure calculations predict that all of them undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. In fact, all neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH{sub 3}OHCH{sub 3}{sup +} by the loss of CH{sub 2}OCH{sub 3} with a 0 K appearance energy of 9.71 ± 0.03 eV and 9.73 ± 0.03 eV for (DME − h{sub 6}){sub 2} and deuterated (DME − d{sub 6}){sub 2}, respectively. The ground state threshold photoelectron spectrum band of the dimethyl ether dimer is broad and exhibits no vibrational structure. Dimerization results in a 350 meV decrease of the valence band appearance energy, a 140 meV decrease of the band maximum, thus an almost twofold increase in the ground state band width, compared with DME − d{sub 6} monomer.

  14. Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Lumetta, Gregg J.

    2005-10-31

    A comparative quantitative analysis of the effect of solvent modifiers on an ion-pair extraction of an inorganic salt by a crown ether was conducted. Two classes of the solvent modifiers that possess electron-pair donor (EPD) or hydrogen-bond donor (HBD) groups were investigated. The equilibrium constants corresponding to the extraction of sodium nitrate into nitrobenzene (NB) employing model neutral host cis-syn-cis-dicyclohexano-18-crown-6 (1) with and without solvent modifier were determined using the SXLSQI computer model. For a series of EPD modifiers—including tri-n-butyl- and tri-phenylphosphate, tri-n-butyl- and tri-phenylphosphine oxide, N,N-di-n-butyl- and N,N-di-phenyl acetamide—the enhancement of the NaNO3 extraction by 1 was found to be dependent on the hydrogen-bond acceptance ability of the modifier quantified by the b solvatochromic parameter. Application of the solvent EPD modifier improved solvation of the sodium ion, lowering the large energy barrier of Na+ partitioning into the extraction phase. A HBD modifier 3,5-di-t-butylphenol 8 that forms strong hydrogen bonds with nitrate anion in NB, exhibited even greater enhancement of the NaNO3 extraction by 1. The determined extraction constants were correlated with the b or a solvatochromic parameters of the solvent modifiers and linear trends were observed. Hydrogen bond interaction between 3,5-di-t-butylphenol 8 and nitrate anion in the presence of the sodium-loaded crown ether in the extraction phases was studied by vibrational spectroscopy. Formation of the simple 1:1 adduct was demonstrated.

  15. Conversion of Lignocellulosic Biomass to Ethanol and Butyl Acrylate

    SciTech Connect (OSTI)

    Binder, Thomas; Erpelding, Michael; Schmid, Josef; Chin, Andrew; Sammons, Rhea; Rockafellow, Erin

    2015-04-10

    Conversion of Lignocellulosic Biomass to Ethanol and Butyl Acrylate. The purpose of Archer Daniels Midlands Integrated Biorefinery (IBR) was to demonstrate a modified acetosolv process on corn stover. It would show the fractionation of crop residue to distinct fractions of cellulose, hemicellulose, and lignin. The cellulose and hemicellulose fractions would be further converted to ethanol as the primary product and a fraction of the sugars would be catalytically converted to acrylic acid, with butyl acrylate the final product. These primary steps have been demonstrated.

  16. Crown ethers in graphene (Journal Article) | DOE PAGES

    Office of Scientific and Technical Information (OSTI)

    Crown ethers in graphene Prev Next Title: Crown ethers in graphene You are ... them for many uses that demand higher binding affinity and selectivity9,10. In this ...

  17. Crown ethers in graphene (Journal Article) | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    Crown ethers in graphene Citation Details In-Document Search Title: Crown ethers in ... them for many uses that demand higher binding affinity and selectivity9,10. In this ...

  18. CH Packaging Operations Manual

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2003-06-26

    Introduction - This procedure provides instructions for assembling the following CH packaging payload: -Drum payload assembly -Standard Waste Box (SWB) assembly -Ten-Drum Overpack (TDOP).

  19. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOE Patents [OSTI]

    Crivello, J.V.

    1996-01-23

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} (V) wherein n is an integer from one to six and A is selected from cyclic ethers, polyether, and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  20. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOE Patents [OSTI]

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  1. Conversion of Lignocellulosic Biomass to Ethanol Butyl Acrylate

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Conversion of Lignocellulosic Biomass to Ethanol and Butyl Acrylate March 25, 2015 Principal Investigator Thomas P. Binder ARCHER DANIELS MIDLAND COMPANY 2 Where does ADM fit with the IBR? * Ensuring a supply of technology for future growth is a priority for ADM Research * Corn stover utilization may enable continued growth in starch supply while starting a new industry around a currently underutilized material James R Randall Research Center Decatur, IL ARCHER DANIELS MIDLAND COMPANY 3 Quad

  2. TABLE33.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update (EIA)

    ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ethers intended for motor gasoline blending...

  3. TABLE34.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update (EIA)

    ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ethers intended for motor gasoline blending...

  4. Alternative Fuels lDimethyl Ether Rheology and Materials Studies |

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Department of Energy Alternative Fuels lDimethyl Ether Rheology and Materials Studies Alternative Fuels lDimethyl Ether Rheology and Materials Studies 2004 Diesel Engine Emissions Reduction (DEER) Conference Presentation: The Pennsylvania State University 2004_deer_perez.pdf (548.66 KB) More Documents & Publications Research on Fuels & Lubricants Development of a Dimethyl Ether (DME)-Fueled Shuttle Bus Ionic Liquids as Multifunctional Ashless Additives for Engine Lubrication

  5. CH Packaging Operations Manual

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2005-06-13

    This procedure provides instructions for assembling the CH Packaging Drum payload assembly, Standard Waste Box (SWB) assembly, Abnormal Operations and ICV and OCV Preshipment Leakage Rate Tests on the packaging seals, using a nondestructive Helium (He) Leak Test.

  6. Computational and experimental study of the effects of adding dimethyl ether and ethanol to nonpremixed ethylene/air flames

    SciTech Connect (OSTI)

    Bennett, Beth Anne V.; McEnally, Charles S.; Pfefferle, Lisa D.; Smooke, Mitchell D.; Colket, Meredith B.

    2009-06-15

    Two sets of axisymmetric laminar coflow flames, each consisting of ethylene/air nonpremixed flames with various amounts (up to 10%) of either dimethyl ether (CH{sub 3}-O-CH{sub 3}) or ethanol (CH{sub 3}-CH{sub 2}-OH) added to the fuel stream, have been examined both computationally and experimentally. Computationally, the local rectangular refinement method, which incorporates Newton's method, is used to solve the fully coupled nonlinear conservation equations on solution-adaptive grids for each flame in two spatial dimensions. The numerical model includes C6 chemical kinetic mechanisms with up to 59 species, detailed transport, and an optically thin radiation submodel. Experimentally, thermocouples are used to measure gas temperatures, and mass spectrometry is used to determine concentrations of over 35 species along the flame centerline. Computational results are examined throughout each flame, and validation of the model occurs through comparison with centerline measurements. Very good agreement is observed for temperature, major species, and several minor species. As the level of additive is increased, temperatures, some major species (CO{sub 2}, C{sub 2}H{sub 2}), flame lengths, and residence times are essentially unchanged. However, peak centerline concentrations of benzene (C{sub 6}H{sub 6}) increase, and this increase is largest when dimethyl ether is the additive. Computational and experimental results support the hypothesis that the dominant pathway to C{sub 6}H{sub 6} formation begins with the oxygenates decomposing into methyl radical (CH{sub 3}), which combines with C2 species to form propargyl (C{sub 3}H{sub 3}), which reacts with itself to form C{sub 6}H{sub 6}. (author)

  7. Divinyl ether synthase gene, and protein and uses thereof

    DOE Patents [OSTI]

    Howe, Gregg A.; Itoh, Aya

    2006-12-26

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  8. Divinyl ether synthase gene and protein, and uses thereof

    SciTech Connect (OSTI)

    Howe, Gregg A.; Itoh, Aya

    2011-09-13

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  9. Arylations of coal model systems. [Benzyl phenyl ether and l-naphthylmethyl phenyl ether

    SciTech Connect (OSTI)

    Smith, B.F.; Venier, C.G.; Squires, T.G.

    1984-01-01

    Currently, coal is converted to clean liquids or low melting solids by processes which utilize high temperature, high pressure, or both. These processes occur by thermal bond cleavages and involve the intermediacy of free radicals. In a search for chemistry which could liquefy coal under milder conditions, the authors have focussed on thermally less demanding ionic reactions. Of the functional groups which commonly occur in coals, ethers are the easiest to cleave under acid conditions. Depending on the density of these linkages and their importance as crosslinks in the macromolecular structure of coals, solubilization might be greatly enhanced solely by cleaving and capping either bonds. Benzylic ethers are particularly reactive and have been implicated in the initiation of coal pyrolysis and hydropyrolysis. Arylation, the use of acids to cleave bonds in coals in the presence of aromatic rings to trap the consequent incipient carbonium ions, has a long history. This paper discusses the use of benzyl phenyl ether and l-naphthylmethyl phenyl ether and polymers related to them as models to develop and evaluate the chemistry involved in the arylations. 9 references, 1 figure, 4 tables.

  10. Separation of Dimethyl Ether from Syn-Gas Components by Poly(dimethylsiloxane) and Poly(4-methyl-1-pentene) Membranes

    SciTech Connect (OSTI)

    Christopher J. Orme; Frederick F. Stewart

    2011-05-01

    Permeability and selectivity in gas transport through poly(4-methyl-1-pentene) (TPX) and poly(dimethylsiloxane) (PDMS) using variable temperature mixed gas experiments is reported. Selected gases include H2, CO, CH4, CO2, and dimethyl ether (DME). The DME data is the first to be reported through these membranes. In this paper, the chosen polymers reflect both rubbery and crystalline materials. Rubbery polymers tend to be weakly size sieving, which, in this work, has resulted in larger permeabilities, lower separation factors, and lower activation energies of permeation (Ep). Conversely, the crystalline TPX membranes showed much greater sensitivity to penetrant size; although the gas condensability also played a role in transport.

  11. N-butyl Cyanoacrylate Glue Embolization of Arterial Networks to Facilitate

    Office of Scientific and Technical Information (OSTI)

    Hepatic Arterial Skeletonization before Radioembolization (Journal Article) | SciTech Connect N-butyl Cyanoacrylate Glue Embolization of Arterial Networks to Facilitate Hepatic Arterial Skeletonization before Radioembolization Citation Details In-Document Search Title: N-butyl Cyanoacrylate Glue Embolization of Arterial Networks to Facilitate Hepatic Arterial Skeletonization before Radioembolization Purpose. Avoidance of nontarget microsphere deposition via hepatoenteric anastomoses is

  12. Development of a Dimethyl Ether (DME)-Fueled Shuttle Bus | Department...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Development of a Dimethyl Ether (DME)-Fueled Shuttle Bus Chapter 7 - Advancing Systems and Technologies to Produce Cleaner Fuels Alternative Fuels lDimethyl Ether Rheology and ...

  13. Process for producing dimethyl ether from synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, R.

    1985-06-04

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  14. Process for producing dimethyl ether form synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, Ronald

    1985-01-01

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  15. Hydrogen production from the steam reforming of Dinethyl Ether and Methanol

    SciTech Connect (OSTI)

    Semelsberger, T. A.; Borup, R. L.

    2004-01-01

    This study investigates dimethyl ether (DME) steam reforming for the generation of hydrogen rich fuel cell feeds for fuel cell applications. Methanol has long been considered as a fuel for the generation of hydrogen rich fuel cell feeds due to its high energy density, low reforming temperature, and zero impurity content. However, it has not been accepted as the fuel of choice due its current limited availability, toxicity and corrosiveness. While methanol steam reforming for the generation of hydrogen rich fuel cell feeds has been extensively studied, the steam reforming of DME, CH{sub 3}OCH{sub 3} + 3H{sub 2}O = 2CO{sub 2} + 6H{sub 2}, has had limited research effort. DME is the simplest ether (CH{sub 3}OCH{sub 3}) and is a gas at ambient conditions. DME has physical properties similar to those of LPG fuels (i.e. propane and butane), resulting in similar storage and handling considerations. DME is currently used as an aerosol propellant and has been considercd as a diesel substitute due to the reduced NOx, SOx and particulate emissions. DME is also being considered as a substitute for LPG fuels, which is used extensively in Asia as a fuel for heating and cooking, and naptha, which is used for power generation. The potential advantages of both methanol and DME include low reforming temperature, decreased fuel proccssor startup energy, environmentally benign, visible flame, high heating value, and ease of storage and transportation. In addition, DME has the added advantages of low toxicity and being non-corrosive. Consequently, DME may be an ideal candidate for the generation of hydrogen rich fuel cell feeds for both automotive and portable power applications. The steam reforming of DME has been demonstrated to occur through a pair of reactions in series, where the first reaction is DME hydration followed by MeOH steam reforming to produce a hydrogen rich stream.

  16. Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

    SciTech Connect (OSTI)

    Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang; Boyer, François; Olivier, Philippe; Sapelkin, Andrei; King, Stephen; Heenan, Richard; Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri

    2014-06-21

    Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

  17. Development of specialty chemicals from dimethyl ether

    SciTech Connect (OSTI)

    Tartamella, T.L.; Lee, S.

    1996-12-31

    Dimethyl ether (DME) may be efficiently produced from coal-bases syngas in a high pressure, mechanically agitated slurry reactor. DME synthesis occurs in the liquid phase using a dual catalyst. By operating in a dual catalyst mode, DME may be converted from in-situ produced methanol resulting in higher methyl productivities and syngas conversions over methanol conversion alone. The feasibility of utilizing DME as a building block for more valuable specialty chemicals has been examined. A wide variety of petrochemicals may be produced from DME including light olefins, gasoline range hydrocarbons, oxygenates, and glycol precursors. These chemicals represent an important part of petroleum industries inventory of fine chemicals. Carbonylation, hydrocarbonylation, and oxidative dimerization are but a few of the reactions in which DME may undergo conversion. DME provides an additional route for the production of industrially important petrochemicals.

  18. High pressure injection of dimethyl ether

    SciTech Connect (OSTI)

    Glensvig, M.; Sorenson, S.C.; Abata, D.

    1996-12-31

    Partially oxygenated hydrocarbons produced from natural gas have been shown to be viable alternate fuels for the diesel engine, showing favorable combustion characteristics similar to that of diesel fuel but without exhaust particulates and with significantly reduced NO{sub x} emissions and lower engine noise. Further, engine studies have demonstrated that such compounds, like dimethyl ether (DME), can be injected at much lower pressures than conventional diesel fuel with better overall performance. This experimental study compares the injection of DME to that of conventional diesel fuel. Both fuels were injected into a quiescent high pressure chamber containing Nitrogen at pressures up to 25 atmospheres at room temperature with a pintle nozzle and jerk pump. Comparisons were obtained with high speed photography using a Hycam camera. Results indicate that there are significant differences in spray geometry and penetration which are not predictable with analytical models currently used for diesel fuels.

  19. CH-TRUCON Rev. 21, January 2008

    Office of Environmental Management (EM)

    DOEWIPP 01-3194 Rev. 21 CH-TRU WASTE CONTENT CODES (CH-TRUCON) Revision 21 January 2008 ... 01-3194 2 DOEWIPP 01-3194 Rev. 21 CH-TRU WASTE CONTENT CODES (CH-TRUCON) Revision 21 ...

  20. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  1. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  2. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  3. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  4. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  5. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  6. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  7. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  8. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  9. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  10. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  11. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  12. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  13. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  14. CH-TRU Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  15. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  16. CH-TRU Waste Content Codes (CH TRUCON)

    SciTech Connect (OSTI)

    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

  17. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  18. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  19. CH-TRU Waste Content Codes (CH-TRUCON)

    SciTech Connect (OSTI)

    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

  20. NOPR CH2M | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    CH2M NOPR CH2M NOPR CH2M (62.16 KB) More Documents & Publications NOPR NEI NEI Statement DOE Workshop 02 20 FINAL NOPR CIGNL

  1. Mechanisms of Selective Cleavage of C-O Bonds in Di-aryl Ethers...

    Office of Scientific and Technical Information (OSTI)

    Selective Cleavage of C-O Bonds in Di-aryl Ethers in Aqueous Phase Citation Details In-Document Search Title: Mechanisms of Selective Cleavage of C-O Bonds in Di-aryl Ethers in ...

  2. Li-air batteries having ether-based electrolytes

    DOE Patents [OSTI]

    Amine, Khalil; Curtiss, Larry A; Lu, Jun; Lau, Kah Chun; Zhang, Zhengcheng; Sun, Yang-Kook

    2015-03-03

    A lithium-air battery includes a cathode including a porous active carbon material, a separator, an anode including lithium, and an electrolyte including a lithium salt and polyalkylene glycol ether, where the porous active carbon material is free of a metal-based catalyst.

  3. Study on systems based on coal and natural gas for producing dimethyl ether

    SciTech Connect (OSTI)

    Zhou, L.; Hu, S.Y.; Chen, D.J.; Li, Y.R.; Zhu, B.; Jin, Y.

    2009-04-15

    China is a coal-dependent country and will remain so for a long time. Dimethyl ether (DME), a potential substitute for liquid fuel, is a kind of clean diesel motor fuel. The production of DME from coal is meaningful and is studied in this article. Considering the C/H ratios of coal and natural gas (NG), the cofeed (coal and NG) system (CFS), which does not contain the water gas shift process, is studied. It can reduce CO{sub 2} emission and increase the conversion rate of carbon, producing more DME. The CFS is simulated and compared with the coal-based and NG-based systems with different recycling ratios. The part of the exhaust gas that is not recycled is burned, producing electricity. On the basis of the simulation results, the thermal efficiency, economic index, and CO{sub 2} emission ratio are calculated separately. The CFS with a 100% recycling ratio has the best comprehensive evaluation index, while the energy, economy, and environment were considered at the same time.

  4. DISCOVERY OF THE METHOXY RADICAL, CH{sub 3}O, TOWARD B1: DUST GRAIN AND GAS-PHASE CHEMISTRY IN COLD DARK CLOUDS

    SciTech Connect (OSTI)

    Cernicharo, J.; Jimenez-Escobar, A.; Munoz Caro, G. M.; Marcelino, N.; Roueff, E.; Gerin, M.

    2012-11-10

    We report on the discovery of the methoxy radical (CH{sub 3}O) toward the cold and dense core B1-b based on the observation, with the IRAM 30 m radio telescope, of several lines at 3 and 2 mm wavelengths. Besides this new molecular species we also report on the detection of many lines arising from methyl mercaptan (CH{sub 3}SH), formic acid (HCOOH), propynal (HCCCHO), acetaldehyde (CH{sub 3}CHO), dimethyl ether (CH{sub 3}OCH{sub 3}), methyl formate (CH{sub 3}OCOH), and the formyl radical (HCO). The column density of all these species is {approx_equal}10{sup 12} cm{sup -2}, corresponding to abundances of {approx_equal}10{sup -11}. The similarity in abundances for all these species strongly suggest that they are formed on the surface of dust grains and ejected to the gas phase through non-thermal desorption processes, most likely cosmic rays or secondary photons. Nevertheless, laboratory experiments indicate that the CH{sub 3}O isomer released to the gas phase is CH{sub 2}OH rather than the methoxy one. Possible gas-phase formation routes to CH{sub 3}O from OH and methanol are discussed.

  5. On the competition between hydrogen abstraction versus C-O bond fission in initiating dimethyl ether combustion

    SciTech Connect (OSTI)

    Francisco, J.

    1999-07-01

    There has been a growing interest in the potential use of dimethyl ether (DME) as a diesel fuel in compression ignition engines. There are two initiation steps involved in the combustion of DME, one involving C-O bond fission and the other involving hydrogen abstraction by molecular oxygen. The kinetics and thermodynamics of C-O bond fission were explored computationally in a previous paper. The present paper addresses the competing process--hydrogen abstraction by molecular oxygen. Ab initio molecular orbital calculations are used to study the structures and energetics of the reactants, products, and the transition state for the CH{sub 3}OCH{sub 3} + O{sub 2} reaction. The calculations predict a barrier for hydrogen abstraction from CH{sub 3}OCH{sub 3} by O{sub 2} of 47.4 kcal/mol. This is lower than the barrier height for C-O bond fission previously calculated to be 81.1 kcal/mol. The results support values used in current models for the combustion of DME. Moreover, an examination of rates for C-O bond fission versus hydrogen abstraction by O{sub 2} suggests that the bimolecular process is the dominant pathway.

  6. CATALYSTS FOR HIGH CETANE ETHERS AS DIESEL FUELS

    SciTech Connect (OSTI)

    Kamil Klier; Richard G. Herman; James G.C. Shen; Qisheng Ma

    2000-08-31

    A novel 1,2-ethanediol, bis(hydrogen sulfate), disodium salt precursor-based solid acid catalyst with a zirconia substrate was synthesized and demonstrated to have significantly enhanced activity and high selectivity in producing methyl isobutyl ether (MIBE) or isobutene from methanol-isobutanol mixtures. The precursor salt was synthesized and provided by Dr. T. H. Kalantar of the M.E. Pruitt Research Center, Dow Chemical Co., Midland, MI 48674. Molecular modeling of the catalyst synthesis steps and of the alcohol coupling reaction is being carried out. A representation of the methyl transfer from the surface activated methanol molecule (left) to the activated oxygen of the isobutanol molecule (right) to form an ether linkage to yield MIBE is shown.

  7. 2' and 3' Carboranyl uridines and their diethyl ether adducts

    DOE Patents [OSTI]

    Soloway, Albert H.; Barth, Rolf F.; Anisuzzaman, Abul K.; Alam, Fazlul; Tjarks, Werner

    1992-01-01

    There is disclosed a process for preparing carboranyl uridine nucleoside compounds and their diethyl ether adducts, which exhibit a tenfold increase in boron content over prior art boron containing nucleoside compounds. Said carboranyl uridine nucleoside compounds exhibit enhanced lipophilicity and hydrophilic properties adequate to enable solvation in aqueous media for subsequent incorporation of said compounds in methods for boron neutron capture therapy in mammalian tumor cells.

  8. High octane ethers from synthesis gas-derived alcohol

    SciTech Connect (OSTI)

    Klier, K.; Herman, R.G.; Bastian, R.D.; DeTavernier, S. . Dept. of Chemistry Lehigh Univ., Bethlehem, PA . Zettlemoyer Center for Surface Studies)

    1991-01-01

    The objective of the proposed research is to synthesize high octane ethers directly from coal-derived synthesis gas via alcohol mixtures that are rich in methanol and isobutanol. The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers. Commercial acid and superacid resin catalysts were obtained and tested under one set of conditions to compare the activities and selectivities for forming the unsymmetric methylisobutylether (MIBE) by coupling methanol with isobutanol. It was found that both Nafion-H microsaddles and Amberlyst-15 resins are active for this synthesis reaction. While and the Nafion-H catalyst does form the MIBE product fairly selectively under the reaction conditions utilized, the Amberlyst-15 catalyst formed dimethylether (DME) as the major product. In addition, significantly larger quantities of the C{sub 4} hydrocarbon products were observed over the Amberlyst-15 catalyst at 123{degree}C and 13.6 atm. It has been demonstrated that methyltertiarybutylether (MTBE) MIBE, DME and diisobutylether (DIBE) are separated and quantitatively determined by using the proper analytical conditions. In order to gain insight into the role of superacidity in promoting the selective coupling of the alcohols to form the unsymmetric ether, the strengths of the acid sites on the catalysts are being probed by thermometric titrations in non-aqueous solutions. 18 refs., 20 figs., 4 tabs.

  9. CH-TRUCON Rev. 21, January 2008

    Office of Environmental Management (EM)

    DOE/WIPP 01-3194 Rev. 21 CH-TRU WASTE CONTENT CODES (CH-TRUCON) Revision 21 January 2008 This document supercedes DOE/WIPP 01-3194, Revision 20 CH-TRUCON, Rev. 21, January 2008 DOE/WIPP 01-3194 2 DOE/WIPP 01-3194 Rev. 21 CH-TRU WASTE CONTENT CODES (CH-TRUCON) Revision 21 January 2008 Approved by: [Signature on File] Date:____________ D. Casey Gadbury, National TRU Program Director CH-TRUCON, Rev. 21, January 2008 DOE/WIPP 01-3194 3 This document has been submitted as required to: Office of

  10. Methyl aryl ethers from coal liquids as gasoline extenders and octane improvers

    SciTech Connect (OSTI)

    Singerman, G.M.

    1980-11-01

    A mixture of methyl aryl ethers derived from the phenols present in direct liquefaction coal liquids shows considerable promise as a gasoline blending agent and octane improver. The mixture of methyl aryl ethers was blended at five volume percent with a commercial, unleaded gasoline. The properties and performance of the blend in a variety of laboratory and automotive tests is reported. The tests show that the mixture of methyl aryl ethers improves gasoline octane without degrading other gasoline properties.

  11. Thermodynamics of Hydrogen Production from Dimethyl Ether Steam Reforming and Hydrolysis

    SciTech Connect (OSTI)

    T.A. Semelsberger

    2004-10-01

    The thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the process of dimethyl ether (DME) steam reforming were investigated as a function of steam-to-carbon ratio (0-4), temperature (100 C-600 C), pressure (1-5 atm), and product species: acetylene, ethanol, methanol, ethylene, methyl-ethyl ether, formaldehyde, formic acid, acetone, n-propanol, ethane and isopropyl alcohol. Results of the thermodynamic processing of dimethyl ether with steam indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure was observed to shift the equilibrium toward the reactants; increasing the pressure from 1 atm to 5 atm decreased the conversion of dimethyl ether from 99.5% to 76.2%. The order of thermodynamically stable products in decreasing mole fraction was methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol--formaldehyde, formic acid, and acetylene were not observed. The optimal processing conditions for dimethyl ether steam reforming occurred at a steam-to-carbon ratio of 1.5, a pressure of 1 atm, and a temperature of 200 C. Modeling the thermodynamics of dimethyl ether hydrolysis (with methanol as the only product considered), the equilibrium conversion of dimethyl ether is limited. The equilibrium conversion was observed to increase with temperature and steam-to-carbon ratio, resulting in a maximum dimethyl ether conversion of approximately 68% at a steam-to-carbon ratio of 4.5 and a processing temperature of 600 C. Thermodynamically, dimethyl ether processed with steam can produce hydrogen-rich fuel-cell feeds--with hydrogen concentrations exceeding 70%. This substantiates dimethyl ether as a viable source of hydrogen for PEM fuel cells.

  12. Supply Impacts of an MTBE Ban

    Reports and Publications (EIA)

    2002-01-01

    This paper analyzes the supply impacts of removing methyl tertiary butyl ether (MTBE) from gasoline.

  13. On the radiation stability of crown ethers in ionic liquids.

    SciTech Connect (OSTI)

    Shkrob, I.; Marin, T.; Dietz, M.

    2011-04-14

    Crown ethers (CEs) are macrocyclic ionophores used for the separation of strontium-90 from acidic nuclear waste streams. Room temperature ionic liquids (ILs) are presently being considered as replacements for traditional molecular solvents employed in such separations. It is desirable that the extraction efficacy obtained with such solvents should not deteriorate in the strong radiation fields generated by decaying radionuclides. This deterioration will depend on the extent of radiation damage to both the IL solvent and the CE solute. While radiation damage to ILs has been extensively studied, the issue of the radiation stability of crown ethers, particularly in an IL matrix, has not been adequately addressed. With this in mind, we have employed electron paramagnetic resonance (EPR) spectroscopy to study the formation of CE-related radicals in the radiolysis of selected CEs in ILs incorporating aromatic (imidazolium and pyridinium) cations. The crown ethers have been found to yield primarily hydrogen loss radicals, H atoms, and the formyl radical. In the low-dose regime, the relative yield of these radicals increases linearly with the mole fraction of the solute, suggesting negligible transfer of the excitation energy from the solvent to the solute; that is, the solvent has a 'radioprotective' effect. The damage to the CE in the loading region of practical interest is relatively low. Under such conditions, the main chemical pathway leading to decreased extraction performance is protonation of the macrocycle. At high radiation doses, sufficient to increase the acidity of the IL solvent significantly, such proton complexes compete with the solvent cations as electron traps. In this regime, the CEs will rapidly degrade as the result of H abstraction from the CE ring by the released H atoms. Thus, the radiation dose to which a CE/IL system is exposed must be maintained at a level sufficiently low to avoid this regime.

  14. An aging study of wire chambers with dimethyl ether

    SciTech Connect (OSTI)

    Jibaly, M.; Chrusch, P. Jr.; Hilgenberg, G.; Majewski, S.; Wojcik, R.; Sauli, F.; Gaudaen, J.

    1989-02-01

    The authors report results on the aging of different types of resistive and non-resistive wires in wire chambers filled with dimethyl ether (DME) of varying degrees of purity. Among the Freon impurities detected in our DME batches, only Freon-11 was found to contribute to the aging process. Of the resistive wires, Nicotin and Stablohm produced fast aging, whereas stainless steel withstood extended irradiation in purified DME (up to 1 C/cm) without any apparent damage. Gold-plated tungsten and molybdenum wires produced results comparable to those of the stainless steel.

  15. Dimethyl ether production from methanol and/or syngas

    DOE Patents [OSTI]

    Dagle, Robert A; Wang, Yong; Baker, Eddie G; Hu, Jianli

    2015-02-17

    Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DME directly from syngas, such as syngas from biomass. Also disclosed are apparatus for DME production. The disclosed processes generally function at higher temperatures with lower contact times and at lower pressures than conventional processes so as to produce higher DME yields than do conventional processes. Certain embodiments of the processes are carried out in reactors providing greater surface to volume ratios than the presently used DME reactors. Certain embodiments of the processes are carried out in systems comprising multiple microchannel reactors.

  16. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Andre L. Boehman; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. Within the Combustion Laboratory of the Penn State Energy Institute, they have installed and equipped a Navistar V-8 direct-injection turbodiesel engine for measurement of gaseous and particulate emissions and examination of the impact of fuel composition on diesel combustion. They have also reconfigured a high-pressure viscometer for studies of the viscosity, bulk modulus (compressibility) and miscibility of blends of diesel fuel, dimethyl ether and lubricity additives. The results include baseline emissions, performance and combustion measurements on the Navistar engine for operation on a federal low sulfur diesel fuel (300 ppm S). Most recently, they have examined blends of an oxygenated fuel additive (a liquid fuel called CETANER{trademark}) produced by Air Products, for comparison with dimethyl ether blended at the same weight of oxygen addition, 2 wt.%. While they have not operated the engine on DME yet, they are now preparing to do so. A fuel system for delivery of DME/Diesel blends has been configured

  17. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO2(111) Model Catalysts

    SciTech Connect (OSTI)

    F Calaza; T Chen; D Mullins; S Overbury

    2011-12-31

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  18. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO(2)(111) Model Catalysts

    SciTech Connect (OSTI)

    Calaza, Florencia C; Chen, Tsung-Liang; Mullins, David R; Overbury, Steven {Steve} H

    2011-01-01

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  19. Dimethyl ether synthesis from syngas in slurry phase

    SciTech Connect (OSTI)

    Han, Y.Z.; Fujimoto, K.; Shikata, T.

    1997-12-31

    Dimethyl ether (DME) is one of the important chemicals derived from synthesis gas. It can be widely used in syngas conversion, production of olefins, or MTG gasoline. Recently, is has been noticed as a substitute of LPG used as home fuel. In the present study, dimethyl ether was effectively synthesized from CO rich syngas (H{sub 2}/CO=1/1) over hybrid catalyst containing a Cu-Zn-Al(O) based methanol synthesis catalyst and {gamma}-alumina in an agitated slurry reactor under relatively mild reaction conditions: temperature 230--300 C, pressure 2.0--5.0 MPa, contact time 2.0--10 gram-cat.-h/mol. The catalysts used as the methanol active components were commercially available Cu-Zn-Al(O) based catalysts, BASF S385 and ICI 51-2. Two kinds of {gamma}-alumina ALO4 (standard catalyst of the Catalysis Society of Japan) and N612N (NIKKI Co., Japan) were used as the methanol dehydration components. The slurry was prepared by mixing the fine powder (<100 mesh) of catalyst components with purified n-hexadecane. The catalysts were reduced by a mixing gas containing 20% syngas and 80% nitrogen with a three-hour programmed temperature raising from room temperature to the final temperature. All products were analyzed by gas chromatographs. Results are given and discussed.

  20. Rational Design of Cesium-Selective Ionophores and Chemosensors: Dihydrocalix[4]arene Crown-6 Ethers

    SciTech Connect (OSTI)

    Sachleben, Richard A.; Bryan, Jeffrey C.; Brown, Gilbert M.; Engle, Nancy L.; Haverlock, Tamara J.; Hay, Benjamin P.; Urvoas, Agathe; Moyer, Bruce A.

    2003-12-15

    Molecular mechanics calculations performed on calix[4]arene crown-6 ethers predict that the 1,3-dihydro derivatives will exhibit greater complementarity for potassium and cesium ions than the parent 1,3-dialkoxy calix crowns. The X-ray crystal structures of 1,3-alt bis-octyloxycalix[4]arene benzocrown-6 ether, dihydrocalix[4]arene benzocrown-6 ether, and the cesium nitrate complex of dihydrocalix[4]arene benzocrown-6 ether were determined. The cesium complex structure corresponds closely to the structure predicted by molecular mechanics. The dihydrocalix[4]arene crown-6 ethers exhibit enhanced cesium selectivity in the extraction of alkali metal salts and provide a platform for a highly sensitive and selective cesium chemosensor.

  1. CH

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    signal is readily suppressed using time-delay methods enabled by femtosecond laser pulses. ... in situ, without the need of labels and without damage to the carbon substrates. ...

  2. CH Packaging Operations for High Wattage Waste

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2006-01-06

    This document provides instructions for assembling the following CH packaging payload: Drum payload assembly Standard Waste Box (SWB) assembly Ten-Drum Overpack (TDOP)

  3. Role of acid catalysis in dimethyl ether conversion processes

    SciTech Connect (OSTI)

    Tartamella, T.L.; Lee, S.

    1996-12-31

    Acidity plays an important role in the conversion of methanol and dimethyl ether (DME) to hydrocarbons and oxygenates. In the conversion to hydrocarbons over zeolite catalyst, Broensted acidity is the main contributor to the first hydrocarbon formed. Here, acidity is also an important factor in determining olefin, paraffin, and aromatic content in the final product distribution. Catalyst life has also been found to be related to acidity content in zeolites. DME conversion to oxygenates is especially dependent on high acidity catalysts. Superacids like BF{sub 3}, HF-BF{sub 3}, and CF{sub 3}COOH have been used in the past for conversion of DME in carbonylation reactions to form methyl acetate and acetic acid at high pressures. Recently, heteropoly acids and their corresponding metal substituted salts have been used to convert DME to industrially important petrochemicals resulting in shorter reaction times and without the use of harsh operating conditions.

  4. Dimethyl ether fuel proposed as an alternative to LNG

    SciTech Connect (OSTI)

    Kikkawa, Yoshitsugi; Aoki, Ichizo

    1998-04-06

    To cope with the emerging energy demand in Asia, alternative fuels to LNG must be considered. Alternative measures, which convert the natural gas to liquid fuel, include the Fischer-Tropsch conversion, methanol synthesis, and dimethyl ether (DME) synthesis. Comparisons are evaluated based on both transportation cost and feed-gas cost. The analysis will show that DME, one alternative to LNG as transportation fuel, will be more economical for longer distances between the natural-gas source and the consumer. LNG requires a costly tanker and receiving terminal. The break-even distance will be around 5,000--7,000 km and vary depending on the transported volume. There will be risk, however, since there has never been a DME plant the size of an LNG-equivalent plant [6 million metric tons/year (mty)].

  5. Shape-selective catalysis in dimethyl ether conversion

    SciTech Connect (OSTI)

    Sardesai, A.; Lee, S.

    1999-07-01

    Coal-derived syngas can be effectively converted to dimethyl ether (DME) in a single-stage, liquid-phase process. This Liquid Phase Dimethyl Ether (LPDME) process utilizes a dual catalytic system, which comprises of a physical blend between the methanol synthesis and the methanol dehydration catalyst slurried in an inert mineral oil. Such produced DME has vast potential as a building block chemical in the petrochemical industry to produce value-added specialty chemicals. The current research efforts are made to exploit the utilization of shape-selective catalysis using zeolites to produce targeted petrochemicals, including lower olefinic hydrocarbons. The catalysts probed in this investigation include zeolites of different physical, morphological, and chemical configurations. The effect of acidity of ZSM-5 type zeolites as well as the effect of the different channel size and orientation of the zeolites on product selectivity and catalyst deactivation are examined. Results obtained from experimentation of this study show that ZSM-5 type zeolite with low acidity (high SiO{sub 2}/Al{sub 2}O{sub 3} ratio, in this case 150) exhibits the highest selectivity towards lower (C{sub 2}-C{sub 4}) olefins in general. Controlled selectivity toward targeted olefinic species can be accomplished via devising catalytic reaction systems in such a way that the structural property of the catalyst and reactive interaction between molecules in the pores are geared toward formation of targeted molecular species which also at the same time prevent the formation of less desirable products. The internal morphology of the catalyst also has a pronounced effect on the deactivation phenomenon, where it is observed that zeolites possessing high acidity and a unidimensional channel structure are prone towards catalyst deactivation by coking and pore blockage.

  6. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Andre L. Boehman; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The laboratory studies have included work with a Navistar V-8 turbodiesel engine, demonstration of engine operation on DME-diesel blends and instrumentation for evaluating fuel properties. The field studies have involved performance, efficiency and emissions measurements with the Champion Motorcoach ''Defender'' shuttle bus which will be converted to DME-fueling. The results include baseline emissions, performance and combustion measurements on the Navistar engine for operation on a federal low sulfur diesel fuel (300 ppm S). Most recently, they have completed engine combustion studies on DME-diesel blends up to 30 wt% DME addition.

  7. Synergistic effect of mixing dimethyl ether with methane, ethane, propane, and ethylene fuels on polycyclic aromatic hydrocarbon and soot formation

    SciTech Connect (OSTI)

    Yoon, S.S.; Anh, D.H.; Chung, S.H.

    2008-08-15

    Characteristics of polycyclic aromatic hydrocarbon (PAH) and soot formation in counterflow diffusion flames of methane, ethane, propane, and ethylene fuels mixed with dimethyl ether (DME) have been investigated. Planar laser-induced incandescence and fluorescence techniques were employed to measure relative soot volume fractions and PAH concentrations, respectively. Results showed that even though DME is known to be a clean fuel in terms of soot formation, DME mixture with ethylene fuel increases PAH and soot formation significantly as compared to the pure ethylene case, while the mixture of DME with methane, ethane, and propane decreases PAH and soot formation. Numerical calculations adopting a detailed kinetics showed that DME can be decomposed to produce a relatively large number of methyl radicals in the low-temperature region where PAH forms and grows; thus the mixture of DME with ethylene increases CH{sub 3} radicals significantly in the PAH formation region. Considering that the increase in the concentration of O radicals is minimal in the PAH formation region with DME mixture, the enhancement of PAH and soot formation in the mixture flames of DME and ethylene can be explained based on the role of methyl radicals in PAH and soot formation. Methyl radicals can increase the concentration of propargyls, which could enhance incipient benzene ring formation through the propargyl recombination reaction and subsequent PAH growth. Thus, the result substantiates the importance of methyl radicals in PAH and soot formation, especially in the PAH formation region of diffusion flames. (author)

  8. Conversion of dimethyl ether--boron trifluoride complex to potassium fluoborate

    DOE Patents [OSTI]

    Eberle, A.R.

    1957-06-18

    A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

  9. CONVERSION OF DIMETHYL ETHER-BORON TRIFLUORIDE COMPLEX TO POTASSIUM FLUOBORATE

    DOE Patents [OSTI]

    Eberle, A.R.

    1957-06-18

    A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

  10. Green polymer electrolytes based on chitosan and 1-butyl-3-methylimidazolium acetate

    SciTech Connect (OSTI)

    Shamsudin, Intan Juliana; Ahmad, Azizan; Hassan, Nur Hasyareeda

    2014-09-03

    Green polymer electrolytes based on chitosan as the polymer matrix and ionic liquid 1-butyl-3-methylimidazolium acetate [Bmim][OAc] as charge carriers were prepared by solution casting technique. Complexes with various amount of ionic liquid loading were investigated as possible ionic conducting polymers. The ionic conductivity was found to increase with increasing weight percent of ionic liquid. The highest ionic conductivity of the charged chitosan-[Bmim][OAc] was 2.44 × 10{sup −3} S cm{sup −1} at 90 wt.% of [Bmim][OAc] content at ambient temperature. Attenuated Total Reflection Fourier Transform infrared (ATR-FTIR) spectroscopy has proven the interaction between chitosan and [Bmim][OAc]. X-ray Diffraction (XRD) has shown that the amorphosity of the complexes increase as the amount of [Bmim][OAc] increase.

  11. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOE Patents [OSTI]

    Crabtree, Robert H. (Bethany, CT); Brown, Stephen H. (East Haven, CT)

    1988-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  12. Metal ion complexation by ionizable crown ethers. Final report, January 1, 1988--June 30, 1994

    SciTech Connect (OSTI)

    Bartsch, R.A.

    1994-12-31

    During the report period a variety of new lipophilic ionizable crown ethers with pendent proton-ionizable groups has been synthesized. The ligands possess one or more ionizable group (carboxylic acid, phosphonic acid monoethyl ester, para-nitrophenol, phosphonic acid) attached to crown ether, monoazacrown ether or diazacrown ether frameworks. These novel chelating agents have either pendent or inward-facing proton-ionizable groups. Such lipophilic proton-ionizable crown ethers are designed for use in multiphase metal ion separations (solvent extraction, liquid membrane transport). In addition a series of proton-ionizable crown ethers without lipophilic groups was prepared to study how structural variations within the ligand influence metal ion complexation in homogeneous media as assessed by NMR spectroscopy or titration calorimetry. A third class of new metal ion-complexing agents is a series of lipophilic acyclic polyether dicarboxylic acids. Competitive solvent extractions of alkali metal and alkaline earth cations and of the mixed species have been conducted to reveal the influence of ring size, nature and attachment site of the lipophilic group, sidearm length, and proton-ionizable group identity and location upon the selectivity and efficiency of metal ion complexation. In addition to such studies of structural variation within the lipophilic proton-ionizable crown ether, the effect of changing the organic solvent and variation of the stripping conditions have been assessed. The influence of structural variations within lipophilic acyclic polyether dicarboxylic acids upon competitive solvent extraction of alkaline earth cations has been probed. Also a new chromogenic, di-ionizable crown ether with extremely high selectivity for Hg{sup 2+} has been discovered.

  13. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOE Patents [OSTI]

    Crabtree, R.H.; Brown, S.H.

    1988-02-16

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  14. CH-TRU Waste Content Codes

    SciTech Connect (OSTI)

    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

  15. Independent Oversight Review, Hanford Site CH2M Hill Plateau...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    CH2M Hill Plateau Remediation Company - November 2012 Independent Oversight Review, Hanford Site CH2M Hill Plateau Remediation Company - November 2012 November 2012 Review of the...

  16. Newport News in Review, ch. 47, segment includes TEDF groundbreaking...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    https:www.jlab.orgnewsarticlesnewport-news-review-ch-47-segment-includes-tedf-groundbreaking-event Newport News in Review, ch. 47, segment includes TEDF groundbreaking event...

  17. Central Characterization Program (CCP) Contact-Handled (CH) TRU...

    Office of Environmental Management (EM)

    Contact-Handled (CH) TRU Waste Certification and Waste Information SystemWaste Data System (WWISWDS) Data Entry Central Characterization Program (CCP) Contact-Handled (CH) TRU...

  18. Wide range modeling study of dimethyl ether oxidation

    SciTech Connect (OSTI)

    Pitz, W.J.; Marinov, N.M.; Westbrook, C.K.; Dagaut, P.; Boettner, J-C; Cathonnet, M.

    1997-04-01

    A detailed chemical kinetic model has been used to study dimethyl ether (DME) oxidation over a wide range of conditions. Experimental results obtained in a jet-stirred reactor (JSR) at I and 10 atm, 0.2 < 0 < 2.5, and 800 < T < 1300 K were modeled, in addition to those generated in a shock tube at 13 and 40 bar, 0 = 1.0 and 650 :5 T :5 1300 K. The JSR results are particularly valuable as they include concentration profiles of reactants, intermediates and products pertinent to the oxidation of DME. These data test the Idnetic model severely, as it must be able to predict the correct distribution and concentrations of intermediate and final products formed in the oxidation process. Additionally, the shock tube results are very useful, as they were taken at low temperatures and at high pressures, and thus undergo negative temperature dependence (NTC) behavior. This behavior is characteristic of the oxidation of saturated hydrocarbon fuels, (e.g. the primary reference fuels, n-heptane and iso- octane) under similar conditions. The numerical model consists of 78 chemical species and 336 chemical reactions. The thermodynamic properties of unknown species pertaining to DME oxidation were calculated using THERM.

  19. ARM - Datastreams - avhrr11ch4

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  7. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Howard Glunt; Andre L. Boehman; Allen Homan; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. Their strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The bulk of the efforts over the past year were focused on the conversion of the campus shuttle bus. This process, started in August 2001, took until April 2002 to complete. The process culminated in an event to celebrate the launching of the shuttle bus on DME-diesel operation on April 19, 2002. The design of the system on the shuttle bus was patterned after the system developed in the engine laboratory, but also was subjected to a rigorous failure modes effects analysis (FMEA, referred to by Air Products as a ''HAZOP'' analysis) with help from Dr. James Hansel of Air Products. The result of this FMEA was the addition of layers of redundancy and over-pressure protection to the system on the shuttle bus. The system became operational in February 2002. Preliminary emissions tests and basic operation of the shuttle bus took place at the Pennsylvania Transportation Institute's test track facility near the University Park airport. After modification and optimization of the system on the bus, operation on the

  8. Understanding chemical reactions of CO{sub 2} and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS{sub 2} in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

    SciTech Connect (OSTI)

    Cabao, M. Isabel, E-mail: isabelcabaco@ist.utl.pt [Departamento de Fsica, Instituto Superior Tcnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Fsica Atmica da UL, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Besnard, Marcel; Danten, Yann [GSM Institut des Sciences Molculaires, CNRS (UMR 5255), Universit de Bordeaux, 351, Cours de la Libration 33405 Talence Cedex (France); Chvez, Fabin Vaca [Centro de Fsica da Matria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Pinaud, Nol [CESAMO Institut des Sciences Molculaires, CNRS (UMR 5255), Universit de Bordeaux, 351, Cours de la Libration 33405 Talence Cedex (France); Sebastio, Pedro J. [Departamento de Fsica, Instituto Superior Tcnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Fsica da Matria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Coutinho, Joo A. P. [CICECO, Departamento de Qumica, Universidade de Aveiro 3810-193 Aveiro (Portugal)

    2014-06-28

    NMR spectroscopy ({sup 1}H, {sup 13}C, {sup 15}N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS{sub 2} leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH{sub 3}COS{sup ?}), CO{sub 2}, OCS, and trithiocarbonate (CS{sub 3}{sup 2?}). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro]{sup +} cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS{sub 2}-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO{sub 2}-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS{sub 2} reacts with the acetate anion leading to the formation of CH{sub 3}COS{sup ?}, CO{sub 2}, and OCS. After these reactions have proceeded the nascent CO{sub 2} and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO{sub 2}) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO{sub 2}-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO{sub 2} molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO{sub 2}, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated

  9. Comparison of SPME headspace analysis to U.S. EPA method5030/8260B for MTBE monitoring

    SciTech Connect (OSTI)

    Stringfellow, William T.; Oh, Kuen-Chan

    2005-02-01

    A novel method for analysis of methyl tert-butyl ether andtert-butyl alcohol using solid phase microextraction is described andcompared to a standard method.

  10. CH2M HILL Plateau Remediation Company - Hanford Site

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Contracting CH2M HILL Plateau Remediation Company Contracting ORP Contracts and Procurements RL Contracts and Procurements CH2M HILL Plateau Remediation Company Mission Support Alliance Washington Closure Hanford HPM Corporation (HPMC) Wastren Advantage, Inc. Bechtel National, Inc. Washington River Protection Solutions CH2M HILL Plateau Remediation Company Email Email Page | Print Print Page | Text Increase Font Size Decrease Font Size CH2M CH2M HILL Plateau Remediation Company is the prime

  11. Method for photochemical reduction of uranyl nitrate by tri-N-butyl phosphate and application of this method to nuclear fuel reprocessing

    DOE Patents [OSTI]

    De Poorter, Gerald L.; Rofer-De Poorter, Cheryl K.

    1978-01-01

    Uranyl ion in solution in tri-n-butyl phosphate is readily photochemically reduced to U(IV). The product U(IV) may effectively be used in the Purex process for treating spent nuclear fuels to reduce Pu(IV) to Pu(III). The Pu(III) is readily separated from uranium in solution in the tri-n-butyl phosphate by an aqueous strip.

  12. Synthesis of methanol and dimethyl ether from syngas over Pd/ZnO/Al2O3 catalysts

    SciTech Connect (OSTI)

    Lebarbier, Vanessa M.; Dagle, Robert A.; Kovarik, Libor; Lizarazo-Adarme, Jair A.; King, David L.; Palo, Daniel R.

    2012-01-01

    A Pd/ZnO/Al2O3 catalyst was developed for the synthesis of methanol and dimethyl ether (DME) from syngas. Studied were temperatures of operation ranging from 250C to 380C. High temperatures (e.g. 380C) are necessary when combining methanol and DME synthesis with a methanol to gasoline (MTG) process in a single reactor bed. A commercial Cu/ZnO/Al2O3 catalyst, utilized industrially for the synthesis of methanol at 220-280C, suffers from a rapid deactivation when the reaction is conducted at high temperature (>320C). On the contrary, a Pd/ZnO/Al2O3 catalyst was found to be highly stable for methanol and DME synthesis at 380C. The Pd/ZnO/Al2O3 catalyst was thus further investigated for methanol and DME synthesis at P=34-69 bars, T= 250-380C, GHSV= 5 000-18 000 h-1, and molar feeds H2/CO= 1, 2, and 3. Selectivity to DME increased with decreasing operating temperature, and increasing operating pressure. Increased GHSVs and H2/CO syngas feed ratios also enhanced DME selectivity. Undesirable CH4 formation was observed, however, can be minimized through choice of process conditions and by catalyst design. By studying the effect of the Pd loading and the Pd:Zn molar ratio the formulation of the Pd/ZnO/Al2O3 catalyst was optimized. A catalyst with 5% Pd and a Pd:Zn molar ratio of 0.25:1 has been identified as the preferred catalyst. Results indicate that PdZn particles are more active than Pd particles for the synthesis of methanol and less active for CH4 formation. A correlation between DME selectivity and the concentration of acid sites of the catalysts has been established. Hence, two types of sites are required for the direct conversion of syngas to DME: 1) PdZn particles are active for the synthesis of methanol from syngas, and 2) acid sites which are active for the conversion of methanol to DME. Additionally, CO2 formation was problematic as PdZn was found to be active for the water-gas-shift (WGS) reaction, under all the conditions evaluated.

  13. N-butyl Cyanoacrylate Glue Embolization of Arterial Networks to Facilitate Hepatic Arterial Skeletonization before Radioembolization

    SciTech Connect (OSTI)

    Samuelson, Shaun D.; Louie, John D.; Sze, Daniel Y.

    2013-06-15

    Purpose. Avoidance of nontarget microsphere deposition via hepatoenteric anastomoses is essential to the safety of yttrium-90 radioembolization (RE). The hepatic hilar arterial network may remain partially patent after coil embolization of major arteries, resulting in persistent risk. We retrospectively reviewed cases where n-butyl cyanoacrylate (n-BCA) glue embolization was used to facilitate endovascular hepatic arterial skeletonization before RE. Methods. A total of 543 RE procedures performed between June 2004 and March 2012 were reviewed, and 10 were identified where n-BCA was used to embolize hepatoenteric anastomoses. Arterial anatomy, prior coil embolization, and technical details were recorded. Outcomes were reviewed to identify subsequent complications of n-BCA embolization or nontarget RE. Results. The rate of complete technical success was 80 % and partial success 20 %, with one nontarget embolization complication resulting in a minor change in treatment plan. No evidence of gastrointestinal or biliary ischemia or infarction was identified, and no microsphere-related gastroduodenal ulcerations or other evidence of nontarget RE were seen. Median volume of n-BCA used was <0.1 ml. Conclusion. n-BCA glue embolization is useful to eliminate hepatoenteric networks that may result in nontarget RE, especially in those that persist after coil embolization of major vessels such as the gastroduodenal and right gastric arteries.

  14. MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Stavila, Vitalie; Parthasarathi, Ramakrishnan; Davis, Ryan W.; El Gabaly, Farid; Sale, Kenneth L.; Simmons, Blake A.; Singh, Seema; Allendorf, Mark D.

    2015-11-23

    We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H2 and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Thus repeated cycling induces no loss ofmore » activity, making this a promising route for mild aryl-ether bond scission.« less

  15. MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds

    SciTech Connect (OSTI)

    Stavila, Vitalie; Parthasarathi, Ramakrishnan; Davis, Ryan W.; El Gabaly, Farid; Sale, Kenneth L.; Simmons, Blake A.; Singh, Seema; Allendorf, Mark D.

    2015-11-23

    We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H2 and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Thus repeated cycling induces no loss of activity, making this a promising route for mild aryl-ether bond scission.

  16. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Howard Glunt; Andre L. Boehman; Allen Homan; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethylether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The bulk of the efforts over the past year were focused on the conversion of the campus shuttle bus. This process, started in August 2001, took until April 2002 to complete. The process culminated in an event to celebrate the launching of the shuttle bus on DME-diesel operation on April 19, 2002. The design of the system on the shuttle bus was patterned after the system developed in the engine laboratory, but also was subjected to a rigorous failure modes effects analysis with help from Dr. James Hansel of Air Products. The result of this FMEA was the addition of layers of redundancy and over-pressure protection to the system on the shuttle bus. The system became operation in February 2002. Preliminary emissions tests and basic operation of the shuttle bus took place at the Pennsylvania Transportation institute's test track facility near the University Park airport. After modification and optimization of the system on the bus, operation on the campus shuttle route began in early June 2002. However, the work

  17. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOE Patents [OSTI]

    Crabtree, Robert H. (Bethany, CT); Brown, Stephen H. (East Haven, CT)

    1989-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  18. Catalyst system and process for benzyl ether fragmentation and coal liquefaction

    DOE Patents [OSTI]

    Zoeller, Joseph Robert (Kingsport, TN)

    1998-04-28

    Dibenzyl ether can be readily cleaved to form primarily benzaldehyde and toluene as products, along with minor amounts of bibenzyl and benzyl benzoate, in the presence of a catalyst system comprising a Group 6 metal, preferably molybdenum, a salt, and an organic halide. Although useful synthetically for the cleavage of benzyl ethers, this cleavage also represents a key model reaction for the liquefaction of coal; thus this catalyst system and process should be useful in coal liquefaction with the advantage of operating at significantly lower temperatures and pressures.

  19. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOE Patents [OSTI]

    Crabtree, R.H.; Brown, S.H.

    1989-10-17

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  20. Effect of antisymmetric CH stretching excitation on the dynamics of O({sup 1}D) + CH{sub 4} ? OH + CH{sub 3}

    SciTech Connect (OSTI)

    Pan, Huilin; Yang, Jiayue; Zhang, Dong; Shuai, Quan; Jiang, Bo [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China)] [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Dai, Dongxu; Wu, Guorong, E-mail: wugr@dicp.ac.cn, E-mail: xmyang@dicp.ac.cn; Yang, Xueming, E-mail: wugr@dicp.ac.cn, E-mail: xmyang@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China) [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China)

    2014-04-21

    The effect of antisymmetric CH stretching excitation of CH{sub 4} on the dynamics and reactivity of the O({sup 1}D) + CH{sub 4} ? OH + CD{sub 3} reaction at the collision energy of 6.10 kcal/mol has been investigated using the crossed-beam and time-sliced velocity map imaging techniques. The antisymmetric CH stretching mode excited CH{sub 4} molecule was prepared by direct infrared excitation. From the measured images of the CH{sub 3} products with the infrared laser on and off, the product translational energy and angular distributions were derived for both the ground and vibrationally excited reactions. Experimental results show that the vibrational energy of the antisymmetric stretching excited CH{sub 4} reagent is channeled exclusively into the vibrational energy of the OH co-products and, hence, the OH products from the excited-state reaction are about one vibrational quantum hotter than those from the ground-state reaction, and the product angular distributions are barely affected by the vibrational excitation of the CH{sub 4} reagent. The reactivity was found to be suppressed by the antisymmetric stretching excitation of CH{sub 4} for all observed CH{sub 3} vibrational states. The degree of suppression is different for different CH{sub 3} vibrational states: the suppression is about 40%60% for the ground state and the umbrella mode excited CH{sub 3} products, while for the CH{sub 3} products with one quantum symmetric stretching mode excitation, the suppression is much less pronounced. In consequence, the vibrational state distribution of the CH{sub 3} product from the excited-state reaction is considerably different from that of the ground-state reaction.

  1. Enforcement Letter, CH2M Hill- October 4, 2004

    Broader source: Energy.gov [DOE]

    Issued to CH2M Hill related to at a Lapse in Dosimetry Accreditation at the Separations Process Research Unit

  2. Distribution of 1-Butyl-3-methylimidazolium Bistrifluoromethylsulfonimide in Mesoporous Silica as a Function of Pore Filling

    SciTech Connect (OSTI)

    Han, Kee Sung; Wang, Xiqing; Hagaman, Edward {Ed} W; Dai, Sheng

    2013-01-01

    Rotational dynamics of the ionic liquid (IL) 1-butyl-3-methlyimidazolium bistrifluoromethylsulfonimide, [C4mim][Tf2N], 1, as a neat liquid and confined in mesoporous silica were investigated by 1H spin-spin (T2) and spin-lattice (T1) relaxation measurements and 13C NMR spectroscopy. Translational dynamics (self-diffusion) were monitored via the diffusion coefficient, D, obtained with 1H pulsed field gradient NMR measurements. These data were used to determine the distribution of 1 in the pores of KIT-6, a mesoporous silica with a bicontinuous gyroid pore structure, as a function of filling fraction. Relaxation studies performed as a function of filling factor and temperature, reveal a dynamic heterogeneity in both translational and rotational motions for 1 at filling factors, f, = 0.2-1.0 (f = 1 corresponds to fully filled pores). Spin-lattice and spin-spin relaxation times reveal the motion of 1 in silica mesopores conform to that expected for a two-dimensional relaxation model. The relaxation dynamics are interpreted using a two-state, fast exchange model for all motions; a slow rotation (and translation) of molecules in contact with the surface and a faster motion approximated by the values for bulk relaxation and diffusion. 1 retains liquid like behavior at all filling factors and temperatures that extend to ca. 50 degrees below the bulk melting point. Translational motion in these systems, interpreted with MD-simulated diffusivity limits, confirms the high propensity of 1 to form a monolayer film on the silica surface at low filling factors.. The attractive interaction of 1 with the surface is greater than that for self-association of 1. The trends in diffusion data at short and long diffusion time suggest that the population of surface-bound 1 is in intimate contact with 1 in the pores. This condition is most easily met at higher filling fractions with successive additions of 1 increasing the layer thickness built up on the surface layer.

  3. 1

    Office of Environmental Management (EM)

    Tetrachloroethylene, Trichloroethylene, Trichloroflouromethane, Acetone, Ethyl ether, Methanol, Methyl isobutyl ketone, n-Butyl alcohol, Xylene, Cresols, Cresylic acid,...

  4. MTBE Production Economics (Released in the STEO April 2001)

    Reports and Publications (EIA)

    2001-01-01

    The purpose of this analysis is to evaluate the causes of methyl tertiary butyl ether (MTBE) price increases in 2000.

  5. Dosimetric measurements of an n-butyl cyanoacrylate embolization material for arteriovenous malformations

    SciTech Connect (OSTI)

    Labby, Zacariah E.; Chaudhary, Neeraj; Gemmete, Joseph J.; Pandey, Aditya S.; Roberts, Donald A.

    2015-04-15

    Purpose: The therapeutic regimen for cranial arteriovenous malformations often involves both stereotactic radiosurgery and endovascular embolization. Embolization agents may contain tantalum or other contrast agents to assist the neurointerventionalists, leading to concerns regarding the dosimetric effects of these agents. This study investigated dosimetric properties of n-butyl cyanoacrylate (n-BCA) plus lipiodol with and without tantalum powder. Methods: The embolization agents were provided cured from the manufacturer with and without added tantalum. Attenuation measurements were made for the samples and compared to the attenuation of a solid water substitute using a 6 MV photon beam. Effective linear attenuation coefficients (ELAC) were derived from attenuation measurements made using a portal imager and derived sample thickness maps projected in an identical geometry. Probable dosimetric errors for calculations in which the embolized regions are overridden with the properties of water were calculated using the ELAC values. Interface effects were investigated using a parallel plate ion chamber placed at set distances below fixed samples. Finally, Hounsfield units (HU) were measured using a stereotactic radiosurgery CT protocol, and more appropriate HU values were derived from the ELAC results and the CT scanners HU calibration curve. Results: The ELAC was 0.0516 0.0063 cm{sup ?1} and 0.0580 0.0091 cm{sup ?1} for n-BCA without and with tantalum, respectively, compared to 0.0487 0.0009 cm{sup ?1} for the water substitute. Dose calculations with the embolized region set to be water equivalent in the treatment planning system would result in errors of ?0.29% and ?0.93% per cm thickness of n-BCA without and with tantalum, respectively. Interface effects compared to water were small in magnitude and limited in distance for both embolization materials. CT values at 120 kVp were 2082 and 2358 HU for n-BCA without and with tantalum, respectively; dosimetrically

  6. The effect of catalyst ratio on catalytic performance in liquid phase dimethyl ether process

    SciTech Connect (OSTI)

    Guo Junwang; Niu Yuqin; Zhang Bijiang

    1997-12-31

    In the liquid phase dimethyl ether (LPDME) process, two functionally different catalysts are slurried together in an inert liquid medium. Syngas reacts on the surface of the methanol catalyst and methanol is dehydrated on the surface of the dehydration catalyst dispersed in the liquid. The process is adaptable to carbon monoxide-rich syngas derived from second generation coal gasifiers. The effect of catalyst ratio on catalytic performances of the dual catalyst was studied in liquid phase dimethyl ether synthesis from syngas at 280 C, 4.0 MPa. CO conversion, H{sub 2} conversion and DME productivity increased with an increase of catalyst ratio initially, reached their maximum at a catalyst ratio of 4.0--5.0, and then decreased. Methanol productivity and methanol equivalent productivity had a similar trend to that of DME productivity. DME selectivity and hydrocarbon selectivity increased with an increase in catalyst ratio whereas methanol selectivity decreased with catalyst ratio.

  7. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOE Patents [OSTI]

    Diebold, James P.; Scahill, John W.; Chum, Helena L.; Evans, Robert J.; Rejai, Bahman; Bain, Richard L.; Overend, Ralph P.

    1996-01-01

    A process for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols.

  8. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOE Patents [OSTI]

    Diebold, J.P.; Scahill, J.W.; Chum, H.L.; Evans, R.J.; Rejai, B.; Bain, R.L.; Overend, R.P.

    1996-04-02

    A process is described for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols. 35 figs.

  9. Molecular modeling of the morphology and transport properties of two direct methanol fuel cell membranes: phenylated sulfonated poly(ether ether ketone ketone) versus Nafion

    SciTech Connect (OSTI)

    Devanathan, Ramaswami; Idupulapati, Nagesh B.; Dupuis, Michel

    2012-08-14

    We have used molecular dynamics simulations to examine membrane morphology and the transport of water, methanol and hydronium in phenylated sulfonated poly ether ether ketone ketone (Ph-SPEEKK) and Nafion membranes at 360 K for a range of hydration levels. At comparable hydration levels, the pore diameter is smaller, the sulfonate groups are more closely packed, the hydronium ions are more strongly bound to sulfonate groups, and the diffusion of water and hydronium is slower in Ph-SPEEKK relative to the corresponding properties in Nafion. The aromatic carbon backbone of Ph-SPEEKK is less hydrophobic than the fluorocarbon backbone of Nafion. Water network percolation occurs at a hydration level ({lambda}) of {approx}8 H{sub 2}O/SO{sub 3}{sup -}. At {lambda} = 20, water, methanol and hydronium diffusion coefficients were 1.4 x 10{sup -5}, 0.6 x 10{sup -5} and 0.2 x 10{sup -5} cm{sup 2}/s, respectively. The pore network in Ph-SPEEKK evolves dynamically and develops wide pores for {lambda} > 20, which leads to a jump in methanol crossover and ion transport. This study demonstrates the potential of aromatic membranes as low-cost challengers to Nafion for direct methanol fuel cell applications and the need to develop innovative strategies to combat methanol crossover at high hydration levels.

  10. 2[prime] and 3[prime] Carboranyl uridines and their diethyl ether adducts

    DOE Patents [OSTI]

    Soloway, A.H.; Barth, R.F.; Anisuzzaman, A.K.; Alam, F.; Tjarks, W.

    1992-12-15

    A process is described for preparing carboranyl uridine nucleoside compounds and their diethyl ether adducts, which exhibit a tenfold increase in boron content over prior art boron containing nucleoside compounds. The carboranyl uridine nucleoside compounds exhibit enhanced lipophilicity and hydrophilic properties adequate to enable solvation in aqueous media for subsequent incorporation of the compounds in methods for boron neutron capture therapy in mammalian tumor cells. No Drawings

  11. Ch. I, Report on Waunita Hot Springs Project, Gunnison County...

    Open Energy Info (EERE)

    Report: Ch. I, Report on Waunita Hot Springs Project, Gunnison County, Colorado Author K. W. Nickerson and Associates Editor T. G. Zacharakis Published Colorado Geological...

  12. Voluntary Protection Program Onsite Review, CH2M HILL Plateau...

    Broader source: Energy.gov (indexed) [DOE]

    Programs Participants' Association (VPPPA) Presentation: Conducting your Annual VPP Self Assessment Voluntary Protection Program Onsite Review, CH2M HILL Analytical Technical...

  13. Graphene Oxide Catalyzed C-H Bond Activation: The Importance...

    Office of Scientific and Technical Information (OSTI)

    Graphene Oxide Catalyzed C-H Bond Activation: The Importance Oxygen Functional Groups for Biaryl Construction Citation Details In-Document Search Title: Graphene Oxide Catalyzed C-...

  14. CH Packaging Operations for High Wattage Waste at LANL

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2005-04-04

    This procedure provides instructions for assembling the following CH packaging payload: Drum payload assembly Standard Waste Box (SWB) assembly Ten-Drum Overpack (TDOP).

  15. CH Packaging Operations for High Wattage Waste at LANL

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2005-04-13

    This procedure provides instructions for assembling the following CH packaging payload: Drum payload assembly Standard Waste Box (SWB) assembly Ten-Drum Overpack (TDOP).

  16. 2011 Annual Planning Summary for Chicago Operations Office (CH...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    2011 Annual Planning Summary for Chicago Operations Office (CH) The ongoing and projected Environmental Assessments and Environmental Impact Statements for 2011 and 2012 within ...

  17. Experimental Confirmation of CH Mandrel Removal from Be Shells...

    Office of Scientific and Technical Information (OSTI)

    Experimental Confirmation of CH Mandrel Removal from Be Shells Citation Details ... Although the plastic mandrel may not be a design issue, it is a fielding issue because at ...

  18. Ch. VII, Temperature, heat flow maps and temperature gradient...

    Open Energy Info (EERE)

    Report: Ch. VII, Temperature, heat flow maps and temperature gradient holes Author T. G. Zacharakis Editor T. G. Zacharakis Published Colorado Geological Survey in Cooperation...

  19. Preparation and characterization of polymer blend based on sulfonated poly (ether ether ketone) and polyetherimide (SPEEK/PEI) as proton exchange membranes for fuel cells

    SciTech Connect (OSTI)

    Hashim, Nordiana; Ali, Ab Malik Marwan; Lepit, Ajis; Rasmidi, Rosfayanti; Subban, Ri Hanum Yahaya; Yahya, Muhd Zu Azhan

    2015-08-28

    Blends of sulfonated poly (ether ether ketone) (SPEEK) and polyetherimide (PEI) were prepared in five different weight ratios using N-methyl-2-pyrrolidone (NMP) as solvent by the solution cast technique. The degree of sulfonation (DS) of the sulfonated PEEK was determined from deuterated dimethyl sulfoxide (DMSO-d{sub 6}) solution of the purified polymer using {sup 1}H NMR method. The properties studied in the present investigation includes conductivity, water uptake, thermal stability and structure analysis of pure SPEEK as well as SPEEK-PEI polymer blend membranes. The experimental results show that the conductivity of the membranes increased with increase in temperature from 30 to 80°C, except for that of pure SPEEK membrane which increased with temperature from 30 to 60°C while its conductivity decreased with increasing temperature from 60 to 80°C. The conductivity of 70wt.%SPEEK-30wt.%PEI blend membrane at 80% relative humidity (RH) is found to be 1.361 × 10{sup −3} Scm{sup −1} at 30°C and 3.383 × 10{sup −3} Scm{sup −1} at 80°C respectively. It was also found that water uptake and thermal stability of the membranes slightly improved upon blending with PEI. Structure analysis was carried out using Fourier Transform Infrared (FTIR) spectroscopy which revealed considerable interactions between sulfonic acid group of SPEEK and imide groups of PEI. Modification of SPEEK by blending with PEI shows good potential for improving the electrical and physical properties of proton exchange membranes.

  20. A laser and molecular beam mass spectrometer study of low-pressure dimethyl ether flames

    SciTech Connect (OSTI)

    Andrew McIlroy; Toby D. Hain; Hope A. Michelsen; Terrill A. Cool

    2000-12-15

    The oxidation of dimethyl ether (DME) is studied in low-pressure flames using new molecular beam mass spectrometer and laser diagnostics. Two 30.0-Torr, premixed DME/oxygen/argon flames are investigated with stoichiometries of 0.98 and 1.20. The height above burner profiles of nine stable species and two radicals are measured. These results are compared to the detailed chemical reaction mechanism of Curran and coworkers. Generally good agreement is found between the model and data. The largest discrepancies are found for the methyl radical profiles where the model predicts qualitatively different trends in the methyl concentration with stoichiometry than observed in the experiment.

  1. Improvement of performance and emissions of a compression ignition methanol engine with dimethyl ether

    SciTech Connect (OSTI)

    Guo, J.; Chikahisa, Takemi; Murayama, Tadashi; Miyano, Masaharu

    1994-10-01

    Dimethyl ether (DME) has very good compression ignition characteristics and can be converted from methanol using a {gamma}-alumina catalyst. In this study a torch ignition chamber (TIC) head with TIC close to the center of the main combustion chamber was designed for the TIC method. The possibility of improvements in reducing the quantities of DME and emission were investigated by optimizing the TIC position, methanol injection timing, DME injection timing, and intake and exhaust throttling. It was found that the necessary amount of DME was greatly reduced when optimizing methanol and DME injection timings. 2 refs., 16 figs., 1 tab.

  2. High octane ethers from synthesis gas-derived alcohols. Quarterly technical progress report, April--June 1993

    SciTech Connect (OSTI)

    Klier, K.; Herman, R.G.; Menszak, J.; Johansson, M.A.; Feeley, O.C.; Kim, D.

    1993-07-01

    The results shown in Figures 10 and 11 demonstrate that the formation of butenes was very sensitive to the alcohol partial pressure. A small elevation of the alcohol pressure suppressed the formation of butenes rather drastically at both 90 and 117{degree}C. The synthesis rates of DME, MIBE, and MTBE ethers were not significantly affected at 90{degree}C, although there was a trend to increase the space time yield of DME as the alcohol pressure was increased. At the reaction temperature of 117{degree}C, all of the ethers showed increasing productivities as the pressure of the reactants was increased (Figure 11). An isotope labelling experiment was carried out to provide mechanistic insight into the manner in which methanol and isobutanol react together to form DME, MIBE, and MTBE ethers and to determine if MTBE were derived from MIBE.

  3. Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) Process. Peroxide formation of dimethyl ether in methanol mixtures

    SciTech Connect (OSTI)

    Waller, F.J.

    1997-11-01

    Organic peroxides could form when dimethyl ether in methanol is stored for three to six months at a time. The objective of this work was to determine the level of peroxide formation from dimethyl ether in reagent grade methanol and raw methanol at room temperature under 3 atmospheres (45 psig) of air. Raw methanol is methanol made from syngas by the LPMEOH Process without distillation. Aliphatic ethers tend to react slowly with oxygen from the air to form unstable peroxides. However, there are no reports on peroxide formation from dimethyl ether. After 172 days of testing, dimethyl ether in either reagent methanol or raw methanol at room temperature and under 60--70 psig pressure of air does not form detectable peroxides. Lack of detectable peroxides suggests that dimethyl ether or dimethyl ether and methanol may be stored at ambient conditions. Since the compositions of {approximately} 1.3 mol% or {approximately} 4.5 mol% dimethyl ether in methanol do not form peroxides, these compositions can be considered for diesel fuel or an atmospheric turbine fuel, respectively.

  4. Calixarene crown ether solvent composition and use thereof for extraction of cesium from alkaline waste solutions

    DOE Patents [OSTI]

    Moyer, Bruce A. (Oak Ridge, TN); Sachleben, Richard A. (Knoxville, TN); Bonnesen, Peter V. (Knoxville, TN); Presley, Derek J. (Ooltewah, TN)

    2001-01-01

    A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.

  5. Catalyst activity maintenance study for the liquid phase dimethyl ether process

    SciTech Connect (OSTI)

    Peng, X.D.; Toseland, B.A.; Underwood, R.P.

    1995-12-31

    The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizes a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.

  6. Assessing the toxic effects of ethylene glycol ethers using Quantitative Structure Toxicity Relationship models

    SciTech Connect (OSTI)

    Ruiz, Patricia; Mumtaz, Moiz; Gombar, Vijay

    2011-07-15

    Experimental determination of toxicity profiles consumes a great deal of time, money, and other resources. Consequently, businesses, societies, and regulators strive for reliable alternatives such as Quantitative Structure Toxicity Relationship (QSTR) models to fill gaps in toxicity profiles of compounds of concern to human health. The use of glycol ethers and their health effects have recently attracted the attention of international organizations such as the World Health Organization (WHO). The board members of Concise International Chemical Assessment Documents (CICAD) recently identified inadequate testing as well as gaps in toxicity profiles of ethylene glycol mono-n-alkyl ethers (EGEs). The CICAD board requested the ATSDR Computational Toxicology and Methods Development Laboratory to conduct QSTR assessments of certain specific toxicity endpoints for these chemicals. In order to evaluate the potential health effects of EGEs, CICAD proposed a critical QSTR analysis of the mutagenicity, carcinogenicity, and developmental effects of EGEs and other selected chemicals. We report here results of the application of QSTRs to assess rodent carcinogenicity, mutagenicity, and developmental toxicity of four EGEs: 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, and 2-butoxyethanol and their metabolites. Neither mutagenicity nor carcinogenicity is indicated for the parent compounds, but these compounds are predicted to be developmental toxicants. The predicted toxicity effects were subjected to reverse QSTR (rQSTR) analysis to identify structural attributes that may be the main drivers of the developmental toxicity potential of these compounds.

  7. dimethyl ether

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Predictive Simulation of Engines Transportation Energy Consortiums Engine Combustion ... Schematic representation of the experimental set-up. Shown in the figure is the jet-stirre...

  8. Identification of volatile butyl rubber thermal-oxidative degradation products by cryofocusing gas chromatography/mass spectrometry (cryo-GC/MS).

    SciTech Connect (OSTI)

    Smith, Jonell Nicole; White, Michael Irvin; Bernstein, Robert; Hochrein, James Michael

    2013-02-01

    Chemical structure and physical properties of materials, such as polymers, can be altered as aging progresses, which may result in a material that is ineffective for its envisioned intent. Butyl rubber formulations, starting material, and additives were aged under thermal-oxidative conditions for up to 413 total days at up to 124 %C2%B0C. Samples included: two formulations developed at Kansas City Plant (KCP) (%236 and %2310), one commercially available formulation (%2321), Laxness bromobutyl 2030 starting material, and two additives (polyethylene AC-617 and Vanax MBM). The low-molecular weight volatile thermal-oxidative degradation products that collected in the headspace over the samples were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). The majority of identified degradation species were alkanes, alkenes, alcohols, ketones, and aldehydes. Observations for Butyl %2310 aged in an oxygen-18 enriched atmosphere (18O2) were used to verify when the source of oxygen in the applicable degradation products was from the gaseous environment rather than the polymeric mixture. For comparison purposes, Butyl %2310 was also aged under non-oxidative thermal conditions using an argon atmosphere.

  9. Molecular dynamics simulations of n-hexane at 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide interface

    SciTech Connect (OSTI)

    Lisal, Martin; Izak, Pavel

    2013-07-07

    Molecular dynamics simulations of n-hexane adsorbed onto the interface of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([bmim][Tf{sub 2}N]) are performed at three n-hexane surface densities, ranged from 0.7 to 2.3 {mu}mol/m{sup 2} at 300 K. For [bmim][Tf{sub 2}N] room-temperature ionic liquid, we use a non-polarizable all-atom force field with the partial atomic charges based on ab initio calculations for the isolated ion pair. The net charges of the ions are {+-}0.89e, which mimics the anion to cation charge transfer and polarization effects. The OPLS-AA force field is employed for modeling of n-hexane. The surface tension is computed using the mechanical route and its value decreases with increase of the n-hexane surface density. The [bmim][Tf{sub 2}N]/n-hexane interface is analyzed using the intrinsic method, and the structural and dynamic properties of the interfacial, sub-interfacial, and central layers are computed. We determine the surface roughness, global and intrinsic density profiles, and orientation ordering of the molecules to describe the structure of the interface. We further compute the survival probability, normal and lateral self-diffusion coefficients, and re-orientation correlation functions to elucidate the effects of n-hexane on dynamics of the cations and anions in the layers.

  10. Computational Study of Molecular Structure and Self-Association of Tri-n-butyl Phosphates in n-Dodecane

    SciTech Connect (OSTI)

    Vo, Quynh N.; Hawkins, Cory; Dang, Liem X.; Nilsson, Mikael; Nguyen, Hung D.

    2015-01-29

    Tri-n-butyl phosphate is an important extractant used in solvent extraction process for the recovery of uranium and plutonium from spent nuclear fuel. To understand the fundamental molecular level behavior of extracting agents in solution, an atomistic parameterization study was carried out using the AMBER force field to model TBP molecule and n-dodecane molecule, a commonly used organic solvent, for molecular dynamics simulations. For validation of the optimized force field, various thermophysical properties of pure TBP and pure n-dodecane in the bulk liquid phase such as mass density, dipole moment, self-diffusion coefficient and heat of vaporization were calculated and compared favorably with experimental values. The molecular structure of TBPs in n-dodecane at various TBP concentrations was examined based on radial distribution functions and 2D potential mean force, which was used as criteria for identifying TBP aggregates. The dimerization constant of TBP in n-dodecane was also obtained and matches the experimental value. The U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences funded the work performed by LXD.

  11. Molecular Dynamics Simulations of Tri-n-butyl-phosphate/n-Dodecane Mixture: Thermophysical Properties and Molecular Structure

    SciTech Connect (OSTI)

    de Almeida, Valmor F; Cui, Shengting; Khomami, Bamin

    2014-01-01

    Molecular dynamics simulations of tri-n-butyl-phosphate (TBP)/n-dodecane mixture in the liquid phase have been carried out using two recently developed TBP force field models (J. Phys. Chem. B 2012, 116, 305) in combination with the all-atom optimized potentials for liquid simulations (OPLS-AA) force field model for n-dodecane. Specifically, the electric dipole moment of TBP, mass density of the mixture, and the excess volume of mixing were computed with TBP mole fraction ranging from 0 to 1. It is found that the aforementioned force field models accurately predict the mass density of the mixture in the entire mole fraction range. Commensurate with experimental measurements, the electric dipole moment of the TBP was found to slightly increase with the mole fraction of TBP in the mixture. Also, in accord with experimental data, the excess volume of mixing is positive in the entire mole fraction range, peaking at TBP mole fraction range 0.3 0.5. Finally, a close examination of the spatial pair correlation functions between TBP molecules, and between TBP and n-dodecane molecules, revealed formation of TBP dimers through self-association at close distance, a phenomenon with ample experimental evidence.

  12. CH2M HILL Plateau Remediation Company | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    CH2M HILL Plateau Remediation Company CH2M HILL Plateau Remediation Company The Office of Hea1th, Safety and Security's Office of Enforcement and Oversight has evaluated the facts and circumstances of a series of radiological work deficiencies at the Plutonium Finishing Plant (PFP) and the 105 K-East Reactor Facility (105KE Reactor) by CH2M HILL Plateau Remediation Company (CHPRC). The radiological work deficiencies at PFP are documented in the April 29, 2011, Department of Energy Richland

  13. Degradation of Imidazolium- and Quaternary Ammonium-Functionalized Poly(fluorenyl ether ketone sulfone) Anion Exchange Membranes

    SciTech Connect (OSTI)

    Chen, DY; Hickner, MA

    2012-11-01

    Imidazolium and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone)s were synthesized successfully with the same degree of cationic functionalization and identical polymer backbones for a comparative study of anion exchange membranes (AEMs) for solid-state alkaline membrane fuel cells (AMFCs). Both anion exchange membranes were synthesized using a new methyl-containing monomer that avoided the use of toxic chloromethylation reagents. The polymer chemical structures were confirmed by H-1 NMR and FTIR. The derived AEMs were fully characterized by water uptake, anion conductivity, stability under aqueous basic conditions, and thermal stability. Interestingly, both the cationic groups and the polymer backbone were found to be degraded in 1 M NaOH solution at 60 degrees C over 48 h as measured by changes of ion exchange capacity and intrinsic viscosity. Imidazolium-functionalized poly(fluorenyl ether ketone sulfone)s had similar aqueous alkaline stability to quaternary ammonium-functionalized materials at 60 degrees C but much lower stability at 80 degrees C. This work demonstrates that quaternary ammonium and imidazolium cationic groups are not stable on poly(arylene ether sulfone) backbones under relatively mild conditions. Additionally, the poly(arylene ether sulfone) backbone, which is one of the most common polymers used in ion exchange membrane applications, is not stable in the types of molecular configurations analyzed.

  14. CH2M Hill Ltd | Open Energy Information

    Open Energy Info (EERE)

    in consulting, design, engineering, procurement, construction, and operations and maintenance. References: CH2M Hill Ltd1 This article is a stub. You can help OpenEI by...

  15. Voluntary Protection Program Onsite Review, CH2M HILL Analytical...

    Broader source: Energy.gov (indexed) [DOE]

    Evaluation to determine whether CH2M HILL Analytical Technical Services is continuing to perform at a level deserving DOE-VPP Star recognition. The Team conducted its review during...

  16. Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

    DOE Patents [OSTI]

    Ramprasad, Dorai; Waller, Francis Joseph

    1998-01-01

    This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

  17. Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

    DOE Patents [OSTI]

    Ramprasad, D.; Waller, F.J.

    1998-04-28

    This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

  18. Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process

    DOE Patents [OSTI]

    Peng, Xiang-Dong; Parris, Gene E.; Toseland, Bernard A.; Battavio, Paula J.

    1998-01-01

    The present invention pertains to a process for the coproduction of methanol and dimethyl ether (DME) directly from a synthesis gas in a single step (hereafter, the "single step DME process"). In this process, the synthesis gas comprising hydrogen and carbon oxides is contacted with a dual catalyst system comprising a physical mixture of a methanol synthesis catalyst and a methanol dehydration catalyst. The present invention is an improvement to this process for providing an active and stable catalyst system. The improvement comprises the use of an aluminum phosphate based catalyst as the methanol dehydration catalyst. Due to its moderate acidity, such a catalyst avoids the coke formation and catalyst interaction problems associated with the conventional dual catalyst systems taught for the single step DME process.

  19. Mixed ether electrolytes for secondary lithium batteries with improved low temperature performance

    SciTech Connect (OSTI)

    Abraham, K.M.; Pasquariello, D.M.; Martin, F.J.

    1986-04-01

    Tetrahydrofuran (THF): 2-methyl-tetrahydrofuran (2Me-THF)/LiAsF/sub 6/ mixed solutions, despite their lower conductivity, have allowed significantly better low temperature performance in Li/TiS/sub 2/ cells than have THF/LiAsF/sub 6/, /sup 13/C NMR data suggest that this may be related to the structurally disordered Li/sup +/-solvates that exist in the mixed ether solutions. High cycling efficiencies for the Li electrode in THF:2Me-THF/LiAsF/sub 6/ solutions have been achieved by the use of 2Me-F as an additive. A 5 Ah capacity Li/TiS/sub 2/ cell has been cycled more than 100 times at 100, depth-of-discharge, with the cell capacity remaining at over 3 Ah at the 100th cycle.

  20. Methanol with dimethyl ether ignition promotor as fuel for compression ignition engines

    SciTech Connect (OSTI)

    Brook, D.L.; Cipolat, D.; Rallis, C.J.

    1984-08-01

    Reduction of the world dependence upon crude oil necessitates the use of long term alternative fuels for internal combustion engines. Alcohols appear to offer a solution as in the short term they can be manufactured from natural gas and coal, while ultimately they may be produced from agricultural products. A fair measure of success has been achieved in using alcohols in spark ignition engines. However the more widely used compression ignition engines cannot utilize unmodified pure alcohols. The current techniques for using alcohol fuels in compression ignition engines all have a number of shortcomings. This paper describes a novel technique where an ignition promotor, dimethyl ether (DME), is used to increase the cetane rating of methanol. The systems particular advantage is that the DME can be catalyzed from the methanol base fuel, in situ. This fuel system matches the performance characteristics of diesel oil fuel.

  1. Using Heteropolyacids in the Anode Catalyst Layer of Dimethyl Ether PEM Fuel Cells

    SciTech Connect (OSTI)

    Ferrell III, J. R.; Turner, J. A.; Herring, A. M.

    2008-01-01

    In this study, polarization experiments were performed on a direct dimethyl ether fuel cell (DMEFC). The experimental setup allowed for independent control of water and DME flow rates. Thus the DME flow rate, backpressure, and water flow rate were optimized. Three heteropoly acids, phosphomolybdic acid (PMA), phosphotungstic acid (PTA), and silicotungstic acid (STA) were incorporated into the anode catalyst layer in combination with Pt/C. Both PTA-Pt and STA-Pt showed higher performance than the Pt control at 30 psig of backpressure. Anodic polarizations were also performed, and Tafel slopes were extracted from the data. The trends in the Tafel slope values are in agreement with the polarization data. The addition of phosphotungstic acid more than doubled the power density of the fuel cell, compared to the Pt control.

  2. Portal Vein Embolization before Right Hepatectomy: Improved Results Using n-Butyl-Cyanoacrylate Compared to Microparticles Plus Coils

    SciTech Connect (OSTI)

    Guiu, Boris Bize, Pierre; Gunthern, Daniel; Demartines, Nicolas; Halkic, Nermin; Denys, Alban

    2013-10-15

    Background: There is currently no consensus in the literature on which embolic agent induces the greatest degree of liver hypertrophy after portal vein embolization (PVE). Only experimental results in a pig model have demonstrated an advantage of n-butyl-cyanoacrylate (NBCA) over 3 other embolic materials (hydrophilic gel, small and large polyvinyl alcohol particles) for PVE. Therefore, the aim of this human study was to retrospectively compare the results of PVE using NBCA with those using spherical microparticles plus coils. Methods: A total of 34 patients underwent PVE using either NBCA (n = 20), or spherical microparticles plus coils (n = 14). PVE was decided according to preoperative volumetry on the basis of contrast-enhanced CT. Groups were compared for age, sex, volume of the left lobe before PVE and future remnant liver ratio (FRL) (volume of the left lobe/total liver volume - tumor volume). The primary end point was the increase in left lobe volume 1 month after PVE. Secondary end points were procedure complications and biological tolerance. Results: Both groups were similar in terms of age, sex ratio, left lobe volume, and FRL before PVE. NBCA induced a greater increase in volume after PVE than did microparticles plus coils (respectively, +74 {+-} 69 % and +23 {+-} 14 %, p < 0.05). The amount of contrast medium used for the procedure was significantly larger when microparticles and coils rather than NBCA were used (respectively, 264 {+-} 43 ml and 162 {+-} 34 ml, p < 0.01). The rate of PVE complications as well as the biological tolerance was similar in both groups. Conclusion: NBCA seems more effective than spherical microparticles plus coils to induce left-lobe hypertrophy.

  3. Catalytic Consequences of Acid Strength in the Conversion of Methanol to Dimethyl Ether

    SciTech Connect (OSTI)

    Carr, Robert T.; Neurock, Matthew; Iglesia, Enrique

    2011-02-14

    The effects of acid identity on CH{sub 3}OH dehydration are examined here using density functional theory (DFT) estimates of acid strength (as deprotonation energies, DPE) and reaction energies, combined with rate data on Keggin polyoxometalate (POM) clusters and zeolite H-BEA. Measured first-order (k{sub mono}) and zero-order (k{sub dimer}) CH3OH dehydration rate constants depend exponentially on DPE for POM clusters; the value of k{sub mono} depends more strongly on DPE than k{sub dimer} does. The chemical significance of these rate parameters and the basis for their dependences on acid strength were established by using DFT to estimate the energies of intermediates and transition states involved in elementary steps that are consistent with measured rate equations. We conclude from this treatment that CH{sub 3}OH dehydration proceeds via direct reactions of co-adsorbed CH{sub 3}OH molecules for relevant solid acids and reaction conditions. Methyl cations formed at ion-pair transition states in these direct routes are solvated by H{sub 2}O and CH{sub 3}OH more effectively than those in alternate sequential routes involving methoxide formation and subsequent reaction with CH{sub 3}OH. The stability of ion-pairs, prevalent as intermediates and transition states on solid acids, depends sensitively on DPE because of concomitant correlations between the stability of the conjugate anionic cluster and DPE. The chemical interpretation of k{sub mono} and k{sub dimer} from mechanism-based rate equations, together with thermochemical cycles of their respective transition state formations, show that similar charge distributions in the intermediate and transition state involved in k{sub dimer} cause its weaker dependence on DPE. Values of k{sub mono} involve uncharged reactants and the same ion-pair transition state as k{sub dimer}; these species sense acid strength differently and cause the larger effects of DPE on k{sub mono}. Confinement effects in H-BEA affect the value of

  4. The use of dimethyl ether as a starting aid for methanol-fueled SI engines at low temperatures

    SciTech Connect (OSTI)

    Kozole, K.H.; Wallace, J.S

    1988-01-01

    Methanol-fueled SI engines have proven to be difficult to start at ambient temperatures below approximately 10/sup 0/C. The use of dimethyl ether (DME) is proposed to improve the cold starting performance of methanol-fueled SI engines. Tests to evaluate this idea were carried out with a modified single-cylinder CFR research engine having a compression ratio of 12:1. The engine was fueled with combinations of gaseous dimethyl ether and liquid methanol having DME mass fractions of 30%, 40%, 60% and 70%. For comparison, tests were also carried out with 100% methanol and with winter grade premium unleaded gasoline. Overall stoichiometric mixtures were used in all tests.

  5. Carbon-carbon bond cleavage of 1,2-hydroxy ethers b7 vanadium(V) dipicolinate complexes

    SciTech Connect (OSTI)

    Hanson, Susan K; Gordon, John C; Thorn, David L; Scott, Brian L; Baker, R Tom

    2009-01-01

    The development of alternatives to current petroleum-based fuels and chemicals is becoming increasingly important due to concerns over climate change, growing world energy demand, and energy security issues. Using non-food derived biomass to produce renewable feedstocks for chemicals and fuels is a particularly attractive possibility. However, the majority of biomass is in the form of lignocellulose, which is often not fully utilized due to difficulties associated with breaking down both lignin and cellulose. Recently, a number of methods have been reported to transform cellulose directly into more valuable materials such as glucose, sorbitol, 5-(chloromethyl)furfural, and ethylene glycol. Less progress has been made with selective transformations of lignin, which is typically treated in paper and forest industries by kraft pulping (sodium hydroxide/sodium sulfide) or incineration. Our group has begun investigating aerobic oxidative C-C bond cleavage catalyzed by dipicolinate vanadium complexes, with the idea that a selective C-C cleavage reaction of this type could be used to produce valuable chemicals or intermediates from cellulose or lignin. Lignin is a randomized polymer containing methoxylated phenoxy propanol units. A number of different linkages occur naturally; one of the most prevalent is the {beta}-O-4 linkage shown in Figure 1, containing a C-C bond with 1,2-hydroxy ether substituents. While the oxidative C-C bond cleavage of 1,2-diols has been reported for a number of metals, including vanadium, iron, manganese, ruthenium, and polyoxometalate complexes, C-C bond cleavage of 1,2-hydroxy ethers is much less common. We report herein vanadium-mediated cleavage of C-C bonds between alcohol and ether functionalities in several lignin model complexes. In order to explore the scope and potential of vanadium complexes to effect oxidative C-C bond cleavage in 1,2-hydroxy ethers, we examined the reactivity of the lignin model complexes pinacol monomethyl ether (A

  6. CH Packaging Operations for High Wattage Waste at LANL

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2003-05-06

    This procedure provides instructions for assembling the following contact-handled (CH) packaging payloads: - Drum payload assembly - Standard Waste Box (SWB) assembly - Ten-Drum Overpack (TDOP) In addition, this procedure also provides operating instructions for the TRUPACT-II CH waste packaging. This document also provides instructions for performing ICV and OCV preshipment leakage rate tests on the following packaging seals, using a nondestructive helium (He) leak test: - ICV upper main O-ring seal - ICV outer vent port plug O-ring seal - OCV upper main O-ring seal - OCV vent port plug O-ring seal.

  7. CH Packaging Operations for High Wattage Waste at LANL

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2003-08-28

    This procedure provides instructions for assembling the following contact-handled (CH) packaging payloads: - Drum payload assembly - Standard Waste Box (SWB) assembly - Ten-Drum Overpack (TDOP) In addition, this procedure also provides operating instructions for the TRUPACT-II CH waste packaging. This document also provides instructions for performing ICV and OCV preshipment leakage rate tests on the following packaging seals, using a nondestructive helium (He) leak test: - ICV upper main O-ring seal - ICV outer vent port plug O-ring seal - OCV upper main O-ring seal - OCV vent port plug O-ring seal.

  8. CH Packaging Operations for High Wattage Waste at LANL

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2003-03-21

    This procedure provides instructions for assembling the following contact-handled (CH) packaging payloads: - Drum payload assembly - Standard Waste Box (SWB) assembly - Ten-Drum Overpack (TDOP) In addition, this procedure also provides operating instructions for the TRUPACT-II CH waste packaging. This document also provides instructions for performing ICV and OCV preshipment leakage rate tests on the following packaging seals, using a nondestructive helium (He) leak test: - ICV upper main O-ring seal - ICV outer vent port plug O-ring seal - OCV upper main O-ring seal - OCV vent port plug O-ring seal.

  9. CH Packaging Operations for High Wattage Waste at LANL

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2002-10-17

    This procedure provides instructions for assembling the following contact-handled (CH) packaging payloads: - Drum payload assembly - Standard Waste Box (SWB) assembly - Ten-Drum Overpack (TDOP) In addition, this procedure provides operating instructions for the TRUPACT-II CH waste packaging. This document also provides instructions for performing ICV and OCV preshipment leakage rate tests on the following packaging seals, using a nondestructive helium (He) leak test: - ICV upper main O-ring seal - ICV outer vent port plug O-ring seal - OCV upper main O-ring seal - OCV vent port plug O-ring seal.

  10. CH Packaging Operations for High Wattage Waste at LANL

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2002-12-18

    This procedure provides instructions for assembling the following contact-handled (CH) packaging payloads: - Drum payload assembly - Standard Waste Box (SWB) assembly - Ten-Drum Overpack (TDOP) In addition, this procedure also provides operating instructions for the TRUPACT-II CH waste packaging. This document also provides instructions for performing ICV and OCV preshipment leakage rate tests on the following packaging seals, using a nondestructive helium (He) leak test: - ICV upper main O-ring seal - ICV outer vent port plug O-ring seal - OCV upper main O-ring seal - OCV vent port plug O-ring seal.

  11. Contract No. DE-AC02-07CH11358

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Contract No. DE-AC02-07CH11358 Modification No. 0171 Section B i PART I SECTION B SUPPLIES OR SERVICES AND PRICES/COSTS TABLE OF CONTENTS PAGE NO. B.1 - SERVICE BEING ACQUIRED B-1 B.2 - OBLIGATION OF FUNDS AND FINANCIAL LIMITATIONS B-1 B.3 - PERFORMANCE AND OTHER INCENTIVE FEES B-1 B.4 - ALLOWABILITY OF SUBCONTRACTOR FEE B-3 B.5 - PROVISIONAL PAYMENT OF PERFORMANCE FEE B-3 Contract No. DE-AC02-07CH11358 Modification No. 0171 Section B B-1 PART I SECTION B - SUPPLIES OR SERVICES AND PRICES/COSTS

  12. Structural basis of stereospecificity in the bacterial enzymatic cleavage of β-aryl ether bonds in lignin

    SciTech Connect (OSTI)

    Helmich, Kate E.; Pereira, Jose Henrique; Gall, Daniel L.; Heins, Richard A.; McAndrew, Ryan P.; Bingman, Craig; Deng, Kai; Holland, Keefe C.; Noguera, Daniel R.; Simmons, Blake A.; Sale, Kenneth L.; Ralph, John; Donohue, Timothy J.; Adams, Paul D.; Phillips, George N.

    2015-12-04

    Here, lignin is a combinatorial polymer comprising monoaromatic units that are linked via covalent bonds. Although lignin is a potential source of valuable aromatic chemicals, its recalcitrance to chemical or biological digestion presents major obstacles to both the production of second-generation biofuels and the generation of valuable coproducts from lignin's monoaromatic units. Degradation of lignin has been relatively well characterized in fungi, but it is less well understood in bacteria. A catabolic pathway for the enzymatic breakdown of aromatic oligomers linked via β-aryl ether bonds typically found in lignin has been reported in the bacterium Sphingobium sp. SYK-6. Here, we present x-ray crystal structures and biochemical characterization of the glutathione-dependent β-etherases, LigE and LigF, from this pathway. The crystal structures show that both enzymes belong to the canonical two-domain fold and glutathione binding site architecture of the glutathione S-transferase family. Mutagenesis of the conserved active site serine in both LigE and LigF shows that, whereas the enzymatic activity is reduced, this amino acid side chain is not absolutely essential for catalysis. The results include descriptions of cofactor binding sites, substrate binding sites, and catalytic mechanisms. Because β-aryl ether bonds account for 50–70% of all interunit linkages in lignin, understanding the mechanism of enzymatic β-aryl ether cleavage has significant potential for informing ongoing studies on the valorization of lignin.

  13. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas. Final technical report

    SciTech Connect (OSTI)

    Not Available

    1993-02-01

    Through the mid-1980s, Air Products has brought the liquid phase approach to a number of other synthesis gas reactions where effective heat management is a key issue. In 1989, in response to DOE`s PRDA No. DE-RA22-88PC88805, Air Products proposed a research and development program entitled ``Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal Derived Syngas.`` The proposal aimed at extending the LPMEOH experience to convert coal-derived synthesis gas to other useful fuels and chemicals. The work proposed included development of a novel one-step synthesis of dimethyl ether (DME) from syngas, and exploration of other liquid phase synthesis of alternative fuel directly from syngas. The one-step DME process, conceived in 1986 at Air Products as a means of increasing syngas conversion to liquid products, envisioned the concept of converting product methanol in situ to DME in a single reactor. The slurry reactor based liquid phase technology is ideally suited for such an application, since the second reaction (methanol to DME) can be accomplished by adding a second catalyst with dehydration activity to the methanol producing reactor. An area of exploration for other alternative fuels directly from syngas was single-step slurry phase synthesis of hydrocarbons via methanol and DME as intermediates. Other possibilities included the direct synthesis of mixed alcohols and mixed ethers in a slurry reactor.

  14. Structural basis of stereospecificity in the bacterial enzymatic cleavage of β-aryl ether bonds in lignin

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Helmich, Kate E.; Pereira, Jose Henrique; Gall, Daniel L.; Heins, Richard A.; McAndrew, Ryan P.; Bingman, Craig; Deng, Kai; Holland, Keefe C.; Noguera, Daniel R.; Simmons, Blake A.; et al

    2015-12-04

    Here, lignin is a combinatorial polymer comprising monoaromatic units that are linked via covalent bonds. Although lignin is a potential source of valuable aromatic chemicals, its recalcitrance to chemical or biological digestion presents major obstacles to both the production of second-generation biofuels and the generation of valuable coproducts from lignin's monoaromatic units. Degradation of lignin has been relatively well characterized in fungi, but it is less well understood in bacteria. A catabolic pathway for the enzymatic breakdown of aromatic oligomers linked via β-aryl ether bonds typically found in lignin has been reported in the bacterium Sphingobium sp. SYK-6. Here, wemore » present x-ray crystal structures and biochemical characterization of the glutathione-dependent β-etherases, LigE and LigF, from this pathway. The crystal structures show that both enzymes belong to the canonical two-domain fold and glutathione binding site architecture of the glutathione S-transferase family. Mutagenesis of the conserved active site serine in both LigE and LigF shows that, whereas the enzymatic activity is reduced, this amino acid side chain is not absolutely essential for catalysis. The results include descriptions of cofactor binding sites, substrate binding sites, and catalytic mechanisms. Because β-aryl ether bonds account for 50–70% of all interunit linkages in lignin, understanding the mechanism of enzymatic β-aryl ether cleavage has significant potential for informing ongoing studies on the valorization of lignin.« less

  15. THE SEARCH FOR A COMPLEX MOLECULE IN A SELECTED HOT CORE REGION: A RIGOROUS ATTEMPT TO CONFIRM TRANS-ETHYL METHYL ETHER TOWARD W51 e1/e2

    SciTech Connect (OSTI)

    Carroll, P. Brandon; McGuire, Brett A.; Blake, Geoffrey A.; Apponi, A. J.; Ziurys, L. M.; Remijan, Anthony

    2015-01-20

    An extensive search has been conducted to confirm transitions of trans-ethyl methyl ether (tEME, C{sub 2}H{sub 5}OCH{sub 3}), toward the high-mass star forming region W51 e1/e2 using the 12 m Telescope of the Arizona Radio Observatory at wavelengths from 2 mm and 3 mm. In short, we cannot confirm the detection of tEME toward W51 e1/e2 and our results call into question the initial identification of this species by Fuchs et al. Additionally, re-evaluation of the data from the original detection indicates that tEME is not present toward W51 e1/e2 in the abundance reported by Fuchs and colleagues. Typical peak-to-peak noise levels for the present observations of W51 e1/e2 were between 10 and 30 mK, yielding an upper limit of the tEME column density of ≤1.5 × 10{sup 15} cm{sup –2}. This would make tEME at least a factor of two times less abundant than dimethyl ether (CH{sub 3}OCH{sub 3}) toward W51 e1/e2. We also performed an extensive search for this species toward the high-mass star forming region Sgr B2(N-LMH) with the National Radio Astronomy Observatory 100 m Green Bank Telescope. No transitions of tEME were detected and we were able to set an upper limit to the tEME column density of ≤4 × 10{sup 14} cm{sup –2} toward this source. Thus, we are able to show that tEME is not a new molecular component of the interstellar medium and that an exacting assessment must be carried out when assigning transitions of new molecular species to astronomical spectra to support the identification of large organic interstellar molecules.

  16. Direct Numerical Simulations of Autoignition in Stratified Dimethyl-ether (DME)/Air Turbulent Mixtures

    SciTech Connect (OSTI)

    Bansal, Gaurav; Mascarenhas, Ajith; Chen, Jacqueline H.

    2014-10-01

    In our paper, two- and three-dimensional direct numerical simulations (DNS) of autoignition phenomena in stratified dimethyl-ether (DME)/air turbulent mixtures are performed. A reduced DME oxidation mechanism, which was obtained using rigorous mathematical reduction and stiffness removal procedure from a detailed DME mechanism with 55 species, is used in the present DNS. The reduced DME mechanism consists of 30 chemical species. This study investigates the fundamental aspects of turbulence-mixing-autoignition interaction occurring in homogeneous charge compression ignition (HCCI) engine environments. A homogeneous isotropic turbulence spectrum is used to initialize the velocity field in the domain. Moreover, the computational configuration corresponds to a constant volume combustion vessel with inert mass source terms added to the governing equations to mimic the pressure rise due to piston motion, as present in practical engines. DME autoignition is found to be a complex three-staged process; each stage corresponds to a distinct chemical kinetic pathway. The distinct role of turbulence and reaction in generating scalar gradients and hence promoting molecular transport processes are investigated. Then, by applying numerical diagnostic techniques, the different heat release modes present in the igniting mixture are identified. In particular, the contribution of homogeneous autoignition, spontaneous ignition front propagation, and premixed deflagration towards the total heat release are quantified.

  17. Direct Numerical Simulations of Autoignition in Stratified Dimethyl-ether (DME)/Air Turbulent Mixtures

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bansal, Gaurav; Mascarenhas, Ajith; Chen, Jacqueline H.

    2014-10-01

    In our paper, two- and three-dimensional direct numerical simulations (DNS) of autoignition phenomena in stratified dimethyl-ether (DME)/air turbulent mixtures are performed. A reduced DME oxidation mechanism, which was obtained using rigorous mathematical reduction and stiffness removal procedure from a detailed DME mechanism with 55 species, is used in the present DNS. The reduced DME mechanism consists of 30 chemical species. This study investigates the fundamental aspects of turbulence-mixing-autoignition interaction occurring in homogeneous charge compression ignition (HCCI) engine environments. A homogeneous isotropic turbulence spectrum is used to initialize the velocity field in the domain. Moreover, the computational configuration corresponds to amore » constant volume combustion vessel with inert mass source terms added to the governing equations to mimic the pressure rise due to piston motion, as present in practical engines. DME autoignition is found to be a complex three-staged process; each stage corresponds to a distinct chemical kinetic pathway. The distinct role of turbulence and reaction in generating scalar gradients and hence promoting molecular transport processes are investigated. Then, by applying numerical diagnostic techniques, the different heat release modes present in the igniting mixture are identified. In particular, the contribution of homogeneous autoignition, spontaneous ignition front propagation, and premixed deflagration towards the total heat release are quantified.« less

  18. New clean fuel from coal -- Direct dimethyl ether synthesis from hydrogen and carbon monoxide

    SciTech Connect (OSTI)

    Ogawa, T.; Ono, M.; Mizuguchi, M.; Tomura, K.; Shikada, T.; Ohono, Y.; Fujimoto, K.

    1997-12-31

    Dimethyl ether (DME), which has similar physical properties to propane and is easily liquefied at low pressure, has a significant possibility as a clean and non-toxic fuel from coal or coal bed methane. Equilibrium calculation also shows a big advantage of high carbon monoxide conversion of DME synthesis compared to methanol synthesis. By using a 50 kg/day DME bench scale test plant, direct synthesis of DME from hydrogen and carbon monoxide has been studied with newly developed catalysts which are very fine particles. This test plant features a high pressure three-phase slurry reactor and low temperature DME separator. DME is synthesized at temperatures around 533--553 K and at pressures around 3--5 MPa. According to the reaction stoichiometry, the same amount of hydrogen and carbon monoxide react to DME and carbon dioxide. Carbon conversion to DME is one third and the rest of carbon is converted to carbon dioxide. As a result of the experiments, make-up CO conversion is 35--50% on an once-through basis, which is extremely high compared to that of methanol synthesis from hydrogen and carbon monoxide. DME selectivity is around 60 c-mol %. Most of the by-product is CO{sub 2} with a small amount of methanol and water. No heavy by-products have been recognized. Effluent from the reactor is finally cooled to 233--253 K in a DME separator and liquid DME is recovered as a product.

  19. Experimental and Computational Study of Nonpremixed Ignition of Dimethyl Ether in Counterflow

    SciTech Connect (OSTI)

    Zheng, X L; Lu, T F; Law, C K; Westbrook, C K

    2003-12-19

    The ignition temperature of nitrogen-diluted dimethyl ether (DME) by heated air in counterflow was experimentally determined for DME concentration from 5.9 to 30%, system pressure from 1.5 to 3.0 atmospheres, and pressure-weighted strain rate from 110 to 170/s. These experimental data were compared with two mechanisms that were respectively available in 1998 and 2003, with the latter being a substantially updated version of the former. The comparison showed that while the 1998-mechanism uniformly over-predicted the ignition temperature, the 2003-mechanism yielded surprisingly close agreement for all experimental data. Sensitivity analysis for the near-ignition state based on both mechanisms identified the deficiencies of the 1998-mechanism, particularly the specifics of the low-temperature cool flame chemistry in effecting ignition at higher temperatures, as the fuel stream is being progressively heated from its cold boundary to the high-temperature ignition region around the hot-stream boundary. The 2003-mechanism, consisting of 79 species and 398 elementary reactions, was then systematically simplified by using the directed relation graph method to a skeletal mechanism of 49 species and 251 elementary reactions, which in turn was further simplified by using computational singular perturbation method and quasi-steady-state species assumption to a reduced mechanism consisting of 33 species and 28 lumped reactions. It was demonstrated that both the skeletal and reduced mechanisms mimicked the performance of the detailed mechanism with high accuracy.

  20. Slurry phase synthesis of dimethyl ether from syngas -- A reactor model simulation

    SciTech Connect (OSTI)

    Mizuguchi, Masatsugu; Ogawa, Takashi; Ono, Masami,; Tomura, Keiji; Shikada, Tsutomu; Ohno, Yotaro; Fujimoto, Kaoru

    1998-12-31

    Dimethyl ether (DME) would be an attractive alternative fuel for diesel, domestic use, and power generation, if it is economically synthesized directly from syngas (derived from coal gasification or natural gas reforming). DME, which is a colorless gas with a boiling point of {minus}25 C, is chemically stable and easily liquefied under pressure. Since the properties of DME are similar to LPG, it can be handled and stored with the same manner as LPG. The authors have performed the slurry phase DME synthesis by using the 50 kg/day bench-scale unit. DME was synthesized at high yield from syngas (H{sub 2}+CO) with the newly developed catalyst system. To establish the scale-up methodology, the reactor simulation technique is essential. The authors developed a mathematical model of the slurry phase bubble column reactor for DME synthesis, which is based on their experimental results. The performance of a commercial-scale DME reactor was simulated by this model, and the results were discussed.

  1. Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

    SciTech Connect (OSTI)

    Marin, T.; Shkrob, I.; Dietz, M.

    2011-04-14

    Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between different clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.

  2. A fluorescence-based method for rapid and direct determination of polybrominated diphenyl ethers in water

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Shan, Huimei; Liu, Chongxuan; Wang, Zheming; Ma, Teng; Shang, Jianying; Pan, Duoqiang

    2015-01-01

    A new method was developed for rapid and direct measurement of polybrominated diphenyl ethers (PBDEs) in aqueous samples using fluorescence spectroscopy. The fluorescence spectra of tri- to deca-BDE (BDE 28, 47, 99, 153, 190, and 209) commonly found in environment were measured at variable emission and excitation wavelengths. The results revealed that the PBDEs have distinct fluorescence spectral profiles and peak positions that can be exploited to identify these species and determine their concentrations in aqueous solutions. The detection limits as determined in deionized water spiked with PBDEs are 1.71-5.82 ng/L for BDE 28, BDE 47, BDE 190, and BDEmore » 209 and 45.55–69.95 ng/L for BDE 99 and BDE 153. The effects of environmental variables including pH, humic substance, and groundwater chemical composition on PBDEs measurements were also investigated. These environmental variables affected fluorescence intensity, but their effect can be corrected through linear additivity and separation of spectral signal contribution. Compared with conventional GC-based analytical methods, the fluorescence spectroscopy method is more efficient as it only uses a small amount of samples (2-4 mL), avoids lengthy complicated concentration and extraction steps, and has a low detection limit of a few ng/L.« less

  3. Electron momentum spectroscopy of dimethyl ether taking account of nuclear dynamics in the electronic ground state

    SciTech Connect (OSTI)

    Morini, Filippo; Deleuze, Michael Simon; Watanabe, Noboru; Kojima, Masataka; Takahashi, Masahiko

    2015-10-07

    The influence of nuclear dynamics in the electronic ground state on the (e,2e) momentum profiles of dimethyl ether has been analyzed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of fundamental methodological differences, results obtained with both approaches consistently demonstrate that molecular vibrations in the electronic ground state have a most appreciable influence on the momentum profiles associated to the 2b{sub 1}, 6a{sub 1}, 4b{sub 2}, and 1a{sub 2} orbitals. Taking this influence into account considerably improves the agreement between theoretical and newly obtained experimental momentum profiles, with improved statistical accuracy. Both approaches point out in particular the most appreciable role which is played by a few specific molecular vibrations of A{sub 1}, B{sub 1}, and B{sub 2} symmetries, which correspond to C–H stretching and H–C–H bending modes. In line with the Herzberg-Teller principle, the influence of these molecular vibrations on the computed momentum profiles can be unraveled from considerations on the symmetry characteristics of orbitals and their energy spacing.

  4. A fluorescence-based method for rapid and direct determination of polybrominated diphenyl ethers in water

    SciTech Connect (OSTI)

    Shan, Huimei; Liu, Chongxuan; Wang, Zheming; Ma, Teng; Shang, Jianying; Pan, Duoqiang

    2015-01-01

    A new method was developed for rapid and direct measurement of polybrominated diphenyl ethers (PBDEs) in aqueous samples using fluorescence spectroscopy. The fluorescence spectra of tri- to deca-BDE (BDE 28, 47, 99, 153, 190, and 209) commonly found in environment were measured at variable emission and excitation wavelengths. The results revealed that the PBDEs have distinct fluorescence spectral profiles and peak positions that can be exploited to identify these species and determine their concentrations in aqueous solutions. The detection limits as determined in deionized water spiked with PBDEs are 1.71-5.82 ng/L for BDE 28, BDE 47, BDE 190, and BDE 209 and 45.5569.95 ng/L for BDE 99 and BDE 153. The effects of environmental variables including pH, humic substance, and groundwater chemical composition on PBDEs measurements were also investigated. These environmental variables affected fluorescence intensity, but their effect can be corrected through linear additivity and separation of spectral signal contribution. Compared with conventional GC-based analytical methods, the fluorescence spectroscopy method is more efficient as it only uses a small amount of samples (2-4 mL), avoids lengthy complicated concentration and extraction steps, and has a low detection limit of a few ng/L.

  5. Equilibria and dissociation kinetics of lanthanide complexes of diaza crown ether carboxylic acids

    SciTech Connect (OSTI)

    Chang, C.A.; Chang, P.H.L.; Manchanda, V.K.; Kasprzyk, S.P.

    1988-10-19

    The equilibria and dissociation kinetics of lanthanide and several transition-metal and Pb(II) complexes of some diaza crown ether carboxylic acids are studied. The ligands are K22MA (1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N-acetic acid), K22DP (1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-di-..beta..-propionic acid), and K22MP (1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N-..beta..-propionic acid). The protonation constants of these ligands are similar to those of the structural analogues and are in the range log K/sub 1/ = 8.80-9.01 and log K/sub 2/ = 7.26-8.16. The stability constants are all lower than that of their structural analogue K22DA (1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid) due to the reduction of the chelate effect or an unfavorable steric effect or both. The kinetic dissociation rates are all faster as compared to those of K22DA complexes. Acid-dependent (k/sub H/) and acid-independent (k/sub d/) rate constants are obtained by the measurement of rates at various pH values, and they correlate inversely with the values of stability constants. 15 references, 1 figure, 4 tables.

  6. Electronic structure, transport, and phonons of SrAgChF (Ch = S,Se,Te): Bulk superlattice thermoelectrics

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Gudelli, Vijay Kumar; Kanchana, V.; Vaitheeswaran, G.; Singh, David J.; Svane, Axel; Christensen, Niels Egede; Mahanti, Subhendra D.

    2015-07-15

    Here, we report calculations of the electronic structure, vibrational properties, and transport for the p-type semiconductors, SrAgChF (Ch = S, Se, and Te). We find soft phonons with low frequency optical branches intersecting the acoustic modes below 50 cm–1, indicative of a material with low thermal conductivity. The bands at and near the valence-band maxima are highly two-dimensional, which leads to high thermopowers even at high carrier concentrations, which is a combination that suggests good thermoelectric performance. These materials may be regarded as bulk realizations of superlattice thermoelectrics.

  7. Preliminary Notice of Violation, CH2M-Washington Group Idaho...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    M-Washington Group Idaho, LLC - EA-2007-03 Preliminary Notice of Violation, CH2M-Washington Group Idaho, LLC - EA-2007-03 June 14, 2007 Issued to CH2M-Washington Group Idaho, LLC,...

  8. Selectivity of Chemisorbed Oxygen in C-H Bond Activation and...

    Office of Scientific and Technical Information (OSTI)

    Selectivity of Chemisorbed Oxygen in C-H Bond Activation and CO Oxidation and Kinetic ... Title: Selectivity of Chemisorbed Oxygen in C-H Bond Activation and CO Oxidation and ...

  9. Letter from DOE to URS | CH2M Oak Ridge LLC on Award Fee Determination...

    Office of Environmental Management (EM)

    DOE to URS | CH2M Oak Ridge LLC on Award Fee Determination for April to September 2015 Letter from DOE to URS | CH2M Oak Ridge LLC on Award Fee Determination for April to September ...

  10. Hydrogen for X-group exchange in CH3X, X = Cl, Br, I, OMe and...

    Office of Scientific and Technical Information (OSTI)

    Hydrogen for X-group exchange in CH3X, X Cl, Br, I, OMe and NMe2 byMonomeric ... Citation Details In-Document Search Title: Hydrogen for X-group exchange in CH3X, X Cl, ...

  11. DOE Selects CH2M Hill Plateau Remediation Company for Plateau...

    Office of Environmental Management (EM)

    CH2M Hill Plateau Remediation Company for Plateau Remediation Contract at its Hanford Site DOE Selects CH2M Hill Plateau Remediation Company for Plateau Remediation Contract at its ...

  12. Enforcement Letter, CH2M Hill Hanford Group, Inc - July 8, 2005...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Inc - July 8, 2005 Enforcement Letter, CH2M Hill Hanford Group, Inc - July 8, 2005 July 8, 2005 Issued to CH2M Hill Hanford Group, Inc., related to Neutron Exposure at the Hanford...

  13. Preliminary Notice of Violation, CH2M Hill Hanford Group, Inc...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Preliminary Notice of Violation, CH2M Hill Hanford Group, Inc. - EA-2006-06 November 16, 2006 Issued to CH2M Hill Hanford Group, Inc., related to Radiological Contamination Events ...

  14. Independent Activity Report, CH2M Hill Plateau Remediation Company- January 2011

    Broader source: Energy.gov [DOE]

    Review of the CH2M Hill Plateau Remediation Company Unreviewed Safety Question Procedure [ARPT-RL-2011-003

  15. Preliminary Notice of Violation, CH2M Hill Hanford Group, Inc- EA-2005-01

    Broader source: Energy.gov [DOE]

    Issued to CH2M Hill Hanford Group, Inc., related to Radiological and Operational Events at the Hanford Tank Farms

  16. Enforcement Letter, CH2M Hill Hanford Group Inc,- September 6, 2007

    Broader source: Energy.gov [DOE]

    Issued to CH2M Hill Hanford Group, Inc., related to Quality Improvement Deficiencies at the Hanford Tank Farms

  17. Enforcement Letter, CH2M Hill Hanford Group, Inc.- April 24, 2001

    Broader source: Energy.gov [DOE]

    Issued to CH2M Hill Hanford Group, Inc., related to Nuclear Safety Management at the Hanford Site Tank Farms

  18. ULEV potential of a DI/TCI diesel passenger car engine operated on dimethyl ether

    SciTech Connect (OSTI)

    Kapus, P.E.; Cartellieri, W.P.

    1995-12-31

    This paper describes a feasibility test program on a 2 liter, 4 cylinder DI/TCI passenger car engine operated on the new alternative fuel Dimethyl Ether (DME) with the aim of demonstrating its potential of meeting ULEV (ultra low emission vehicle) emissions (0.2 g/mi NOx in the FTP 75 test cycle) when installed in a full size passenger car. Special attention is drawn to the fuel injection equipment (FIE) as well as combustion system requirements towards the reduction of NOx and combustion noise while keeping energetic fuel consumption at the level of he baseline DI/TCI diesel engine. FIE and combustion system parameters were optimized on the steady state dynamometer by variation of a number of parameters, such as rate of injection, number of nozzle holes, compression ratio, piston bowl shape and exhaust gas recirculation. The paper presents engine test results achieved with DME under various operating conditions and compares these results to those achieved with the diesel version of the same engine.The FTP 75 cycle results were projected from steady state engine maps using a vehicle simulation program taking into account vehicle data and road resistance data of a given vehicle.The cycle results are also compared to actual chassis dynamometer results achieved with the diesel version of the same engine installed in the same vehicle.the passenger car DI/TCI engine adapted for and operated on DME shows very promising results with respect to meeting ULEV NOx emissions without any soot emissions and without the need for a DENOX catalyst. DME fuel consumption on energy basis can be kept very close to the DI diesel value. An oxidation catalyst will be necessary to meet the stringent CO and HC ULEV emission limits.

  19. Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization

    SciTech Connect (OSTI)

    Sturgeon, M. R.; Kim, S.; Chmely, S. C.; Foust, T. D.; Beckham, G. T.

    2013-01-01

    Carbon-oxygen bonds are the primary inter-monomer linkages lignin polymers in plant cell walls, and as such, catalyst development to cleave these linkages is of paramount importance to deconstruct biomass to its constituent monomers for the production of renewable fuels and chemicals. For many decades, acid catalysis has been used to depolymerize lignin. Lignin is a primary component of plant cell walls, which is connected primarily by aryl-ether linkages, and the mechanism of its deconstruction by acid is not well understood, likely due to its heterogeneous and complex nature compared to cellulose. For effective biomass conversion strategies, utilization of lignin is of significant relevance and as such understanding the mechanisms of catalytic lignin deconstruction to constituent monomers and oligomers is of keen interest. Here, we present a comprehensive experimental and theoretical study of the acid catalysis of a range of dimeric species exhibiting the b-O-4 linkage, the most common inter-monomer linkage in lignin. We demonstrate that the presence of a phenolic species dramatically increases the rate of cleavage in acid at 150 degrees C. Quantum mechanical calculations on dimers with the para-hydroxyl group demonstrate that this acid-catalyzed pathway differs from the nonphenolic dimmers. Importantly, this result implies that depolymerization of native lignin in the plant cell wall will proceed via an unzipping mechanism wherein b-O-4 linkages will be cleaved from the ends of the branched, polymer chains inwards toward the center of the polymer. To test this hypothesis further, we synthesized a homopolymer of b-O-4 with a phenolic hydroxyl group, and demonstrate that it is cleaved in acid from the end containing the phenolic hydroxyl group. This result suggests that genetic modifications to lignin biosynthesis pathways in plants that will enable lower severity processes to fractionate lignin for upgrading and for easier access to the carbohydrate fraction of

  20. This Week In Petroleum Printer-Friendly Version

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    this transition from Methyl Tertiary Butyl Ether (MTBE) reformulated gasoline (RFG) to ethanol RFG, since ethanol is not blended into the gasoline mixture until just before the...

  1. 1

    Office of Environmental Management (EM)

    Xylene, Ethyl acetate, Ethyl benzene, Ethyl ether, n-Butyl alcohol, Cyclohexanone, Methanol, Cresols, Cresylic acid, Nitroobenzene, Carbon disulfide, Isobutanol, Pyridine, 2-...

  2. Impact of Renewable Fuels Standard/MTBE Provisions of S. 517 Requested by Sens. Daschle & Murkowski

    Reports and Publications (EIA)

    2002-01-01

    Additional analysis of the impact of the Renewable Fuels Standard (RFS) and methyl tertiary butyl ether (MTBE) ban provisions of S. 517.

  3. Total Blender Net Input of Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    Normal Butane Isobutane Other Liquids OxygenatesRenewables Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) All Other Oxygenates Renewable Fuels (incl. Fuel Ethanol...

  4. Refinery Stocks of Crude Oil and Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    Hydrocarbons Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) All Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Renewable Diesel Fuel Other ...

  5. Motor Gasoline Market Spring 2007 and Implications for Spring...

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    began to decline, and with the transition from methyl tertiary butyl ether (MTBE) to ethanol completed and the end of the summer driving season drawing near, gasoline prices...

  6. untitled

    Gasoline and Diesel Fuel Update (EIA)

    of "other" hydrocarbons and oxygenates include hydrogen and oxygenates especially fuel ethanol and methyl tertiary butyl ether (MTBE). The adjustment is equal to the...

  7. Ligand-Thickness Effect Leads to Enhanced Preference for Large Anions in Alkali Metal Extraction by Crown Ethers

    SciTech Connect (OSTI)

    Haverlock, T.J.; Moyer, B.A.; Sachleben, R.A.

    1999-07-11

    Jean-Marie Lehn (Nobel laureate, 1987) suggested ligand thickness to be an important consideration in the design of host molecules for cation recognition. We have recently expanded the role of this simple ligand property by demonstrating a case in which ligand thickness contributes significantly to anion discrimination. It was found that in the extraction of sodium nitrate and perchlorate by a simple crown ether, bis(t-octylbenzo)-14-crown-4 (BOB 14C4), the normal preference for perchlorate is almost completely lost when the complex cation has the open-face sandwich vs. the sandwich structure.

  8. SYNTHESIS OF NOVEL CROWN ETHERS BEARING THE exo-cis-2,3-NORBORNYL GROUP AS POTENTIAL Na+ AND K+ EXTRACTANTS

    SciTech Connect (OSTI)

    Robeson, R.M.; Bonnesen, P.

    2007-01-01

    The synthesis of a series of novel dinorbornyl-16-crown-5 and dinorbornyl-18-crown-6 ethers that incorporate the exo-cis-2,3-norbornyl moiety within the macrocycle framework is described. The key starting material for the crown ethers, exo-cis-2,3-norbornanediol, was successfully prepared on a large (>30g) scale in 88% yield from norbornylene by osmium tetroxide-catalyzed hydroxylation. The syn and anti isomers of the dinorbornyl-16-crown-5 ether family were prepared using diethylene glycol with ring closure achieved using a methallyl linkage. The isomers cis-syn-cis and cis-anti-cis di-norbornano-15-methyleno-16-crown-5 (6A and 6B) could be separated using column chromatography, and a single crystal of the syn isomer 6A suitable for X-ray crystal structure analysis was obtained, thereby confi rming the syn orientation. The syn and anti isomers of the dinorbornyl-18-crown-6 ether family were successfully prepared employing a different synthetic strategy, involving the potassium–templated cyclization of two bis-hydroxyethoxy-substituted exo-cis-2,3-norbornyl groups under high dilution conditions. Attempts to fully separate cis-syn-cis di-norbornano-18-crown-6 (10A) and cis-anti-cis di-norbornano-18-crown-6 (10B) from one another using column chromatography were unsuccessful. All intermediates and products were checked for purity using either thin layer chromatography or gas chromatography, and characterized by proton and carbon NMR. Crown ethers 6AB and 10AB are to our knowledge the fi rst crown ethers to incorporate the exo-cis-2,3-norbornyl moiety into the crown ring to be successfully synthesized and characterized.

  9. Decomposition and vibrational relaxation in CH{sub 3}I and self-reaction of CH{sub 3} radicals.

    SciTech Connect (OSTI)

    Yang, X.; Goldsmith, C. F.; Tranter, R. S.

    2009-07-01

    Vibrational relaxation and dissociation of CH{sub 3}I, 2-20% in krypton, have been investigated behind incident shock waves in a diaphragmless shock tube at 20, 66, 148, and 280 Torr and 630-2200 K by laser schlieren densitometry. The effective collision energy obtained from the vibrational relaxation experiments has a small, positive temperature dependence, {Delta}E{sub down} = 63 x (T/298){sup 0.56} cm{sup -1}. First-order rate coefficients for dissociation of CH{sub 3}I show a strong pressure dependence and are close to the low-pressure limit. Restricted-rotor Gorin model RRKM calculations fit the experimental results very well with {Delta}E{sub down} = 378 x (T/298){sup 0.457} cm{sup -1}. The secondary chemistry of this reaction system is dominated by reactions of methyl radicals and the reaction of the H atom with CH{sub 3}I. The results of the decomposition experiments are very well simulated with a model that incorporates methyl recombination and reactions of methylene. Second-order rate coefficients for ethane dissociation to two methyl radicals were derived from the experiments and yield k = (4.50 {+-} 0.50) x 10{sup 17} exp(-32709/T) cm{sup 3} mol{sup -1} s{sup -1}, in good agreement with previous measurements. Rate coefficients for H + CH{sub 3}I were also obtained and give k = (7.50 {+-} 1.0) x 10{sup 13} exp(-601/T) cm{sup 3} mol{sup -1} s{sup -1}, in reasonable agreement with a previous experimental value.

  10. Coupling of alcohols to ethers: The dominance of the surface S{sub N}2 reaction pathway

    SciTech Connect (OSTI)

    Klier, K.; Feeley, O.C.; Johansson, M.; Herman, R.G.

    1996-12-31

    Coupling of alcohols to ethers, important high value oxygenates, proceeds on acid catalysts via general pathways that uniquely control product composition, oxygen retention, chirality inversion, and kinetics. The dominant pathway is the S{sub N}2 reaction with competition of the alcohols for the surface acid sites. This is exemplified by formation of methyl(ethyl) isobutylether (M(E)IBE) from methanol(ethanol)/isobutanol mixtures, retention of oxygen ({sup 18}O) of the heavier alcohol, and optimum rate as a function of concentration of either reactant alcohol. The S{sub N}2 pathway in the confinement of zeolite pores exhibits additional features of a near-100% selectivity to dimethylether (DME) in H-mordenite and a near-100% selectivity to chiral inversion in 2-pentanol/ethanol coupling to 2-ethoxypentane in HZSM-5. A minor reaction pathway entails olefin or carbenium intermediates, as exemplified by the formation of methyl tertiarybutyl ether (MTBE) from methanol/isobutanol mixtures with oxygen retention of the lighter alcohol. Calculations of transition state and molecular modeling of the oxonium-involving pathways dramatically demonstrate how the reaction path selects the products.

  11. SAPO-34 Membranes for N-2/CH4 separation: Preparation, characterization, separation performance and economic evaluation

    SciTech Connect (OSTI)

    Li, SG; Zong, ZW; Zhou, SJ; Huang, Y; Song, ZN; Feng, XH; Zhou, RF; Meyer, HS; Yu, M; Carreon, MA

    2015-08-01

    SAPO-34 membranes were synthesized by several routes towards N-2/CH4 separation. Membrane synthesis parameters including water content in the gel, crystallization time, support pore size, and aluminum source were investigated. High performance N-2-selective membranes were obtained on 100-nm-pore alumina tubes by using Al(i-C3H7O)(3) as aluminum source with a crystallization time of 6 h. These membranes separated N-2 from CH, with N-2 permeance as high as 500 GPU with separation selectivity of 8 at 24 degrees C. for a 50/50 N-2/CH4 mixture. Nitrogen and CH, adsorption isotherms were measured on SAPO-34 crystals. The N-2 and CH, heats of adsorption were 11 and 15 kJ/mol, respectively, which lead to a preferential adsorption of CE-H-4 over N-2 in the N-2/CH4 mixture. Despite this, the SAPO-34 membranes were selective for N-2 over CH4 in the mixture because N-2 diffuses much faster than CH4 and differences in diffusivity played a more critical role than the competitive adsorption. Preliminary economic evaluation indicates that the required N-2/CH4 selectivity would be 15 in order to maintain a CH4 loss below 10%. For small nitrogen-contaminated gas wells, our current SAPO-34 membranes have potential to compete with the benchmark technology cryogenic distillation for N-2 rejection. (C) 2015 Elsevier B.V. All rights reserved,

  12. ChEAS Data: The Chequamegon Ecosystem Atmosphere Study

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Davis, Kenneth J. [Penn State

    The Chequamegon Ecosystem-Atmosphere Study (ChEAS) is a multi-organizational research effort studying biosphere/atmosphere interactions within a northern mixed forest in Northern Wisconsin. A primary goal is to understand the processes controlling forest-atmosphere exchange of carbon dioxide and the response of these processes to climate change. Another primary goal is to bridge the gap between canopy-scale flux measurements and the global CO2 flask sampling network. The ChEAS flux towers participate in AmeriFlux, and the region is an EOS-validation site. The WLEF tower is a NOAA-CMDL CO2 sampling site. ChEAS sites are primarily located within or near the Chequamegon-Nicolet National Forest in northern Wisconsin, with one site in the Ottawa National Forest in the upper peninsula of Michigan. Current studies observe forest/atmosphere exchange of carbon dioxide at canopy and regional scales, forest floor respiration, photosynthesis and transpiration at the leaf level and use models to scale to canopy and regional levels. EOS-validation studies quantitatively assess the land cover of the area using remote sensing and conduct extensive ground truthing of new remote sensing data (i.e. ASTER and MODIS). Atmospheric remote sensing work is aimed at understanding atmospheric boundary layer dynamics, the role of entrainment in regulating the carbon dioxide mixing ratio profiles through the lower troposphere, and feedback between boundary layer dynamics and vegetation (especially via the hydrologic cycle). Airborne studies have included include balloon, kite and aircraft observations of the CO2 profile in the troposphere.

  13. Methanogenic Conversion of CO2 Into CH4

    SciTech Connect (OSTI)

    Stevens, S.H., Ferry, J.G., Schoell, M.

    2012-05-06

    This SBIR project evaluated the potential to remediate geologic CO2 sequestration sites into useful methane gas fields by application of methanogenic bacteria. Such methanogens are present in a wide variety of natural environments, converting CO2 into CH4 under natural conditions. We conclude that the process is generally feasible to apply within many of the proposed CO2 storage reservoir settings. However, extensive further basic R&D still is needed to define the precise species, environments, nutrient growth accelerants, and economics of the methanogenic process. Consequently, the study team does not recommend Phase III commercial application of the technology at this early phase.

  14. Voluntary Protection Program Onsite Review, CH2M WG LLC, Idaho Cleanup Project March 2014

    Broader source: Energy.gov [DOE]

    Evaluation to determine whether CH2M WG LLC, Idaho Cleanup Project is performing at a level deserving DOE-VPP Star recognition.

  15. Preliminary Notice of Violation, CH2M Hill Hanford Group, Inc. - EA-2003-06

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    | Department of Energy CH2M Hill Hanford Group, Inc. - EA-2003-06 Preliminary Notice of Violation, CH2M Hill Hanford Group, Inc. - EA-2003-06 August 29, 2003 Issued to CH2M Hill Hanford Group, Inc., related to Quality Assurance Issues at the Hanford Site Tank Farms On August 29, 2003, the U.S. Department of Energy issued a Preliminary Notice of Violation (EA-2003-06) to CH2M Hill Hanford Group, Inc. for violations of 10 C.F.R. 830 related to numerous nuclear safety quality assurance issues

  16. DOE Cites CH2M Hill Hanford for Violating Nuclear Safety Rules | Department

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    of Energy for Violating Nuclear Safety Rules DOE Cites CH2M Hill Hanford for Violating Nuclear Safety Rules March 10, 2005 - 10:44am Addthis Hanford Tank Farm Contractor Faces Fine of more than $300,000 WASHINGTON, DC - The Department of Energy (DOE) today notified the CH2M Hill Hanford Group, Inc. (CH2M Hill) - that it will fine the company $316,250 for violations of the department's nuclear safety requirements. CH2M Hill is the department's contractor responsible for storage of highly

  17. Preliminary Notice of Violation, CH2M HILL Hanford Group, Inc.- NEA-2008-02

    Broader source: Energy.gov [DOE]

    Issued to CH2M Hill Hanford Group, Inc., related to a Radioactive Waste Spill at the Hanford Site Tank Farms

  18. Consent Order, CH2M Hill Hanford Group, Inc.- EA-2000-09

    Broader source: Energy.gov [DOE]

    Issued to CH2M Hill Hanford Group, Inc., related to Quality Problems at the Hanford Site Tank Farms, (EA-2000-09)

  19. Enforcement Letter, CH2M Hill Mound, Inc- December 22, 2004

    Broader source: Energy.gov [DOE]

    Issued to CH2M Hill Mound, Inc. related to a Radioactive Contamination Event during Remediation Activities at the Miamisburg Closure Project

  20. Consent Order, CH2M-WG Idaho, LLC - WCO-2011-01 | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    CH2M-WG Idaho, LLC - WCO-2011-01 Consent Order, CH2M-WG Idaho, LLC - WCO-2011-01 October 6, 2011 Issued to CH2M-WG Idaho, LLC related to a Hoisting Incident that occurred at the Sodium Bearing Waste Treatment Project at the Idaho National Laboratory On October 6, 2011, the U.S. Department of Energy (DOE) Office of Health Safety and Security's Office of Enforcement and Oversight issued a Consent Order to CH2M-WG Idaho, LLC (CWI) for deficiencies in CWI's oversight of its construction

  1. Test Plan: WIPP bin-scale CH TRU waste tests

    SciTech Connect (OSTI)

    Molecke, M.A.

    1990-08-01

    This WIPP Bin-Scale CH TRU Waste Test program described herein will provide relevant composition and kinetic rate data on gas generation and consumption resulting from TRU waste degradation, as impacted by synergistic interactions due to multiple degradation modes, waste form preparation, long-term repository environmental effects, engineered barrier materials, and, possibly, engineered modifications to be developed. Similar data on waste-brine leachate compositions and potentially hazardous volatile organic compounds released by the wastes will also be provided. The quantitative data output from these tests and associated technical expertise are required by the WIPP Performance Assessment (PA) program studies, and for the scientific benefit of the overall WIPP project. This Test Plan describes the necessary scientific and technical aspects, justifications, and rational for successfully initiating and conducting the WIPP Bin-Scale CH TRU Waste Test program. This Test Plan is the controlling scientific design definition and overall requirements document for this WIPP in situ test, as defined by Sandia National Laboratories (SNL), scientific advisor to the US Department of Energy, WIPP Project Office (DOE/WPO). 55 refs., 16 figs., 19 tabs.

  2. Single-Step Syngas-to-Distillates (S2D) Synthesis via Methanol and Dimethyl Ether Intermediates: Final Report

    SciTech Connect (OSTI)

    Dagle, Robert A.; Lebarbier, Vanessa MC; Lizarazo Adarme, Jair A.; King, David L.; Zhu, Yunhua; Gray, Michel J.; Jones, Susanne B.; Biddy, Mary J.; Hallen, Richard T.; Wang, Yong; White, James F.; Holladay, Johnathan E.; Palo, Daniel R.

    2013-11-26

    The objective of the work was to enhance price-competitive, synthesis gas (syngas)-based production of transportation fuels that are directly compatible with the existing vehicle fleet (i.e., vehicles fueled by gasoline, diesel, jet fuel, etc.). To accomplish this, modifications to the traditional methanol-to-gasoline (MTG) process were investigated. In this study, we investigated direct conversion of syngas to distillates using methanol and dimethyl ether intermediates. For this application, a Pd/ZnO/Al2O3 (PdZnAl) catalyst previously developed for methanol steam reforming was evaluated. The PdZnAl catalyst was shown to be far superior to a conventional copper-based methanol catalyst when operated at relatively high temperatures (i.e., >300°C), which is necessary for MTG-type applications. Catalytic performance was evaluated through parametric studies. Process conditions such as temperature, pressure, gas-hour-space velocity, and syngas feed ratio (i.e., hydrogen:carbon monoxide) were investigated. PdZnAl catalyst formulation also was optimized to maximize conversion and selectivity to methanol and dimethyl ether while suppressing methane formation. Thus, a PdZn/Al2O3 catalyst optimized for methanol and dimethyl ether formation was developed through combined catalytic material and process parameter exploration. However, even after compositional optimization, a significant amount of undesirable carbon dioxide was produced (formed via the water-gas-shift reaction), and some degree of methane formation could not be completely avoided. Pd/ZnO/Al2O3 used in combination with ZSM-5 was investigated for direct syngas-to-distillates conversion. High conversion was achieved as thermodynamic constraints are alleviated when methanol and dimethyl are intermediates for hydrocarbon formation. When methanol and/or dimethyl ether are products formed separately, equilibrium restrictions occur. Thermodynamic relaxation also enables the use of lower operating pressures than what

  3. Exploratory study of coal-conversion chemistry. Quarterly report, June 20, 1980-September 19, 1980. [Diphenylmethane, diphenyl ether

    SciTech Connect (OSTI)

    Not Available

    1981-03-04

    This report describes work accomplished under two task: Task A, Mechanism of Cleavage of Key Bond types Present in Coals, and Task B, Catalysis of Conversion in CO-H/sub 2/O Systems. Under Task A, we have made additional measurements of catalytic carbon-carbon and carbon-oxygen bond cleavage in coal-related diphenylmethane and diphenyl ether structures. The results provide further support for, but do not definitely confirm, the tentative conclusion that the highly effective iron oxide catalysts involves oxidation to radical cation species. The homogeneous scission of carbon-oxygen bonds in diphenyl ether structure has also been studied. In the Task B studies of CO-H/sub 2/O systems, we typically obtain 50% benzene-soluble product material from 20 min. reaction of beneficiated Illinois No. 6 coal. This conversion level is obtained with aqueous solutions either at a starting pH above 12.6 or in neutral solutions with water-soluble catalysts present. We have studied a number of catalysts, including the potassium or sodium salts of molybdate, chromate, manganate, and tungstate; all are effective in the 3000 to 6000 ppM range. A striking result is that sodium nitrate at 6000 ppM is as effective as the metal salts. We found that the nitrate was converted to ammonium ion; also, formate was detected in the product aqueous phase. Finally, we find that catalytic quantities of sodium formate in CO/H/sub 2/O at pH 7 are effective in the conversion. However, in a control run in N/sub 2//H/sub 2/O, with a quantity of sodium formate equivalent to twice the molar quantity of hydrogen transferred to the coal in a successful run, the coal was converted to a product totally insoluble in benzene and with a lower hydrogen content than the starting coal.

  4. Low-temperature CVD of iron, cobalt, and nickel nitride thin films from bis[di(tert-butyl)amido]metal(II) precursors and ammonia

    SciTech Connect (OSTI)

    Cloud, Andrew N.; Abelson, John R., E-mail: abelson@illinois.edu [Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, 201 Materials Science and Engineering Building, 1304 W. Green St., Urbana, Illinois 61801 (United States); Davis, Luke M.; Girolami, Gregory S., E-mail: girolami@scs.illinois.edu [School of Chemical Sciences, University of Illinois at Urbana-Champaign, 600 S. Mathews Ave., Urbana, Illinois 61801 (United States)

    2014-03-15

    Thin films of late transition metal nitrides (where the metal is iron, cobalt, or nickel) are grown by low-pressure metalorganic chemical vapor deposition from bis[di(tert-butyl)amido]metal(II) precursors and ammonia. These metal nitrides are known to have useful mechanical and magnetic properties, but there are few thin film growth techniques to produce them based on a single precursor family. The authors report the deposition of metal nitride thin films below 300?C from three recently synthesized M[N(t-Bu){sub 2}]{sub 2} precursors, where M?=?Fe, Co, and Ni, with growth onset as low as room temperature. Metal-rich phases are obtained with constant nitrogen content from growth onset to 200?C over a range of feedstock partial pressures. Carbon contamination in the films is minimal for iron and cobalt nitride, but similar to the nitrogen concentration for nickel nitride. X-ray photoelectron spectroscopy indicates that the incorporated nitrogen is present as metal nitride, even for films grown at the reaction onset temperature. Deposition rates of up to 18?nm/min are observed. The film morphologies, growth rates, and compositions are consistent with a gas-phase transamination reaction that produces precursor species with high sticking coefficients and low surface mobilities.

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

    SciTech Connect (OSTI)

    Novoa, J.J.; Whangbo, Myung-Hwan; Williams, J.M.

    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.

  6. Photolysis of CH{sub 3}CHO at 248 nm: Evidence of triple fragmentation from primary quantum yield of CH{sub 3} and HCO radicals and H atoms

    SciTech Connect (OSTI)

    Morajkar, Pranay; Schoemaecker, Coralie; Fittschen, Christa; Bossolasco, Adriana

    2014-06-07

    Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH{sub 3}CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO{sub 2} radicals by reaction with O{sub 2}. The CH{sub 3} radical yield has been determined using the same technique following their conversion into CH{sub 3}O{sub 2}. Absolute yields have been deduced for HCO radicals and H atoms through fitting of time resolved HO{sub 2} profiles, obtained under various O{sub 2} concentrations, to a complex model, while the CH{sub 3} yield has been determined relative to the CH{sub 3} yield from 248 nm photolysis of CH{sub 3}I. Time resolved HO{sub 2} profiles under very low O{sub 2} concentrations suggest that another unknown HO{sub 2} forming reaction path exists in this reaction system besides the conversion of HCO radicals and H atoms by reaction with O{sub 2}. HO{sub 2} profiles can be well reproduced under a large range of experimental conditions with the following quantum yields: CH{sub 3}CHO?+?h?{sub 248nm} ? CH{sub 3}CHO{sup *}, CH{sub 3}CHO{sup *} ? CH{sub 3}?+?HCO??{sub 1a} = 0.125??0.03, CH{sub 3}CHO{sup *} ? CH{sub 3}?+?H?+?CO??{sub 1e} = 0.205??0.04, CH{sub 3}CHO{sup *}?{sup o{sub 2}}CH{sub 3}CO?+?HO{sub 2}??{sub 1f} = 0.07??0.01. The CH{sub 3}O{sub 2} quantum yield has been determined in separate experiments as ?{sub CH{sub 3}} = 0.33 0.03 and is in excellent agreement with the CH{sub 3} yields derived from the HO{sub 2} measurements considering that the triple fragmentation (R1e) is an important reaction path in the 248 nm photolysis of CH{sub 3}CHO. From arithmetic considerations taking into account the HO{sub 2} and CH{sub 3} measurements we deduce a remaining quantum yield for the molecular pathway: CH{sub 3}CHO{sup *} ? CH{sub 4}?+?CO??{sub 1b} = 0.6. All experiments can be consistently explained with absence of the formerly considered

  7. Method of preparing (CH.sub.3).sub.3 SiNSO and byproducts thereof

    DOE Patents [OSTI]

    Spicer, Leonard D.; Bennett, Dennis W.; Davis, Jon F.

    1984-01-01

    (CH.sub.3).sub.3 SiNSO is produced by the reaction of ((CH.sub.3).sub.3 Si).sub.2 NH with SO.sub.2. Also produced in the reaction are ((CH.sub.3).sub.3 Si).sub.2 O and a new solid compound [NH.sub.4 ][(CH.sub.3).sub.3 SiOSO.sub.2 ]. Both (CH.sub.3).sub.3 SiNSO and [NH.sub.4 ][(CH.sub.3).sub.3 SiOSO.sub.2 ] have fluorescent properties. The reaction of the subject invention is used in a method of measuring the concentration of SO.sub.2 pollutants in gases. By the method, a sample of gas is bubbled through a solution of ((CH.sub.3).sub.3 Si).sub.2 NH, whereby any SO.sub.2 present in the gas will react to produce the two fluorescent products. The measured fluorescence of these products can then be used to calculate the concentration of SO.sub.2 in the original gas sample. The solid product [NH.sub.4 ][(CH.sub.3).sub.3 SiOSO.sub.2 ] may be used as a standard in solid state NMR spectroscopy.

  8. Independent Oversight Review, Richland Operations Office and CH2M Hill Plateau Remediation Company and Mission Support Alliance- April 2012

    Broader source: Energy.gov [DOE]

    Review of Richland Operations Office and CH2M Hill Plateau Remediation Company and Mission Support Alliance Conduct of Operations

  9. Involvement of reactive oxygen species in brominated diphenyl ether-47-induced inflammatory cytokine release from human extravillous trophoblasts in vitro

    SciTech Connect (OSTI)

    Park, Hae-Ryung Kamau, Patricia W.; Loch-Caruso, Rita

    2014-01-15

    Polybrominated diphenyl ethers (PBDEs) are widely used flame retardant compounds. Brominated diphenyl ether (BDE)-47 is one of the most prevalent PBDE congeners found in human breast milk, serum and placenta. Despite the presence of PBDEs in human placenta, effects of PBDEs on placental cell function are poorly understood. The present study investigated BDE-47-induced reactive oxygen species (ROS) formation and its role in BDE-47-stimulated proinflammatory cytokine release in a first trimester human extravillous trophoblast cell line, HTR-8/SVneo. Exposure of HTR-8/SVneo cells for 4 h to 20 ?M BDE-47 increased ROS generation 1.7 fold as measured by the dichlorofluorescein (DCF) assay. Likewise, superoxide anion production increased approximately 5 fold at 10 and 15 ?M and 9 fold at 20 ?M BDE-47 with a 1-h exposure, as measured by cytochrome c reduction. BDE-47 (10, 15 and 20 ?M) decreased the mitochondrial membrane potential by 4764.5% at 4, 8 and 24 h as assessed with the fluorescent probe Rh123. Treatment with 15 and 20 ?M BDE-47 stimulated cellular release and mRNA expression of IL-6 and IL-8 after 12 and 24-h exposures: the greatest increases were a 35-fold increased mRNA expression at 12 h and a 12-fold increased protein concentration at 24 h for IL-6. Antioxidant treatments (deferoxamine mesylate, ()?-tocopherol, or tempol) suppressed BDE-47-stimulated IL-6 release by 54.1%, 56.3% and 37.7%, respectively, implicating a role for ROS in the regulation of inflammatory pathways in HTR-8/SVneo cells. Solvent (DMSO) controls exhibited statistically significantly decreased responses compared with non-treated controls for IL-6 release and IL-8 mRNA expression, but these responses were not consistent across experiments and times. Nonetheless, it is possible that DMSO (used to dissolve BDE-47) may have attenuated the stimulatory actions of BDE-47 on cytokine responses. Because abnormal activation of proinflammatory responses can disrupt trophoblast functions

  10. Changes in mitogen-activated protein kinase in cerebellar granule neurons by polybrominated diphenyl ethers and polychlorinated biphenyls

    SciTech Connect (OSTI)

    Fan Chunyang; Besas, Jonathan

    2010-05-15

    Polybrominated diphenyl ethers (PBDEs) are used as additive flame retardants and have been detected in human blood, adipose tissue, and breast milk. Both in vitro and in vivo studies have shown that the effects of PBDEs are similar to the known human developmental neurotoxicants such as polychlorinated biphenyls (PCBs) on a molar basis. Previously, we reported that PBDE mixtures and congeners, perturbed calcium homeostasis which is critical for the development and function of the nervous system. In the present study, we tested whether environmentally relevant PBDE/PCB mixtures and congeners affected mitogen-activated protein kinase (MAPK) pathways, which are down-stream events of calcium signaling in cerebellar granule neuronal cultures. In this study, phosphorylated extracellular signal-regulated kinase (pERK)1/2, a widely studied MAPK cascade and known to be involved in learning and memory, levels were quantitated using western blot technique with phospho-specific antibodies. Glutamate (a positive control) increased pERK1/2 in a time- and concentration-dependent manner reaching maximum activation at 5-30 min of exposure and at doses >= 10 muM. Both Aroclor 1254 (a commercial penta PCB mixture) and DE-71 (a commercial penta PBDE mixture) elevated phospho-ERK1/2, producing maximum stimulation at 30 min and at concentrations >= 3 mug/ml; Aroclor 1254 was more efficacious than DE-71. DE-79 (an octabrominated diphenyl ether mixture) also elevated phospho-ERK1/2, but to a lesser extent than that of DE-71. PBDE congeners 47, 77, 99, and 153 also increased phospo-ERK1/2 in a concentration-dependent manner. The data indicated that PBDE congeners are more potent than the commercial mixtures. PCB 47 also increased phospho-ERK1/2 like its structural analog PBDE 47, but to a lesser extent, suggesting that these chemicals affect similar pathways. Cytotoxicity, measured as %LDH release, data showed that higher concentrations (> 30 muM) and longer exposures (> 30 min) are

  11. DOE Selects CH2M Hill Plateau Remediation Company for Plateau Remediation

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Contract at its Hanford Site | Department of Energy CH2M Hill Plateau Remediation Company for Plateau Remediation Contract at its Hanford Site DOE Selects CH2M Hill Plateau Remediation Company for Plateau Remediation Contract at its Hanford Site June 19, 2008 - 1:29pm Addthis WASHINGTON, DC - The U.S. Department of Energy (DOE) today announced that CH2M Hill Plateau Remediation Company has been selected as the plateau remediation contractor for DOE's Hanford Site in southeastern Washington

  12. ChIMES: "Limited only by our imaginations" | Y-12 National Security

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Complex ChIMES: "Limited only by ... ChIMES: "Limited only by our imaginations" Posted: March 26, 2015 - 4:18pm The ChIMES team's investigators each brought unique expertise to the project. A three-year collaboration of scientists from Y-12 National Security Complex and The University of Tennessee, Knoxville, resulted in the innovation of a patented chemical sensor that is unique in several aspects: it's inexpensive, tiny and portable; it promises virtually limitless

  13. Microsoft PowerPoint - New Materials for CH4 Capture-slide_AM [Read-Only]

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    We have discovered a handful of zeolite structures that have sufficient methane (CH 4 ) adsorption capacity as well as appropriate CH 4 /CO 2 and CH 4 /N 2 selectivity to be technologically promising for methane capture from dilute and medium-concentration sources. J Kim, A Maiti, L-C Lin, J Stolaroff, B Smit, R Aines, Nat. Commun. (2013). Doi: 10.1038/ncomms2697 New Materials for Methane Capture from Dilute and Medium-concentration Sources Significance and Impact Methane is an important

  14. CH2M HILL Plateau Remediation Company, NEL-2014-01

    Office of Environmental Management (EM)

    CH2M HILL Plateau Remediation Company CH2M HILL Plateau Remediation Company The Office of Hea1th, Safety and Security's Office of Enforcement and Oversight has evaluated the facts and circumstances of a series of radiological work deficiencies at the Plutonium Finishing Plant (PFP) and the 105 K-East Reactor Facility (105KE Reactor) by CH2M HILL Plateau Remediation Company (CHPRC). The radiological work deficiencies at PFP are documented in the April 29, 2011, Department of Energy Richland

  15. Voluntary Protection Program Onsite Review, URS | CH2M Oak Ridge LLC -

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    April 2015 | Department of Energy URS | CH2M Oak Ridge LLC - April 2015 Voluntary Protection Program Onsite Review, URS | CH2M Oak Ridge LLC - April 2015 April 2015 UCOR is admitted to the Department of Energy Voluntary Protection Program as a Star Participant. This report summarizes the results from the evaluation of URS | CH2M OAK RIDGE LLC (UCOR) in Oak Ridge, Tennessee during the period of April 14-23 2015, and provides the Associate Under Secretary for AU with the necessary information

  16. Contract No. DE-AC02-07CH11358 Contract Modification No. 0200

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Attachment J.5, Appendix E J-E-1 ATTACHMENT J.5 APPENDIX E AMES LABORATORY DEPARMENT OF ENERGY (LESSEE) INGRANTS Applicable to the Operation of AMES Laboratory Contract No. DE-AC02-07CH11358 Contract No. DE-AC02-07CH11358 Contract Modification No. 0200 Section J.5, Appendix E CONTRACT NO. BUILDING NAME(s) LESSOR CITY STATE PURPOSE COST EFFECT DATE EXP DATE ACRE DE-RL02-76CH00144* (formerly AT(11-1) 1309) Land Lease Construction Storage Shed Mechanical Maintenance Campus Warehouse Maintenance

  17. Heat Capacity Uncertainty Calculation for the Eutectic Mixture of Biphenyl/Diphenyl Ether Used as Heat Transfer Fluid: Preprint

    SciTech Connect (OSTI)

    Gomez, J. C.; Glatzmaier, G. C.; Mehos, M.

    2012-09-01

    The main objective of this study was to calculate the uncertainty at 95% confidence for the experimental values of heat capacity of the eutectic mixture of biphenyl/diphenyl ether (Therminol VP-1) determined from 300 to 370 degrees C. Twenty-five samples were evaluated using differential scanning calorimetry (DSC) to obtain the sample heat flow as a function of temperature. The ASTM E-1269-05 standard was used to determine the heat capacity using DSC evaluations. High-pressure crucibles were employed to contain the sample in the liquid state without vaporizing. Sample handling has a significant impact on the random uncertainty. It was determined that the fluid is difficult to handle, and a high variability of the data was produced. The heat capacity of Therminol VP-1 between 300 and 370 degrees C was measured to be equal to 0.0025T+0.8672 with an uncertainty of +/- 0.074 J/g.K (3.09%) at 95% confidence with T (temperature) in Kelvin.

  18. Toxicity of polychlorinated diphenyl ethers in hydra attenuata and in rat whole-embryo culture. Master's thesis

    SciTech Connect (OSTI)

    Becker, M.C.

    1991-05-01

    Polychlorinated diphenyl ethers (PCDEs) are a class of biaryl compounds that have little commercial application, but appear to be widespread in the environment. They have been found in wood preservative waste dumpsites and in fly ash from municipal waste incinerators. They have been detected in bird eggs and tissues, fish, and other edible marine organisms in the United States, Canada, and Europe. There are limited reports in the extant literature on the toxicity of PCDEs. This study was designed to evaluate the toxicity of selected PCDEs in cultures of Hydra attenuata and post-implantation rat whole embryos. The toxicity of several closely related polychlorinated biphenyls (PCBs) was evaluated in both cultures and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was evaluated in whole embryo culture. Embryonic growth and development parameters (yolk sac diameter, crown-rump length, somite count, and DNA and protein content) and gross morphology were determined. Findings indicated that these chemicals were neither embryotoxic nor teratogenic. Thus, the PCDEs, which elicit other diverse toxic and biochemical responses in rodents, are relatively inactive in these bioassays for developmental toxicity.

  19. Electrochemical Investigation of Li–Al Anodes in Oligo(ethylene glycol) Dimethyl Ether/LiPF6

    SciTech Connect (OSTI)

    Zhou, Y.N.; Yang, X.; Wang, X.J.; Lee, H.S.; Nam, K.W.; Haas, O.

    2010-11-01

    1 M LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 500 g mol{sup -1} was investigated as a new electrolyte (OEGDME500, 1 M LiPF{sub 6}) for metal deposition and battery applications. At 25 C a conductivity of 0.48 x 10{sup -3} S cm{sup -1} was obtained and at 85 C, 3.78 x 10{sup -3} S cm{sup -1}. The apparent activation barrier for ionic transport was evaluated to be 30.7 kJ mol{sup -1}. OEGDME500, 1 M LiPF{sub 6} allows operating temperature above 100 C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 280 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li-Al alloy formation reaction.

  20. Electrochemical Investigation of Li-Al Anodes in Oligo (ethylene glycol) Dimethyl ether/LiPF6

    SciTech Connect (OSTI)

    Y Zhou; X Wang; H Lee; K Nam; X Yang; O Haas

    2011-12-31

    LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 5 g mol{sup -1} was investigated as a new electrolyte (OEGDME5, 1 M LiPF{sub 6}) for metal deposition and battery applications. At 25 C a conductivity of .48 x 1{sup -3} S cm{sup -1} was obtained and at 85 C, 3.78 x 1{sup -3} S cm{sup -1}. The apparent activation barrier for ionic transport was evaluated to be 3.7 kJ mol{sup -1}. OEGDME5, 1 M LiPF{sub 6} allows operating temperature above 1 C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 28 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li-Al alloy formation reaction.

  1. Calcitriol inhibits Ether-a go-go potassium channel expression and cell proliferation in human breast cancer cells

    SciTech Connect (OSTI)

    Garcia-Becerra, Rocio; Diaz, Lorenza; Camacho, Javier; Barrera, David; Ordaz-Rosado, David; Morales, Angelica; Ortiz, Cindy Sharon; Avila, Euclides; Bargallo, Enrique; Arrecillas, Myrna; Halhali, Ali; Larrea, Fernando

    2010-02-01

    Antiproliferative actions of calcitriol have been shown to occur in many cell types; however, little is known regarding the molecular basis of this process in breast carcinoma. Ether-a-go-go (Eag1) potassium channels promote oncogenesis and are implicated in breast cancer cell proliferation. Since calcitriol displays antineoplastic effects while Eag1 promotes tumorigenesis, and both factors antagonically regulate cell cycle progression, we investigated a possible regulatory effect of calcitriol upon Eag1 as a mean to uncover new molecular events involved in the antiproliferative activity of this hormone in human breast tumor-derived cells. RT real-time PCR and immunocytochemistry showed that calcitriol suppressed Eag1 expression by a vitamin D receptor (VDR)-dependent mechanism. This effect was accompanied by inhibition of cell proliferation, which was potentiated by astemizole, a nonspecific Eag1 inhibitor. Immunohistochemistry and Western blot demonstrated that Eag1 and VDR abundance was higher in invasive-ductal carcinoma than in fibroadenoma, and immunoreactivity of both proteins was located in ductal epithelial cells. Our results provide evidence of a novel mechanism involved in the antiproliferative effects of calcitriol and highlight VDR as a cancer therapeutic target for breast cancer treatment and prevention.

  2. Contract DE-AC02-07CH11358 Modifications Language Changes

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    AC02-07CH11358 Modifications Language Changes Modification 183 October 23, 2015 Part I, Section H - Special Contract Requirements (replace Mod 171) Part II, Section I - Contract...

  3. Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4...

    Office of Scientific and Technical Information (OSTI)

    Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions. Citation Details In-Document Search Title:...

  4. Enforcement Letter, CH2M-Washington Group Idaho LLC , - May 20...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    , - May 20, 2009 May 20, 2009 Issued to CH2M-Washington Group Idaho, LLC, for Electrical Safety Deficiencies at the Idaho National Laboratory On May 20, 2009, the U.S. Department...

  5. Voluntary Protection Program Onsite Review, CH2M HILL B&W West...

    Office of Environmental Management (EM)

    B&W West Valley LLC, West Valley Demonstration Project - October 2013 Voluntary Protection Program Onsite Review, CH2M HILL B&W West Valley LLC, West Valley Demonstration Project - ...

  6. 10 CFR Ch. III (1-1-11 Edition) Pt. 851, App. B

    Broader source: Energy.gov (indexed) [DOE]

    2 10 CFR Ch. III (1-1-11 Edition) Pt. 851, App. B must meet the applicable electrical safety codes and standards referenced in 851.23. 11. NANOTECHNOLOGY SAFETY-RESERVED The ...

  7. Hydrogen Storage in Carbon Nanotubes Through Formation of C-H...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major ... One possible solution to these problems is to use an energy carrier such as hydrogen, and ...

  8. Direct Dynamics Simulation of Dissociation of the [CH3--I--OH...

    Office of Scientific and Technical Information (OSTI)

    Ion-Molecule Complex Citation Details In-Document Search Title: Direct Dynamics Simulation of Dissociation of the CH3--I--OH- Ion-Molecule Complex Direct dynamics ...

  9. Park, Y.J.; Hofmayer, C.H. [Brookhaven National Lab., Upton,...

    Office of Scientific and Technical Information (OSTI)

    Understanding seismic design criteria for Japanese nuclear power plants Park, Y.J.; Hofmayer, C.H. Brookhaven National Lab., Upton, NY (United States); Costello, J.F. US Nuclear...

  10. Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4...

    Office of Scientific and Technical Information (OSTI)

    Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4-CO2- H20) Interactions in Shale Nanopores under ReservoirSAND2o 1T-20" if4pe Yifeng Wang, Yongliang Xiong & Louise ...

  11. Fundamental Understanding of Methane-Carbon Dioxide-Water (CH4...

    Office of Scientific and Technical Information (OSTI)

    ...Water (CH4-CO2-H2O) Interactions in Shale Nanopores under Reservoir Conditions. Citation Details In-Document Search Title: Fundamental Understanding of Methane-Carbon Dioxide-Water ...

  12. Quantitative Visualization of ChIP-chip Data by Using Linked...

    Office of Scientific and Technical Information (OSTI)

    Most analyses of ChIP-chip in vivo DNA binding have focused on qualitative descriptions of ... analyze and explore in vivo DNA binding data of multiple transcription factors. ...

  13. Molecular Simulation Studies of Separation of CO2/N2, CO2/CH4...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    do this, we first identified a suitable force field for describing CO2, N2, and CH4 adsorption in ZIFs. On the basis of the validated force field, adsorption selectivities of the...

  14. Microsoft Word - Ce-CH3X ms-revised.doc

    Office of Scientific and Technical Information (OSTI)

    1 Hydrogen for X-group exchange in CH 3 X, X Cl, Br, I, OMe and NMe 2 by ... in a 1 H NMR spectrum in which a single hydrogen atom is statistically distributed into ...

  15. DOE Cites CH2M Hill Hanford Group for Price-Anderson Violations

    Broader source: Energy.gov [DOE]

    WASHINGTON, DC - The Department of Energy (DOE) today notified CH2M Hill Hanford Group (CHG) that it will fine the company $82,500 for violations of the Department's nuclear safety requirements. ...

  16. DOE Cites CH2M Hill Hanford Group, Inc. for Price-Anderson Violations

    Broader source: Energy.gov [DOE]

    WASHINGTON, DC - The Department of Energy (DOE) today issued a Preliminary Notice of Violation (PNOV) to CH2M Hill Hanford Group, Inc. (CHG) for nuclear safety violations.  CHG is the tank...

  17. Hindering effects in diffusion of CO2/CH4 mixtures in ZIF-8 crystals...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hindering effects in diffusion of CO2CH4 mixtures in ZIF-8 crystals Previous Next List C. Chmelik, J. van Baten, and R. Krishna, J. Membr. Sci. 397, 87 (2012) DOI: 10.1016...

  18. Preliminary Notice of Violation, CH2M-Washington Group Idaho, LLC- EA-2007-03

    Broader source: Energy.gov [DOE]

    Issued to CH2M-Washington Group Idaho, LLC, related to Radiation Protection Program Deficiencies at the Radioactive Waste Management Complex - Accelerated Retrieval Project at the Idaho National Laboratory

  19. Cp* Iridium Precatalysts for Selective C-H Oxidation via Direct...

    Office of Scientific and Technical Information (OSTI)

    The nature of the active species was investigated by TEM, UV-vis, microfiltration, and control experiments. DFT calculations showed that the C-H oxidation of cis-decalin by ...

  20. Electronic structure, transport, and phonons of SrAgChF (Ch = S,Se,Te): Bulk superlattice thermoelectrics

    SciTech Connect (OSTI)

    Gudelli, Vijay Kumar; Kanchana, V.; Vaitheeswaran, G.; Singh, David J.; Svane, Axel; Christensen, Niels Egede; Mahanti, Subhendra D.

    2015-07-15

    Here, we report calculations of the electronic structure, vibrational properties, and transport for the p-type semiconductors, SrAgChF (Ch = S, Se, and Te). We find soft phonons with low frequency optical branches intersecting the acoustic modes below 50 cm–1, indicative of a material with low thermal conductivity. The bands at and near the valence-band maxima are highly two-dimensional, which leads to high thermopowers even at high carrier concentrations, which is a combination that suggests good thermoelectric performance. These materials may be regarded as bulk realizations of superlattice thermoelectrics.

  1. Spectroscopic characterization of rovibrational temperatures in atmospheric pressure He/CH{sub 4} plasmas

    SciTech Connect (OSTI)

    Moon, Se Youn; Kim, D. B.; Gweon, B.; Choe, W.

    2008-10-15

    Atmospheric pressure of helium (He) and methane (CH{sub 4}) mixture discharge characteristics are investigated using emission spectroscopic methods. Plasmas are produced in a radio frequency capacitively coupled device at atmospheric pressure in the ambient air. Without the CH{sub 4} gas introduced in the plasma, the emission spectrum exhibits typical helium discharge characteristics showing helium atomic lines with nitrogen molecular bands and oxygen atomic lines resulting from air impurities. Addition of a small amount (<1%) of CH{sub 4} to the supplied He results in the emission of CN (B{sup 2}{sigma}{sup +}-X{sup 2}{sigma}{sup +}: violet system) and CH (A{sup 2}{delta}-X{sup 2} product : 430 nm system) molecular bands. Analyzing the CN and CH diatomic molecular emission spectra, the vibrational temperature (T{sub vib}) and rotational temperature (T{sub rot}) are simultaneously obtained. As input power levels are raised from 20 W to 200 W, T{sub vib} and T{sub rot} are increased from 4230 K to 6310 K and from 340 K to 500 K, respectively. On the contrary, increasing the CH{sub 4} amount brings about the decrease of both temperatures because CH{sub 4} is harder to ionize than He. The emission intensities of CN and CH radicals, which are important in plasma processing, are also changed along with the temperature variation. From the results, the atmospheric pressure plasma shows strong nonequilibrium discharge properties, which may be effectively utilized for thermal damage free material treatments.

  2. UV absorption spectrum of the C2 Criegee intermediate CH{sub 3}CHOO

    SciTech Connect (OSTI)

    Smith, Mica C.; Ting, Wei-Lun; Chang, Chun-Hung; Takahashi, Kaito; Boering, Kristie A.; Lin, Jim Jr-Min

    2014-08-21

    The UV spectrum of CH{sub 3}CHOO was measured by transient absorption in a flow cell at 295 K. The absolute absorption cross sections of CH{sub 3}CHOO were measured by laser depletion in a molecular beam to be (1.06 ± 0.09) × 10{sup −17} cm{sup 2} molecule{sup −1} at 308 nm and (9.7 ± 0.6) × 10{sup −18} cm{sup 2} molecule{sup −1} at 352 nm. After scaling the UV spectrum of CH{sub 3}CHOO to the absolute cross section at 308 nm, the peak UV cross section is (1.27 ± 0.11) × 10{sup −17} cm{sup 2} molecule{sup −1} at 328 nm. Compared to the simplest Criegee intermediate CH{sub 2}OO, the UV absorption band of CH{sub 3}CHOO is similar in intensity but blue shifted by 14 nm, resulting in a 20% slower photolysis rate estimated for CH{sub 3}CHOO in the atmosphere.

  3. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas

    SciTech Connect (OSTI)

    Bhatt, B.L.

    1992-09-01

    As part of the DOE-sponsored contract for the Synthesis of Dimethyl Ether (DME) and Alternative Fuels in the Liquid Phase from Coal- Derived Syngas, the single-step, slurry phase DME synthesis process was developed. The development involved screening of catalyst systems, process variable studies, and catalyst life studies in two 300 ml stirred autoclaves. As a spin-off of the Liquid Phase Methanol (LPMEOH*) process, the new process significantly improves the syngas conversion efficiency of the LPMEOH process. This improvement can be achieved by replacing a portion of methanol catalyst with a dehydration catalyst in the reactor, resulting in the product methanol being converted to DME, thus avoiding the thermodynamic equilibrium constraint of the methanol reaction. Overall, this increases syngas conversion per-pass. The selectivity and productivity of DME and methanol are affected by the catalyst system employed as well as operating conditions. A preferred catalyst system, consisting of a physical mixture of a methanol catalyst and a gamma alumina, was identified. An improvement of about 50% in methanol equivalent productivity was achieved compared to the LPMEOH process. Results from the process variable study indicate that higher pressure and CO[sub 2] removal benefit the process significantly. Limited life studies performed on the preferred catalyst system suggest somewhat higher than expected deactivation rate for the methanol catalyst. Several DME/methanol mixtures were measured for their key properties as transportation fuels. With small amounts of DME added, significant improvements in both flash points and Reid Vapor Pressure (RVP) were observed over the corresponding values of methanol alone.

  4. Auto-ignition during instationary jet evolution of dimethyl ether (DME) in a high-pressure atmosphere

    SciTech Connect (OSTI)

    Fast, G.; Kuhn, D.; Class, A.G.; Maas, U.

    2009-01-15

    The auto-ignition process during transient injection of gaseous dimethyl ether (DME) in a constant high-pressure atmosphere is studied experimentally by laser-optical methods and compared with numerical calculations. With different non-intrusive measurement techniques jet properties and auto-ignition are investigated at high temporal and spatial resolution. The open jet penetrates a constant pressure oxidative atmosphere of up to 4 MPa. During the transient evolution, the fuel jet entrains air at up to 720 K. The subsequent auto-ignition of the ignitable part of the jet occurs simultaneously over a wide spatial extension. The ignition delay times are not affected by variation of the nozzle exit velocity. Thus, the low-temperature oxidation is slow compared with the shorter time scales of mixing, so that chemical kinetics is dominating the process. The typical two-stage ignition is resolved optically with high-speed shadowgraphy at a sampling rate of 10 kHz. The 2D fields of jet velocity and transient mixture fraction are measured phase-coupled with Particle Image Velocimetry (PIV) and Tracer Laser Induced Fluorescence (LIF) during the time-frame of ignition. The instationary Probability Density Functions (PDF) of mixture fraction are described very well by Beta functions within the complete area of the open jet. Additional 1D flamelet simulations of the auto-ignition process are computed with a detailed reaction mechanism for DME [S. Fischer, F. Dryer, H. Curran, Int. J. Chem. Kinet. 32 (12) (2000) 713-740; H. Curran, S. Fischer, F. Dryer, Int. J. Chem. Kinet. 32 (12) (2000) 741-759]. Calculated ignition delay times are in very good agreement with the measured mean ignition delay times of 3 ms. Supplemental flamelet simulations address the influence of DME and air temperature, pressure and strain. Underneath a critical strain rate the air temperature is identified to be the most sensitive factor on ignition delay time. (author)

  5. Noncentrosymmetric rare-earth copper gallium chalcogenides RE{sub 3}CuGaCh{sub 7} (RE=La–Nd; Ch=S, Se): An unexpected combination

    SciTech Connect (OSTI)

    Iyer, Abishek K.; Rudyk, Brent W.; Lin, Xinsong; Singh, Harpreet; Sharma, Arzoo Z.; Wiebe, Christopher R.; Mar, Arthur

    2015-09-15

    The quaternary rare-earth chalcogenides RE{sub 3}CuGaS{sub 7} and RE{sub 3}CuGaSe{sub 7} (RE=La–Nd) have been prepared by reactions of the elements at 1050 °C and 900 °C, respectively. They crystallize in the noncentrosymmetric La{sub 3}CuSiS{sub 7}-type structure (hexagonal, space group P6{sub 3}, Z=2) in which the a-parameter is largely controlled by the RE component (a=10.0–10.3 Å for the sulfides and 10.3–10.6 Å for the selenides) whereas the c-parameter is essentially fixed by the choice of Ga and chalcogen atoms within tetrahedral units (c=6.1 Å for the sulfides and 6.4 Å for the selenides). They extend the series RE{sub 3}MGaCh{sub 7}, previously known for divalent metal atoms (M=Mn–Ni), differing in that the Cu atoms in RE{sub 3}CuGaCh{sub 7} occupy trigonal planar sites instead of octahedral sites. Among quaternary chalcogenides RE{sub 3}MM′Ch{sub 7}, the combination of monovalent (M=Cu) and trivalent (M′=Ga) metals is unusual because it appears to violate the condition of charge balance satisfied by most La{sub 3}CuSiS{sub 7}-type compounds. The possibility of divalent Cu atoms was ruled out by bond valence sum analysis, magnetic measurements, and X-ray photoelectron spectroscopy. The electron deficiency in RE{sub 3}CuGaCh{sub 7} is accommodated through S-based holes at the top of the valence band, as shown by band structure calculations on La{sub 3}CuGaS{sub 7}. An optical band gap of about 2.0 eV was found for La{sub 3}CuGaSe{sub 7}. - Graphical abstract: The chalcogenides RE{sub 3}CuGaCh{sub 7} contain monovalent Cu in trigonal planes and trivalent Ga in tetrahedra; they are electron-deficient representatives of La{sub 3}CuSiS{sub 7}-type compounds, which normally satisfy charge balance. - Highlights: • Quaternary chalcogenides RE{sub 3}CuGaCh{sub 7} (RE=La–Nd; Ch=S, Se) were prepared. • Bond valence sums, magnetism, and XPS data give evidence for monovalent Cu. • Crystal structures reveal high anisotropy of Cu displacement.

  6. Experimental and theoretical rate constants for CH{sub 4} + O{sub 2} {yields} CH{sub 3} + HO{sub 2}

    SciTech Connect (OSTI)

    Srinivasan, N.K.; Michael, J.V.; Harding, L.B.; Klippenstein, S.J.

    2007-04-15

    In this study, rate constants for the primary initiation process in low to moderate temperature CH{sub 4} oxidation CH{sub 4} + O{sub 2} {yields} CH{sub 3} + HO{sub 2} have been measured in a reflected shock tube apparatus between 1655 and 1822 K using multipass absorption spectrometric detection of OH radicals at 308 nm. After rapid dissociation of HO{sub 2} yielding H atoms, which are instantaneously converted to OH by H + O{sub 2} {yields} OH + O, the temporal concentration of OH radicals was observed as the final product from the rate-controlling title reaction. The present work utilizes 18 optical passes corresponding to a total path length of 1.6 m. This configuration gives a signal to noise ratio of unity at {proportional_to}3 x 10{sup 12} radicals cm{sup -3}. Hence, kinetics experiments could be performed at conditions of low [CH{sub 4}]{sub 0} (60-70 ppm), thereby substantially reducing secondary chemistry. Possible implications of CH{sub 4} dissociation contributing to the OH formation rates were considered. The present experimental results agree with a priori variational transition state theoretical (VTST) calculations, k{sub th}=3.37 x 10{sup -19}T{sup 2.745} exp (-26,041K/T)cm{sup 3}molecule{sup -1} s{sup -1}, clearly showing overlap of experiment and theory, within experimental error. The new rate constant values obtained in this study are 8-10 times higher than the values used in the popular mechanisms GRI-Mech 3.0 and Leeds Methane Mechanism, version 1.5. (author)

  7. Photodissociation and photoisomerization dynamics of CH{sub 2}=CHCHO in solution

    SciTech Connect (OSTI)

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

    2010-03-28

    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 {alpha},{beta}-enones, acrolein (CH{sub 2}=CHCHO) in CH{sub 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{sub 3}CH=C=O with a branching ratio of 0.78 and the less important channel is the {alpha} cleavage of C-H bond yielding radical fragments CH{sub 2}=CHCO+H with a branching ratio of only 0.12. The 1,3-H migration is strongly suggested to correlate with the triplet {sup 3}({pi}{pi}{sup *}) state rather than the ground S{sub 0} state and the {alpha} cleavage of C-H bond is more likely to proceed in the singlet S{sub 1} {sup 1}(n{pi}{sup *}) 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.

  8. Using physiologically based pharmacokinetic modeling to address nonlinear kinetics and changes in rodent physiology and metabolism due to aging and adaptation in deriving reference values for propylene glycol methyl ether and propylene glycol methyl ether acetate.

    SciTech Connect (OSTI)

    Kirman, C R.; Sweeney, Lisa M.; Corley, Rick A.; Gargas, M L.

    2005-04-01

    Reference values, including an oral reference dose (RfD) and an inhalation reference concentration (RfC), were derived for propylene glycol methyl ether (PGME), and an oral RfD was derived for its acetate (PGMEA). These values were based upon transient sedation observed in F344 rats and B6C3F1 mice during a two-year inhalation study. The dose-response relationship for sedation was characterized using internal dose measures as predicted by a physiologically based pharmacokinetic (PBPK) model for PGME and its acetate. PBPK modeling was used to account for changes in rodent physiology and metabolism due to aging and adaptation, based on data collected during weeks 1, 2, 26, 52, and 78 of a chronic inhalation study. The peak concentration of PGME in richly perfused tissues was selected as the most appropriate internal dose measure based upon a consideration of the mode of action for sedation and similarities in tissue partitioning between brain and other richly perfused tissues. Internal doses (peak tissue concentrations of PGME) were designated as either no-observed-adverse-effect levels (NOAELs) or lowest-observed-adverse-effect levels (LOAELs) based upon the presence or absence of sedation at each time-point, species, and sex in the two year study. Distributions of the NOAEL and LOAEL values expressed in terms of internal dose were characterized using an arithmetic mean and standard deviation, with the mean internal NOAEL serving as the basis for the reference values, which was then divided by appropriate uncertainty factors. Where data were permitting, chemical-specific adjustment factors were derived to replace default uncertainty factor values of ten. Nonlinear kinetics are were predicted by the model in all species at PGME concentrations exceeding 100 ppm, which complicates interspecies and low-dose extrapolations. To address this complication, reference values were derived using two approaches which differ with respect to the order in which these extrapolations

  9. Insights into the structure of mixed CO2/CH4 in gas hydrates

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Everett, S. Michelle; Rawn, Claudia J.; Chakoumakos, Bryan C.; Keffer, David J.; Huq, Ashfia; Phelps, Tommy J.

    2015-05-12

    The exchange of carbon dioxide for methane in natural gas hydrates is an attractive approach to harvesting CH4 for energy production while simultaneously sequestering CO2. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH4)1-x(CO2)x·5.75H2O provides a model system to study how the distinct bonding and shapes of CH4 and CO2 influence the structure and properties of the compound. In this paper, high-resolution neutron diffraction was used to examine mixed CO2/CH4 gas hydrates. CO2-rich hydrates had smaller lattice parameters, which were attributed to the higher affinity of the CO2 molecule interacting with H2O molecules thatmore » form the surrounding cages, and resulted in a reduction in the unit-cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. Finally, these results provide important insights on the impact and mechanisms for the structure of mixed CH4/CO2 gas hydrate.« less

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

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Zheng, Haiyan; Li, Kuo; Cody, George D.; Tulk, Christopher A.; Dong, Xiao; Gao, Guoying; Molaison, Jamie J.; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; et al

    2016-08-25

    Acetonitrile (CH3CN) 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. In this study, 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 sp2 and sp3more » bonded carbon. Lastly, 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.« less

  11. Insights into the structure of mixed CO2/CH4 in gas hydrates

    SciTech Connect (OSTI)

    Everett, Susan M; Rawn, Claudia J; Chakoumakos, Bryan C; Keffer, David J.; Huq, Ashfia; Phelps, Tommy Joe

    2015-01-01

    The exchange of CO2 for CH4 in natural gas hydrates is an attractive approach to methane for energy production while simultaneously sequestering CO2. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH4)1-x(CO2)x 5.75H2O provides a model system to study how the distinct bonding and shapes of CH4 and CO2 influence the structure and properties of the compound. High-resolution neutron diffraction was used to examine mixed CO2/CH4 gas hydrates. CO2-rich hydrates had smaller lattice parameters, which were attributed to the higher affinity of the CO2 molecule interacting with H2O molecules that form the surrounding cages, and resulted in a reduction in the unit cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. These results provide important insights on the impact and mechanisms for exchanging CH4 and CO2.

  12. Voluntary Protection Program Onsite Review, CH2M HILL Plateau Remediation Co., Inc., Hanford – Jan 2014

    Broader source: Energy.gov [DOE]

    Evaluation to determine whether CH2M HILL Plateau Remediation Co., Inc., Hanford is performing at a level deserving DOE-VPP Star recognition.

  13. Contract No. DE-AC02-09CH11466 Section J - Appendix F J-F-1

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    52 Contract No. DE-AC02-09CH11466 Section J - Appendix F J-F-1 Attachment J.6 APPENDIX F Contractor Resources, Commitments, and Agreements Contract No. DE-AC02-09CH11466 Modification No. 0152 Contract No. DE-AC02-09CH11466 Section J - Appendix F J-F-2 This page intentionally blank Modification No. 0152 Contract No. DE-AC02-09CH11466 Section J - Appendix F J-F-3 RESOURCES, SERVICES, AND SUPPORT PROVIDED TO PPPL Princeton University has committed substantial resources and services over the first

  14. Investigation on thermal evaporated CH{sub 3}NH{sub 3}PbI{sub 3} thin films

    SciTech Connect (OSTI)

    Li, Youzhen; Xu, Xuemei; Yang, Junliang; Wang, Chenggong; Wang, Congcong; Gao, Yongli; Xie, Fangyan

    2015-09-15

    CH{sub 3}NH{sub 3}I, PbI{sub 2} and CH{sub 3}NH{sub 3}PbI{sub 3} films were fabricated by evaporation and characterized with X-ray Photoelectron Spectroscopy (XPS) and X-ray diffraction (XRD). The XPS results indicate that the PbI{sub 2} and CH{sub 3}NH{sub 3}PbI{sub 3} films are more uniform and stable than the CH{sub 3}NH{sub 3}I film. The atomic ratio of the CH{sub 3}NH{sub 3}I, PbI{sub 2} and CH{sub 3}NH{sub 3}PbI{sub 3} films are C:N:I=1.00:1.01:0.70, Pb:I= 1.00:1.91 and C: N: Pb: I = 1.29:1.07:1.00:2.94, respectively. The atomic ratio of CH{sub 3}NH{sub 3}PbI{sub 3} is very close to that of the ideal perovskite. Small angle x-ray diffraction results demonstrate that the as evaporated CH{sub 3}NH{sub 3}PbI{sub 3} film is crystalline. The valence band maximum (VBM) and work function (WF) of the CH{sub 3}NH{sub 3}PbI{sub 3} film are about 0.85eV and 4.86eV, respectively.

  15. Altered cardiovascular reactivity and osmoregulation during hyperosmotic stress in adult rats developmentally exposed to polybrominated diphenyl ethers (PBDEs)

    SciTech Connect (OSTI)

    Shah, Ashini; Coburn, Cary G.; Watson-Siriboe, Abena; Whitley, Rebecca; Shahidzadeh, Anoush; Gillard, Elizabeth R.; Nichol, Robert; Leon-Olea, Martha; Gaertner, Mark; Kodavanti, Prasada Rao S.

    2011-10-15

    Polybrominated diphenyl ethers (PBDEs) and the structurally similar chemicals polychlorinated biphenyls (PCBs) disrupt the function of multiple endocrine systems. PCBs and PBDEs disrupt the secretion of vasopressin (VP) from the hypothalamus during osmotic activation. Since the peripheral and central vasopressinergic axes are critical for osmotic and cardiovascular regulation, we examined whether perinatal PBDE exposure could impact these functions during physiological activation. Rats were perinatally dosed with a commercial PBDE mixture, DE-71. Dams were given 0 (corn oil control), 1.7 (low dose) or 30.6 mg/kg/day (high dose) in corn oil from gestational day (GD) 6 through postnatal day (PND) 21 by oral gavage. In the male offspring exposed to high dose PBDE plasma thyroxine and triiodothyronine levels were reduced at PND 21 and recovered to control levels by PND 60 when thyroid stimulating hormone levels were elevated. At 14-18 months of age, cardiovascular responses were measured in four groups of rats: Normal (Oil, normosmotic condition), Hyper (Oil, hyperosmotic stress), Hyper PBDE low (1.7 mg/kg/day DE-71 perinatally, hyperosmotic stress), and Hyper PBDE high (30.6 mg/kg/day DE-71 perinatally, hyperosmotic stress). Systolic blood pressure (BP), diastolic BP, and heart rate (HR) were determined using tail cuff sphygmomanometry and normalized to pretreatment values (baseline) measured under basal conditions. Hyperosmotic treatment yielded significant changes in systolic BP in PBDE exposed rats only. Hyper PBDE low and high dose rats showed 36.1 and 64.7% greater systolic BP responses at 3 h post hyperosmotic injection relative to pretreatment baseline, respectively. No treatment effects were measured for diastolic BP and HR. Hyper and Hyper PBDE rats showed increased mean plasma osmolality values by 45 min after injection relative to normosmotic controls. In contrast to Hyper rats, Hyper PBDE (high) rats showed a further increase in mean plasma osmolality at 3

  16. Low cost hydrogen/novel membrane technology for hydrogen separation from synthesis gas, Phase 1. [Poly(etherimide) and poly(ether-ester-amide) membranes

    SciTech Connect (OSTI)

    Not Available

    1986-01-01

    During the last quarter several high performance membranes for the separation of hydrogen from nitrogen, carbon monoxide, hydrogen sulfide and carbon dioxide. The heat-resistant resin poly(etherimide) has been selected as the polymer with the most outstanding properties for the separation of hydrogen from nitrogen and carbon monoxide. Flat sheet and hollow fiber poly(etherimide) membranes have been prepared and evaluated with pure gases and gas mixtures at elevated pressures and temperatures. Multilayer composite poly(ether-ester-amide) membranes were also developed. These membranes are useful for the separation of carbon dioxide and hydrogen sulfide hydrogen. They have very high selectivities and extremely high normalized carbon dioxide and hydrogen sulfide fluxes. Separation of carbon dioxide/hydrogen streams is a key problem in hydrogen production from coal. The development of the two membranes now gives us two approaches to separate these gas streams, depending on the stream's composition. If the stream contains small quantities of hydrogen, the hydrogen- permeable poly(etherimide) membrane would be used to produce a hydrogen-enriched permeate. If the stream contains small quantities of carbon dioxide or hydrogen sulfide, the poly(ether-ester-amide) membrane would be used to produce a carbon dioxide/hydrogen sulfide-free, hydrogen-enriched residue stream. 6 fig., 4 tabs.

  17. The states of carbon and nitrogen atoms after photodissociation of CN, CH, CH(+), C2, C3, and CO in comets

    SciTech Connect (OSTI)

    Singh, P.D.; De almeida, A.A.; Huebner, W.F. Southwest Research Institute, San Antonio, TX )

    1991-03-01

    The photodissociation of carbon compounds by solar UV radiation at a heliocentric distance of 1 AU is examined, comparing published observational data with the predictions of theoretical models and results from laboratory experiments. It is shown that species other than CO, including CN, CH, CH(+), C2, and C3, can contribute to the observed brightness of the VUV lines of C I (156.1, 165.7, and 193.1 nm) and C II (133.5 nm) in comet comae. CN photodissociation is also found to produce metastable 2D0 and 2P0 N I atoms, possibly leading (at heliocentric distances less than 0.25 AU) to 143.9-nm emission via resonance fluorescence. 37 refs.

  18. Cyclic Versus Linear Isomers Produced by Reaction of the Methylidyne Radical (CH) with Small Unsaturated Hydrocarbons

    SciTech Connect (OSTI)

    Goulay, Fabien; Trevitt, Adam J.; Meloni, Giovanni; Selby, Talitha M.; Osborn, David L.; Taatjes, Craig A.; Vereecken, Luc; Leone, Stephen R.

    2008-12-05

    The reactions of the methylidyne radical (CH) with ethylene, acetylene, allene, and methylacetylene are studied at room temperature using tunable vacuum ultraviolet (VUV) photoionization and time-resolved mass spectrometry. The CH radicals are prepared by 248 nm multiphoton photolysis of CHBr3 at 298 K and react with the selected hydrocarbon in a helium gas flow. Analysis of photoionization efficiency versus VUV photon wavelength permits isomer-specific detection of the reaction products and allows estimation of the reaction product branching ratios. The reactions proceed by either CH insertion or addition followed by H atom elimination from the intermediate adduct. In the CH + C2H4 reaction the C3H5 intermediate decays by H atom loss to yield 70(+-8)percent allene, 30(+-8)percent methylacetylene and less than 10percent cyclopropene, in agreement with previous RRKM results. In the CH + acetylene reaction, detection of mainly the cyclic C3H2 isomer is contrary to a previous RRKM calculation that predicted linear triplet propargylene to be 90percent of the total H-atom co-products. High-level CBS-APNO quantum calculations and RRKM calculation for the CH + C2H2 reaction presented in this manuscript predict a higher contribution of the cyclic C3H2 (27.0percent) versus triplet propargylene (63.5percent) than these earlier predictions. Extensive calculations on the C3H3 and C3H2D system combined with experimental isotope ratios for the CD + C2H2 reaction indicate that H-atom assisted isomerization in the present experiments is responsible for the discrepancy between the RRKM calculations and the experimental results. Cyclic isomers are also found to represent 30(+-6)percent of the detected products in the case of CH + methylacetylene, together with 33(+-6)percent 1,2,3-butatriene and 37(+-6)percent vinylacetylene. The CH + allene reaction gives 23(+-5)percent 1,2,3-butatriene and 77(+-5)percent vinylacetylene, whereas cyclic isomers are produced below the detection limit

  19. Observation of CH4 and other Non-CO2 Green House Gas Emissions from California

    SciTech Connect (OSTI)

    Fischer, Marc L.; Zhao, Chuanfeng; Riley, William J.; Andrews, Arlyn C.

    2009-01-09

    In 2006, California passed the landmark assembly bill AB-32 to reduce California's emissions of greenhouse gases (GHGs) that contribute to global climate change. AB-32 commits California to reduce total GHG emissions to 1990 levels by 2020, a reduction of 25 percent from current levels. To verify that GHG emission reductions are actually taking place, it will be necessary to measure emissions. We describe atmospheric inverse model estimates of GHG emissions obtained from the California Greenhouse Gas Emissions Measurement (CALGEM) project. In collaboration with NOAA, we are measuring the dominant long-lived GHGs at two tall-towers in central California. Here, we present estimates of CH{sub 4} emissions obtained by statistical comparison of measured and predicted atmospheric mixing ratios. The predicted mixing ratios are calculated using spatially resolved a priori CH{sub 4} emissions and surface footprints, that provide a proportional relationship between the surface emissions and the mixing ratio signal at tower locations. The footprints are computed using the Weather Research and Forecast (WRF) coupled to the Stochastic Time-Inverted Lagrangian Transport (STILT) model. Integral to the inverse estimates, we perform a quantitative analysis of errors in atmospheric transport and other factors to provide quantitative uncertainties in estimated emissions. Regressions of modeled and measured mixing ratios suggest that total CH{sub 4} emissions are within 25% of the inventory estimates. A Bayesian source sector analysis obtains posterior scaling factors for CH{sub 4} emissions, indicating that emissions from several of the sources (e.g., landfills, natural gas use, petroleum production, crops, and wetlands) are roughly consistent with inventory estimates, but livestock emissions are significantly higher than the inventory. A Bayesian 'region' analysis is used to identify spatial variations in CH{sub 4} emissions from 13 sub-regions within California. Although, only

  20. DOE Cites CH2M-Washington Group Idaho for Price-Anderson Violations |

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Department of Energy M-Washington Group Idaho for Price-Anderson Violations DOE Cites CH2M-Washington Group Idaho for Price-Anderson Violations June 14, 2007 - 1:40pm Addthis WASHINGTON, DC - The U.S. Department of Energy (DOE) today notified CH2M-Washington Group Idaho (CWI) that it will fine the company $55,000 for violations of the Department's nuclear safety requirements. CWI is the prime contractor responsible for managing the Idaho Cleanup Project at the Idaho National Laboratory site.

  1. Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Wednesday, 28 June 2006 00:00 Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store

  2. Voluntary Protection Program Onsite Review, CH2M HILL B&W West Valley LLC,

    Office of Environmental Management (EM)

    West Valley Demonstration Project - October 2013 | Department of Energy B&W West Valley LLC, West Valley Demonstration Project - October 2013 Voluntary Protection Program Onsite Review, CH2M HILL B&W West Valley LLC, West Valley Demonstration Project - October 2013 Octover 24, 2013 Evaluation to determine whether CH2M HILL B&W West Valley LLC, West Valley Demonstration Project is performing at a level deserving DOE-VPP Star recognition. Voluntary Protection Program Onsite Review,

  3. Joint DOE-CH2M News Release Media Contact: For Immediate Release:

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Joint DOE-CH2M News Release Media Contact: For Immediate Release: Destry Henderson, CH2M, (509) 376-8644, April 20, 2015 destry_j_henderson@rl.gov Mark Heeter, DOE, (509)373-1970, mark.heeter@rl.doe.gov WORKERS REMOVE LAST PENCIL TANK FROM KEY AREA OF HANFORD'S PLUTONIUM FINISHING PLANT Removal of contaminated pencil tanks brings facility one step closer toward demolition RICHLAND, Wash. - More than 50 pencil tank assemblies - some two stories tall - contaminated with chemical and radiological

  4. Contract No.: DE-AC02-07CH11358 Contract Modification No. 0159

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    : DE-AC02-07CH11358 Contract Modification No. 0159 Section J, Appendix C ATTACHMENT J.3 APPENDIX C SPECIAL FINANCIAL INSTITUTION ACCOUNT AGREEMENT Applicable to the Operation of AMES Laboratory Contract No. DE-AC02-07CH11358 AMENDMENT 8 TO SPECIAL FINANCIAL INSTITUTION ACCOUNT Page 1 of 2 AGREEMENT FOR USE WITH THE PAYMENTS CLEARED FINANCING ARRANGEMENT between BANKERS TRUST COMPANY, N.A. (hereinafter referred to as the "Financial Institution"), and IOWA STATE UNIVERSITY of Science and

  5. X-ray Thomson scattering measurements of temperature and density from multi-shocked CH capsules

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Fletcher, L. B.; Glenzer, S. H.; Kritcher, A.; Pak, A.; Ma, T.; Doppner, T.; Fortmann, C.; Divol, L.; Landen, O. L.; Vorberger, J.; et al

    2013-05-24

    Proof-of-principle measurements of the electron densities, temperatures, and ionization states of spherically compressed multi-shocked CH (polystyrene) capsules have been achieved using spectrally resolved x-ray Thomson scattering. A total energy of 13.5 kJ incident on target is used to compress a 70 μm thick CH shell above solid-mass density using three coalescing shocks. Separately, a laser-produced zinc He-α x-ray source at 9 keV delayed 200 ps-800 ps after maximum compression is used to probe the plasma in the non-collective scattering regime. The data show that x-ray Thomson scattering enables a complete description of the time-dependent hydrodynamic evolution of shock-compressed CH capsules,more » with a maximum measured density of ρ > 6 g cm–3. Additionally, the results demonstrate that accurate measurements of x-ray scattering from bound-free transitions in the CH plasma demonstrate strong evidence that continuum lowering is the primary ionization mechanism of carbon L-shell electrons.« less

  6. Turbulence and combustion interaction: High resolution local flame front structure visualization using simultaneous single-shot PLIF imaging of CH, OH, and CH{sub 2}O in a piloted premixed jet flame

    SciTech Connect (OSTI)

    Li, Z.S.; Li, B.; Sun, Z.W.; Alden, M. [Division of Combustion Physics, Lund University, P.O. Box 118, S-221 00 Lund (Sweden); Bai, X.S. [Division of Fluid Mechanics, Lund University, P.O. Box 118, S-221 00 Lund (Sweden)

    2010-06-15

    High resolution planar laser-induced fluorescence (PLIF) was applied to investigate the local flame front structures of turbulent premixed methane/air jet flames in order to reveal details about turbulence and flame interaction. The targeted turbulent flames were generated on a specially designed coaxial jet burner, in which low speed stoichiometric gas mixture was fed through the outer large tube to provide a laminar pilot flame for stabilization of the high speed jet flame issued through the small inner tube. By varying the inner tube flow speed and keeping the mixture composition as that of the outer tube, different flames were obtained covering both the laminar and turbulent flame regimes with different turbulent intensities. Simultaneous CH/CH{sub 2}O, and also OH PLIF images were recorded to characterize the influence of turbulence eddies on the reaction zone structure, with a spatial resolution of about 40 {mu}m and temporal resolution of around 10 ns. Under all experimental conditions, the CH radicals were found to exist only in a thin layer; the CH{sub 2}O were found in the inner flame whereas the OH radicals were seen in the outer flame with the thin CH layer separating the OH and CH{sub 2}O layers. The outer OH layer is thick and it corresponds to the oxidation zone and post-flame zone; the CH{sub 2}O layer is thin in laminar flows; it becomes broad at high speed turbulent flow conditions. This phenomenon was analyzed using chemical kinetic calculations and eddy/flame interaction theory. It appears that under high turbulence intensity conditions, the small eddies in the preheat zone can transport species such as CH{sub 2}O from the reaction zones to the preheat zone. The CH{sub 2}O species are not consumed in the preheat zone due to the absence of H, O, and OH radicals by which CH{sub 2}O is to be oxidized. The CH radicals cannot exist in the preheat zone due to the rapid reactions of this species with O{sub 2} and CO{sub 2} in the inner-layer of the

  7. MW and FTFIR transitions of {sup 13}CH{sub 3}OH revisited and review of MW spectra of CH{sub 3}OH and {sup 13}CH{sub 3}OH of astrophysical interest

    SciTech Connect (OSTI)

    Xu, Li-Hong; Walsh, M.S.; Lees, R.M.

    1996-12-31

    Microwave (MW), millimeter-wave (MMW) and Fourier-transform far-infrared (FTFIR) transitions in the first two torsional states (v{sub t} = 0 below the barrier and v{sub t} = 1 straddling the barrier) of the ground vibrational state of C-13 methanol have been globally treated and successfully fitted to within assigned measurement uncertainties using a program (I. Kleiner and M. Godefroid private communication) originally designed for acetaldehyde (CH{sub 3}CHO) based on the formalism of Herbst et al. The {sup 13}CH{sub 3}OH data set (v {sub t} {le} 1, J {le} 20, K{sub max} {le} 14) contains 725 MW and MMW lines, assigned a {+-}50 kHz measurement uncertainty apart from a few K-doublet lines, and 6283 FTFIR lines each assigned an uncertainty of {+-}0.0002 cm{sup -1} = {+-}6 MHz. A very satisfactory convergent fit has been achieved using 55 adjustable and 2 fixed parameters, yielding an overall weighted standard deviation of 0.962. Calculations employing the parameters from the final fit reveal possible C-13 assignments for 28 lines appearing in natural abundance in the newly-measured methanol microwave atlas from 7 to 200 GHz compiled by the group of K. Takagi at Toyama University.

  8. Communication: Photodissociation of CH{sub 3}CHO at 308 nm: Observation of H-roaming, CH{sub 3}-roaming, and transition state pathways together along the ground state surface

    SciTech Connect (OSTI)

    Li, Hou-Kuan; Tsai, Po-Yu; Hung, Kai-Chan; Kasai, Toshio; Lin, King-Chuen

    2015-01-28

    Following photodissociation of acetaldehyde (CH{sub 3}CHO) at 308 nm, the CO(v = 1–4) fragment is acquired using time-resolved Fourier-transform infrared emission spectroscopy. The CO(v = 1) rotational distribution shows a bimodal feature; the low- and high-J components result from H-roaming around CH{sub 3}CO core and CH{sub 3}-roaming around CHO radical, respectively, in consistency with a recent assignment by Kable and co-workers (Lee et al., Chem. Sci. 5, 4633 (2014)). The H-roaming pathway disappears at the CO(v ≥ 2) states, because of insufficient available energy following bond-breaking of H + CH{sub 3}CO. By analyzing the CH{sub 4} emission spectrum, we obtained a bimodal vibrational distribution; the low-energy component is ascribed to the transition state (TS) pathway, consistent with prediction by quasiclassical trajectory calculations, while the high-energy component results from H- and CH{sub 3}-roamings. A branching fraction of H-roaming/CH{sub 3}-roaming/TS contribution is evaluated to be (8% ± 3%)/(68% ± 10%)/(25% ± 5%), in which the TS pathway was observed for the first time. The three pathways proceed concomitantly along the electronic ground state surface.

  9. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived syngas; Quarterly technical progress report No. 3, 1 July--30 September 1990

    SciTech Connect (OSTI)

    1991-01-25

    Contract objectives are: development of a one-step liquid phase dimethyl ether/methanol process; and investigation of the potential of liquid phase synthesis of alternative fuels from coal-derived synthesis gas. Definition of Preferred Catalyst System was completed after several commercial methanol catalysts and dehydration catalysts were tested. BASF S3-86 and Catapal gamma alumina is the preferred catalyst system of choice. Process Variable Scans on the Preferred Catalyst System was started with Shell gas. Data were obtained at various pressures (750 to 1400 psig), temperatures (250 to 280{degrees}C), and space velocities (5000 to 9000 sl/kg-hr). Increase in system pressure seems to have a very significant benefit to both DME and methanol formation. Both Texaco and Shell gases were evaluated. A ``stoichiometric`` feed composition (50% CO, 50% H{sub 2}) that yields maximum DME productivity at equilibrium was evaluated with a fresh batch of the optimum catalyst system. Productivities with the ``stoichiometric`` gas were much higher compared to Shell or Texaco gas. Following that test, Dow gas was evaluated (41% CO, 41% H{sub 2}, 16% CO{sub 2} and 2% N{sub 2}) using the same catalyst to study the effect of CO{sub 2}. Three DME/MEOH (1--4% DME) mixtures were evaluated by SWRI for their fuel properties. Results indicate that, with small amounts of DME added, significant improvements in both flash point and RVP are possible over the properties of LaPorte MEOH. the slurry-phase dehydration of alcohols to ethers was investigated by feeding 10 mol% mixed alcohols in N{sub 2} over an alumina catalyst suspended in mineral oil. Two alcohol mixture compositions were chosen for this study. One mixture contained methanol, ethanol, and 1-propanol in proportions representative of those in IFP Substifuel, while the other mixture contained methanol, ethanol, and isobutanol in proportions representative of those in Lurgi Octamix. 21 figs., 13 tabs.

  10. Rare-earth transition-metal gallium chalcogenides RE{sub 3}MGaCh{sub 7} (M=Fe, Co, Ni; Ch=S, Se)

    SciTech Connect (OSTI)

    Rudyk, Brent W.; Stoyko, Stanislav S.; Oliynyk, Anton O.; Mar, Arthur

    2014-02-15

    Six series of quaternary rare-earth transition-metal chalcogenides RE{sub 3}MGaCh{sub 7} (M=Fe, Co, Ni; Ch=S, Se), comprising 33 compounds in total, have been prepared by reactions of the elements at 1050 °C (for the sulphides) or 900 °C (for the selenides). They adopt noncentrosymmetric hexagonal structures (ordered Ce{sub 3}Al{sub 1.67}S{sub 7}-type, space group P6{sub 3}, Z=2) with cell parameters in the ranges of a=9.5–10.2 Å and c=6.0–6.1 Å for the sulphides and a=10.0–10.5 Å and c=6.3–6.4 Å for the selenides as refined from powder X-ray diffraction data. Single-crystal structures were determined for five members of the sulphide series RE{sub 3}FeGaS{sub 7} (RE=La, Pr, Tb) and RE{sub 3}CoGaS{sub 7} (RE=La, Tb). The highly anisotropic crystal structures consist of one-dimensional chains of M-centred face-sharing octahedra and stacks of Ga-centred tetrahedra all pointing in the same direction. Magnetic measurements on the sulphides reveal paramagnetic behaviour in some cases and long-range antiferromagnetic behaviour with low Néel temperatures (15 K or lower) in others. Ga L-edge XANES spectra support the presence of highly cationic Ga tetrahedral centres with a tendency towards more covalent Ga–Ch character on proceeding from the sulphides to the selenides. Band structure calculations on La{sub 3}FeGaS{sub 7} indicate that the electronic structure is dominated by Fe 3d-based states near the Fermi level. - Graphical abstract: The series of chalcogenides RE{sub 3}MGaS{sub 7}, which form for a wide range of rare-earth and transition metals (M=Fe, Co, Ni), adopt highly anisotropic structures containing chains of M-centred octahedra and stacks of Ga-centred tetrahedra. Display Omitted - Highlights: • Six series (comprising 33 compounds) of chalcogenides RE{sub 3}MGaCh{sub 7} were prepared. • They adopt noncentrosymmetric hexagonal structures with high anisotropy. • Most compounds are paramagnetic; some show antiferromagnetic ordering. • Ga L

  11. M-transfer activity of MCM-41 materials in 1-hexene isomerization reactions

    SciTech Connect (OSTI)

    Dominguez, J.M.; Hernandez, F.; Terres, E.; Toledo, A.; Navarrete, J.

    1996-10-01

    The gasoline reformulation scheme includes the use of oxygenated additives MTBE (methyl-ter-butyl-ether), TAME (ter-amyl-methyl-ether), ETBE (ethyl-ter-butyl-ether) and DIPE (di-isopropyl-ether), which have the iso-olefins (i-C{sub 3}{sup =}, i-C{sub 4}{sup =}, i-C{sub 5}{sup =}) as precursors. In this respect, olefin production from FCC units must be enhanced to cover the demand. A series of new catalytic materials with lower hydrogen transfer activity could enhance the olefin yield from the FCC reactors.

  12. CO2 CH4 flux Air temperature Soil temperature and Soil moisture, Barrow, Alaska 2013 ver. 1

    SciTech Connect (OSTI)

    Margaret Torn

    2015-01-14

    This dataset consists of field measurements of CO2 and CH4 flux, as well as soil properties made during 2013 in Areas A-D of Intensive Site 1 at the Next-Generation Ecosystem Experiments (NGEE) Arctic site near Barrow, Alaska. Included are i) measurements of CO2 and CH4 flux made from June to September (ii) Calculation of corresponding Gross Primary Productivity (GPP) and CH4 exchange (transparent minus opaque) between atmosphere and the ecosystem (ii) Measurements of Los Gatos Research (LGR) chamber air temperature made from June to September (ii) measurements of surface layer depth, type of surface layer, soil temperature and soil moisture from June to September.

  13. CO2 CH4 flux Air temperature Soil temperature and Soil moisture, Barrow, Alaska 2013 ver. 1

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Margaret Torn

    This dataset consists of field measurements of CO2 and CH4 flux, as well as soil properties made during 2013 in Areas A-D of Intensive Site 1 at the Next-Generation Ecosystem Experiments (NGEE) Arctic site near Barrow, Alaska. Included are i) measurements of CO2 and CH4 flux made from June to September (ii) Calculation of corresponding Gross Primary Productivity (GPP) and CH4 exchange (transparent minus opaque) between atmosphere and the ecosystem (ii) Measurements of Los Gatos Research (LGR) chamber air temperature made from June to September (ii) measurements of surface layer depth, type of surface layer, soil temperature and soil moisture from June to September.

  14. High-resolution spectroscopy of jet-cooled CH{sub 5}{sup +}: Progress

    SciTech Connect (OSTI)

    Savage, C.; Dong, F.; Nesbitt, D. J.

    2015-01-22

    Protonated methane (CH{sub 5}{sup +}) is thought to be a highly abundant molecular ion in interstellar medium, as well as a potentially bright μwave- mm wave emitter that could serve as a tracer for methane. This paper describes progress and first successful efforts to obtain a high resolution, supersonically cooled spectrum of CH{sub 5}{sup +} in the 2900-3100 cm{sup −1} region, formed in a slit supersonic discharge at low jet temperatures and with sub-Doppler resolution. Short term precision in frequency measurement (< 5 MHz on an hour time scale) is obtained from a thermally controlled optical transfer cavity servoloop locked onto a frequency stabilized HeNe laser. Long term precision (< 20 MHz day-to-day) due to pressure, temperature and humidity dependent index of refraction effects in the optical transfer cavity is also present and discussed.

  15. APPENDXD.CHP:Corel VENTURA

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    Report The Form EIA-819, "Monthly Oxygenate Report" provides production data for fuel ethanol and methyl tertiary butyl ether (MTBE). End-of-month stock data held at ethanol...

  16. Preparations for Meeting New York and Connecticut MTBE Bans

    Reports and Publications (EIA)

    2003-01-01

    In response to a Congressional request, the Energy Information Administration examined the progress being made to meet the bans on the use of methyl tertiary butyl ether (MTBE) being implemented in New York and Connecticut at the end of 2003.

  17. March 2015 Most Viewed Documents for Geosciences | OSTI, US Dept...

    Office of Scientific and Technical Information (OSTI)

    Poux, B. (2010) 34 Produced water volumes and management practices in the United States. ... Ether and tert-Butyl Alcohol in Water by Solid-Phase MicroextractionHead Space ...

  18. The U.S. Department of Energy and contractor CH2M HILL Plateau Remediation

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    6 . The U.S. Department of Energy and contractor CH2M HILL Plateau Remediation Company manage the Waste Encapsulation and Storage Facility at the Hanford Site in southeast Washington state. Waste Encapsulation and Storage Facility Background The Waste Encapsulation and Storage Facility (WESF) provides safe and compliant underwater storage for 1,936 highly radioactive capsules containing the elements cesium and strontium. In the 1970s, radioactive isotopes of the chemical elements cesium and

  19. Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation

    SciTech Connect (OSTI)

    Watzke, Anja; Wilson, Rebecca; O'Malley, Steven; Bergman, Robert; Ellman, Jonathan

    2007-04-16

    The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

  20. 10 CFR Ch. III (1-1-11 Edition) Pt. 851, App. B

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    2 10 CFR Ch. III (1-1-11 Edition) Pt. 851, App. B must meet the applicable electrical safety codes and standards referenced in § 851.23. 11. NANOTECHNOLOGY SAFETY-RESERVED The Department has chosen to reserve this section since policy and procedures for nano- technology safety are currently being devel- oped. Once these policies and procedures have been approved, the rule will be amended to include them through a rulemaking con- sistent with the Administrative Procedure Act. 12. WORKPLACE

  1. New directions for QA in basic research: The Fermilab/DOE-CH experience

    SciTech Connect (OSTI)

    Bodnarczuk, M.

    1989-09-01

    This paper addresses the underlying problems involved in developing institution-wide QA programs at DOE funded basic research facilities, and suggests concrete ways in which QA professionals and basic researchers can find common ground in describing and analyzing those activities to the satisfaction of both communities. The paper is designed to be a springboard into workshop discussions which can define a path for developing institution-wide QA programs based on the experience gained with DOE-CH and Fermilab.

  2. Communication: Ultraviolet photodissociation dynamics of the simplest Criegee intermediate CH{sub 2}OO

    SciTech Connect (OSTI)

    Lehman, Julia H.; Li, Hongwei; Beames, Joseph M.; Lester, Marsha I.

    2013-10-14

    The velocity and angular distributions of O {sup 1}D photofragments arising from UV excitation of the CH{sub 2}OO intermediate on the B {sup 1}A??X {sup 1}A? transition are characterized using velocity map ion imaging. The anisotropic angular distribution yields the orientation of the transition dipole moment, which reflects the ?*?? character of the electronic transition associated with the COO group. The total kinetic energy release distributions obtained at several photolysis wavelengths provide detail on the internal energy distribution of the formaldehyde cofragments and the dissociation energy of CH{sub 2}OO X {sup 1}A? to O {sup 1}D + H{sub 2}CO X {sup 1}A{sub 1}. A common termination of the total kinetic energy distributions, after accounting for the different excitation energies, gives an upper limit for the CH{sub 2}OO X {sup 1}A? dissociation energy of D{sub 0}? 54 kcal mol{sup ?1}, which is compared with theoretical predictions including high level multi-reference ab initio calculations.

  3. Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH4 on Pt(111)

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Guo, Han; Jackson, Bret

    2016-05-13

    A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v3 and 2v3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v1 symmetric stretch of CH4 is more effective at promoting the dissociative chemisorption of CH4 than exciting the 1v3 antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabaticmore » states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.« less

  4. Aerobic C-H Acetoxylation of 8-Methylquinoline in PdII-Pyridinecarboxylic Acid Systems: Some Structure-Reactivity Relationships

    SciTech Connect (OSTI)

    Wang, Daoyong; Zavalij, Peter Y.; Vedernikov, Andrei N.

    2013-09-09

    Catalytic oxidative CH acetoxylation of 8-methylquinoline as a model substrate with O2 as oxidant was performed using palladium(II) carboxylate catalysts derived from four different pyridinecarboxylic acids able to form palladium(II) chelates of different size. A comparison of the rates of the substrate CH activation and the O2 activation steps shows that the CH activation step is rate-limiting, whereas the O2 activation occurs at a much faster rate already at 20 C. The chelate ring size and the chelate ring strain of the catalytically active species are proposed to be the key factors affecting the rate of the CH activation.

  5. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Ethanol Plant Production Definitions Key Terms Definition Barrel A unit of volume equal to 42 U.S. gallons. Fuel Ethanol An anhydrous alcohol (ethanol with less than 1% water) intended for gasoline blending as described in the Oxygenates definition. Oxygenates Substances which, when added to gasoline, increase the amount of oxygen in that gasoline blend. Ethanol, Methyl Tertiary Butyl Ether (MTBE), Ethyl Tertiary Butyl Ether (ETBE), and methanol are common oxygenates. Fuel Ethanol: Blends of up

  6. ch_11

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    0 11.0 Response Response to to P P ublic ublic Comment Comment 11-1 DOE/EIS-0287 11.1 Introduction This chapter provides responses from the U.S. Department of Energy (DOE) and the State of Idaho to public comments on the Draft Idaho High-Level Waste and Facilities Disposition Environmental Impact Statement (HLW & FD EIS) and identifies where those public comments led to changes to the EIS. The State of Idaho, a cooperating agency in the preparation of the EIS, participated in the process of

  7. ch_12

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    .0 12.0 Distribution Distribution List List - New Information - 12-1 DOE/EIS-0287 The U.S. Department of Energy (DOE) pro- vided copies of this Final Environmental Impact Statement (EIS) to Federal, state, and local elected and appointed officials and agencies of government; Native American groups; national, state, and local environmental and public interest groups; and other organizations and individuals list- ed below. In addition, DOE sent copies of the Final EIS to all persons who comment-

  8. ch_13

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    .0 13.0 Index Index 13-1 DOE/EIS-0287 DOE/EIS-0287 13-2 Index A aesthetics - 3-54, 4-18, 4-35, 5-17, 5-18, 5-214, 5-232, 5-233, 9-9, 10-3, 10-7, C.2-4, C.8-13, C.8-32, C.8-46 airborne releases - 4-32, 4-71, 4-72, 5-48, 5-74, 5-87, 5-184, 5-225, C.2-13, C.2-17, C.8-16, C.8-36 aquifer - 2-30, 2-32, 2-33, 4-40, 4-47, 4-48, 4-49, 4-50, 4-51, 4-53, 4-54, 4-55, 4-56, 4-57, 4-72, 4-79, 5-2, 5-20, 5-44, 5-45, 5-107, 5-121, 5-122, 5-161, 5-165, 5-180, 5-212, 5-221, 5-222, 5-225, 5-227, 5-233, 5-234,

  9. ch_2

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    4 Background 2.1.3 CURRENT MISSION The current INEEL mission is to develop, demonstrate, and deploy advanced engineering technology and systems to improve national competitiveness and security, to make the pro- duction and use of energy more efficient, and to improve the quality of the environment. Areas of primary emphasis at INEEL include waste management and waste minimization, environ- mental engineering and restoration, energy effi- ciency, renewable energy, national security and defense,

  10. ch_2

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    10 Background 2.2 High-Level Waste Overview 2.2.1 HIGH-LEVEL WASTE DESCRIPTION According to Section 2(12) of the Nuclear Waste Policy Act (42 USC 10101), high-level radioac- tive waste means: In July 1999, DOE issued Order 435.1 Radioactive Waste Management. This Order and its associated Manual and Guidance set forth the authorities, responsibilities, and requirements for the management of DOE's inventory of HLW, transuranic waste, and low-level waste. Specific to HLW, DOE uses the Nuclear Waste

  11. ch_3

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    0 3.0 Alterna Alterna tiv tiv es es 3-1 DOE/EIS-0287 This chapter describes the alternatives for waste processing and facility disposi- tion analyzed in this environmental impact statement (EIS) as well as alter- natives eliminated from detailed analy- sis. As required by the Council on Environmental Quality (CEQ) regula- tions implementing the National Environmental Policy Act (NEPA), a No Action alternative is also included. This chapter identifies the U.S. Department of Energy's (DOE's)

  12. ch_3

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    13 DOE/EIS-0287 Idaho HLW & FD EIS except the pillar and panel tanks) would be full of mixed transuranic waste in approximately 2017. Other facilities depending on the capacity of the Tank Farm for operation eventually would be shut down due to their inability to discharge liquid waste. Under this alternative, DOE would not meet its commitment to cease use of the Tank Farm by 2012 or to make its mixed HLW road ready by 2035. Facilities required for the No Action Alternative include the bin

  13. ch_3

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    3-34 Alternatives transuranic waste/SBW. The EIS also presents the impacts for a grout facility (see Project P2001 in Appendix C.6) that could be used to treat the waste generated after 2005. For pur- poses of assessing transportation impacts, DOE assumed the grouted waste would be character- ized as remote-handled transuranic waste and transported to the Waste Isolation Pilot Plant for disposal (see Appendix C.5). 3.2 Facility Disposition Alternatives The waste processing alternatives described

  14. ch_3

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    47 DOE/EIS-0287 Idaho HLW & FD EIS has been provided to the public, committed DOE to restoring the existing contaminated groundwater plume outside the INTEC security fence to meet the current drinking water stan- dard of 4 millirem per year. A performance assessment would be developed for each facility or group of facilities under consideration for disposition, to determine which of the three disposition alternatives would be implemented. The performance assessment results would be used to

  15. ch_4

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    0 4.0 Aff Aff ected ected E E nvir nvir onment onment 4-1 DOE/EIS-0287 4.1 Introduction This chapter describes the environment of the Idaho National Engineering and Environmental Laboratory (INEEL) and surrounding area that could be affected by the alternatives analyzed in this environ- mental impact statement (EIS). One of the alternatives under consideration, the Minimum INEEL Processing Alternative, would involve treatment of INEEL high- level waste (HLW) at the Hanford Site. Appendix C.8

  16. ch_4

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    1998, INEEL contracts paid $1.4 million to the State of Idaho in Idaho sales taxes and an additional $0.9 million in Idaho franchise tax. 4.4 Cultural Resources 4.4.1 CULTURAL RESOURCE MANAGEMENT AND CONSULTATION AT INEEL Cultural resources at INEEL include archaeolog- ical and historic resources, such as prehistoric camp sites and historic buildings and trails, as well as the plants, animals, physical locations, and other features of INEEL environment impor- tant to the culture of the

  17. ch_4

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    18 Affected Environment visual range of the Fort Hall Indian Reservation. The Bitterroot, Lemhi, and Lost River mountain ranges are visible to the north and west of INEEL. East Butte and Middle Butte can be seen near the southern boundary, while Circular and Antelope Buttes are visible to the northeast. Smaller volcanic buttes dot the natural landscape of INEEL, providing a striking contrast to the relatively flat ground surface. The viewscape in general consists of terrain dominated by sage-

  18. ch_4

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    40 Affected Environment playas 15 to 20 miles northeast of INTEC, where the water infiltrates. The water in Birch Creek and the Little Lost River is diverted in summer months for irriga- tion prior to reaching INEEL. During periods of unusually high precipitation or rapid snow melt, water from Birch Creek and the Little Lost River may enter INEEL from the northwest and infil- trate the ground, recharging the underlying aquifer. 4.8.1.2 Local Drainage INTEC is located on an alluvial plain

  19. ch_4

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    58 Affected Environment 4.9.1 PLANT COMMUNITIES AND ASSOCIATIONS INEEL lies within a cool desert ecosystem dom- inated by shrub-steppe vegetation. The area is relatively undisturbed, providing important habi- tat for species native to the region. Vegetation and habitat on INEEL can be grouped into six types: shrub-steppe, juniper woodlands, native grasslands, modified ephemeral playas, lava, and wetland-like areas. Figure 4-16 shows these areas. More than 90 percent of INEEL falls within the

  20. ch_5

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    0 5.0 E E nvir nvir onmental onmental Consequences Consequences 5-1 DOE/EIS-0287 5.1 Introduction Chapter 5 describes the potential environ- mental consequences of implementing each of the alternatives described in Chapter 3. This Final EIS analyzes the alternatives in the Draft EIS and provides corrections and updates as needed. In addition, it analyzes the State of Idaho's Preferred Alternative, Direct Vitrification, and a new option of the Non-Separations Alternative, the Steam Reforming

  1. ch_5

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    25 DOE/EIS-0287 Idaho HLW & FD EIS 5.3 Facility Disposition Impacts Section 5.3 presents a discussion of potential impacts associated with the disposition of exist- ing HLW management facilities at INEEL and disposition of new facilities that would be built in support of the proposed waste processing alternatives. The discussion includes (1) the potential impacts of short-term actions in dispo- sitioning new and existing HLW management facilities, (2) the potential long-term impacts from the

  2. ch_5

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    45 DOE/EIS-0287 Idaho HLW & FD EIS 5.3.4.2 Existing Facilities Associated with High-Level Waste Management The facilities in this group are those that have historically been used at the INTEC to generate, treat, and store HLW. Because of the number of facilities involved, DOE has grouped them in functional groups for purposes of analysis (see Table 3-3). DOE analyzed the HLW tanks and bin sets for closure under all five disposition sce- narios; however, facilities that support the Tank Farm

  3. ch_6

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    0 6.0 Sta Sta tutes tutes , , Regula Regula tions tions , , Consulta Consulta tions tions , , and Other and Other Requir Requir ements ements 6-1 DOE/EIS-0287 This chapter discusses the consultations and coordination the U.S. Department of Energy (DOE) has had with various agen- cies during the preparation of this Environmental Impact Statement (EIS). This chapter also analyzes the complex regulatory issues that arise when consider- ing the various alternatives discussed pre- viously. When

  4. ch_7

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    0 7.0 Glossar Glossar y y 7-1 DOE/EIS-0287 Terms in this glossary are defined based on the context in which they are to be used in this Environmental Impact Statement (EIS). - New Information - DOE/EIS-0287 7-2 Glossary 100-year flood A flood that occurs, on average, every 100 years (equates to a 1 percent probability of occurring in any given year). 500-year flood A flood that occurs, on average, every 500 years (equates to a 0.2 percent probability of occurring in any given year). accident An

  5. ch_8

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    .0 8.0 Contents of Contents of Appendices Appendices 8-1 DOE/EIS-0287 This chapter provides the contents of the appendices supporting this EIS. The appendices contain technical information supporting the analysis in this EIS, and scanned comment response documents received by DOE during the public com- ment period. The appendices are pub- lished separately and are available on request. - New Information - DOE/EIS-0287 8-2 Contents of Appendices TABLE OF CONTENTS Section Appendix A Site

  6. ch_9

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

  7. ch_9

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    COVER SHEET Responsible Agency: Lead Federal Agency: U.S. Department of Energy (DOE) Cooperating Agency: The State of Idaho Title: Contact: For additional information on this EIS and the tribal, agency and public involvement process con- ducted in conjunction with its preparation, write or call: This Final EIS is composed of a Summary, Chapters 1 through 13, and appendices. Copies of the EIS or appendices may be requested from Richard Kimmel at the address, phone number, or email address shown

  8. ch_9

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... and Management of Sodium-Bonded Spent Nuclear Fuel, ... Including the Role of the Fast Flux Test Facility, DOE... the Navy, Office of Naval Reactors, letter to W. R. Dixon, ...

  9. ch_4

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... Low-income populations are identified using statistical poverty thresholds from the Bureau of Census Current Population Reports, Series P-60 on Income and Poverty. In identifying ...

  10. ch_2

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    B B ackgr ackgr ound ound The Idaho National Engineering and Environmental Laboratory (INEEL) cur- rently manages waste associated with the processing of spent nuclear reactor ...

  11. ch_10

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... William R. McDonell Ph.D., Nuclear Chemistry, 1951 M.S., Chemistry, 1948 B.S., Chemistry, 1947 50 years experience in nuclear and radiation technologies including strategies for ...

  12. ch_1

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... The Nuclear Waste Policy Act of 1982, as amended, determined that a geological repository ... obtain- ing representative con- stituent samples from the large volumes of mixed ...

  13. ch_5

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    44 Environmental Consequences 5.2.7 WATER RESOURCES This section presents potential water resource impacts from implement- ing the proposed waste processing alternatives described ...

  14. ch_4

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    47 DOEEIS-0287 Idaho HLW & FD EIS 4.8.2 SUBSURFACE WATER Subsurface water at INEEL occurs in the under- lying Snake River Plain Aquifer and the vadose zone (area of unsaturated ...

  15. ch_5

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... displacement of less disturbance tolerant individuals. ... water, and fossil fuels, and the generation of wastewater. ... An accident analysis is performed to identify environmental ...

  16. ch_3

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Idaho HLW & FD EIS poured into Savannah River Site-type stainless steel canisters. Figure ... The steam reformed product would be packaged in Savannah River Site-type stainless steel ...

  17. ch_5

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... by the application of water, use of soil additives, and ... and health impacts from atmospheric emissions from the waste ... compactors) and portable generators dur- ing construction ...

  18. ch_5

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... As specified by Sections 650 and 651 of Rules for the Control of Air Pollution in Idaho (IDEQ 2001), all reasonable precautions would be taken to prevent the generation of fugitive ...

  19. ch_4

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... Air quality regulations have been established to protect the public from potential harmful effects of air pollution. These regulations (a) designate acceptable levels of pollution ...

  20. Electrochemical Investigation of Al–Li/LixFePO4 Cells in Oligo(ethylene glycol) Dimethyl Ether/LiPF6

    SciTech Connect (OSTI)

    Wang, X.J.; Zhou, Y.N.; Lee, H.S.; Nam, K.W.; Yang, X.Q.; Haas, O.

    2011-02-01

    1 M LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight, 500 g mol{sup -1} (OEGDME500, 1 M LiPF{sub 6}), was investigated as an electrolyte in experimental Al-Li/LiFePO{sub 4} cells. More than 60 cycles were achieved using this electrolyte in a Li-ion cell with an Al-Li alloy as an anode sandwiched between two Li x FePO{sub 4} electrodes (cathodes). Charging efficiencies of 96-100% and energy efficiencies of 86-89% were maintained during 60 cycles at low current densities. A theoretical investigation revealed that the specific energy can be increased up to 15% if conventional LiC{sub 6} anodes are replaced by Al-Li alloy electrodes. The specific energy and the energy density were calculated as a function of the active mass per electrode surface (charge density). The results reveal that for a charge density of 4 mAh cm{sup -2} about 160 mWh g{sup -1} can be reached with Al-Li/LiFePO{sub 4} batteries. Power limiting diffusion processes are discussed, and the power capability of Al-Li/LiFePO{sub 4} cells was experimentally evaluated using conventional electrolytes.

  1. The Radiative Transfer Of CH{sub 4}-N{sub 2} Plasma Arc

    SciTech Connect (OSTI)

    Benallal, R.; Liani, B.

    2008-09-23

    Any physical modelling of a circuit-breaker arc therefore requires an understanding of the radiated energy which is taken into account in the form of a net coefficient. The evaluation of the net emission coefficient is performed by the knowledge of the chemical plasma composition and the resolution of the radiative transfer equation. In this paper, the total radiation which escapes from a CH{sub 4}-N{sub 2} plasma is calculated in the temperature range between 5000 and 30000K on the assumption of a local thermodynamic equilibrium and we have studied the nitrogen effect in the hydrocarbon plasmas.

  2. ASSESSMENT REPORT Audit Coverage of Cost Allowability for URS | CH2M Oak Ridge LLC During

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    for URS | CH2M Oak Ridge LLC During Fiscal Years 2011, 2012, and 2013 Under Department of Energy Contract No. DE-SC0004645 OAI-V-16-09 June 2016 U.S. Department of Energy Office of Inspector General Office of Audits and Inspections Department of Energy Washington, DC 20585 June 10, 2016 MEMORANDUM FOR THE MANAGER, OAK RIDGE OFFICE OF ENVIRONMENTAL MANAGEMENT FROM: Debra K. Solmonson Deputy Assistant Inspector General for Audits and Inspections Office of Inspector General SUBJECT: INFORMATION:

  3. Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

  4. Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

  5. Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

  6. Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

  7. Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Hydrogen Storage in Carbon Nanotubes Through Formation of C-H Bonds Print Two of the major challenges for humanity in the next 20 years are the shrinking availability of fossil fuels and the global warming and potential climate changes that result from their ever-increasing use. One possible solution to these problems is to use an energy carrier such as hydrogen, and ways to produce and store hydrogen in electric power plants and vehicles is a major research focus for materials scientists and

  8. THE CHANDRA ACIS SURVEY OF M33 (ChASeM33): THE FINAL SOURCE CATALOG

    SciTech Connect (OSTI)

    Tuellmann, R.; Gaetz, T. J.; Plucinsky, P. P.; Challis, P.; Edgar, R. J.; Kirshner, R. P.; Kuntz, K. D.; Blair, W. P.; Williams, B. F.; Pietsch, W.; Haberl, F.; Long, K. S.; Sasaki, M.; Winkler, P. F.; Pannuti, T. G.; Helfand, D. J.; Hughes, J. P.; Mazeh, T.; Shporer, A.

    2011-04-01

    This study presents the final source catalog of the Chandra ACIS Survey of M33 (ChASeM33). With a total exposure time of 1.4 Ms, ChASeM33 covers {approx}70% of the D{sub 25} isophote (R {approx} 4.0 kpc) of M33 and provides the deepest, most complete, and detailed look at a spiral galaxy in X-rays. The source catalog includes 662 sources, reaches a limiting unabsorbed luminosity of {approx}2.4x10{sup 34} erg s{sup -1} in the 0.35-8.0 keV energy band, and contains source positions, source net counts, fluxes and significances in several energy bands, and information on source variability. The analysis challenges posed by ChASeM33 and the techniques adopted to address these challenges are discussed. To constrain the nature of the detected X-ray source, hardness ratios were constructed and spectra were fit for 254 sources, follow-up MMT spectra of 116 sources were acquired, and cross-correlations with previous X-ray catalogs and other multi-wavelength data were generated. Based on this effort, 183 of the 662 ChASeM33 sources could be identified. Finally, the luminosity function (LF) for the detected point sources as well as the one for the X-ray binaries (XRBs) in M33 is presented. The LFs in the soft band (0.5-2.0 keV) and the hard band (2.0-8.0 keV) have a limiting luminosity at the 90% completeness limit of 4.0 x 10{sup 34} erg s{sup -1} and 1.6 x 10{sup 35} erg s{sup -1}(for D = 817 kpc), respectively, which is significantly lower than what was reported by previous XRB population studies in galaxies more distant than M33. The resulting distribution is consistent with a dominant population of high-mass XRBs as would be expected for M33.

  9. Protons acceleration in thin CH foils by ultra-intense femtosecond laser pulses

    SciTech Connect (OSTI)

    Kosarev, I. N.

    2015-03-15

    Interaction of femtosecond laser pulses with the intensities 10{sup 21}, 10{sup 22 }W/cm{sup 2} with CH plastic foils is studied in the framework of kinetic theory of laser plasma based on the construction of propagators (in classical limit) for electron and ion distribution functions in plasmas. The calculations have been performed for real densities and charges of plasma ions. Protons are accelerated both in the direction of laser pulse (up to 1 GeV) and in the opposite direction (more than 5 GeV). The mechanisms of forward acceleration are different for various intensities.

  10. Contract No. DE-AC02-09CH11466 Section F

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Modification No. 0164 Contract No. DE-AC02-09CH11466 Section F i PART I SECTION F DELIVERIES OR PERFORMANCE TABLE OF CONTENTS CLAUSE NO. TITLE OF CLAUSE F.1 PERIOD OF PERFORMANCE (Revised by Prime Contract Modification 041 - 07/13/2010; 0137 - 10/28/2013; 0164 - 08/07/2014) F.2 AWARD TERM INCENTIVE (SPECIAL) F.3 FAR 52.242-15 - STOP WORK ORDER (AUG 1989) ALTERNATE I (APR 1984) F.4 STOP WORK AND SHUTDOWN AUTHORITY F.5 PRINCIPAL PLACE OF PERFORMANCE Modification No. 0164 Contract No.

  11. Ed Jascevsky Safety Division ChIcago Operations Office MIT CONTFACT INFCE"ATION

    Office of Legacy Management (LM)

    ;/:4,4 (; . 1.; e octo: ' J : 18, 1976 Ed Jascevsky Safety Division ChIcago Operations Office MIT CONTFACT INFCE"ATION During the discussions on October 8, 1976, you iquired about information relative to work done by MIT as background infomation for survey planning. The enclosed information is parephrased frorc an unpublished history of program work carried out by the Process Eevclopncnt Group of the Dl.ti,si.on of Raw Katerids, I believe this work was done under contract nuder AT(30-1)956.

  12. HA' R$,kAW CH EM I CAL CO,M i=ANY A

    Office of Legacy Management (LM)

    TH Ii ' HA' R$,kAW CH EM I CAL CO,M i=ANY A December 30, 1955 U. S. Atomic Energy Commission Oak Ridge OperationwOfflce Post Office Box "E" Oak Ridge, Tennessee Attention: Mr. T. Carberry Dear Mr. Carberry: ' ..> In the process of removing 'classified documents from the safes at the Main Office for des$ruction we discovered two sample cylinders of hexafluorlde. If memory serves us right these sample6 were prepared at the request of the Commission and shipped to the Unl- versity of

  13. Contract No. DE-AC02-07CH11358 Contract Modification No. 0192

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Contract Modification No. 0192 Section J Appendix H ATTACHMENT J.8 APPENDIX H SMALL BUSINESS SUBCONTRACTING PLAN Applicable to the Operation of AMES Laboratory Contract No. DE-AC02-07CH11358 'I'Hv. Ames Laboratory CtNrlng M*t*rl*l* & En*rgy So/utlotJI U ~ S, 0 £ J 1 A HT.M!NT C H' BNE UGY 2016 Subcontracting Plan Contractor: Ames Laboratory atlowa State Univers'ity (in eSRS a fowa State Equities Corporation) Address: 224 TASF, Ames IA 50011-3020 Solicitation or Contract Number: DE

  14. Contract No. DE-AC02-07CH11358 Section E Contract Modification No. 133

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    E Contract Modification No. 133 i PART I SECTION E INSPECTION AND ACCEPTANCE PAGE NO. E.1 - FAR 52.246-9 - INSPECTION OF RESEARCH AND DEVELOPMENT (SHORT FORM) (APR 1984) E-1 E.2 - CERTIFICATION E-1 Contract No. DE-AC02-07CH11358 Section E Contract Modification No.133 E-1 PART I SECTION E - INSPECTION AND ACCEPTANCE E.1 - FAR 52.246-9 - INSPECTION OF RESEARCH AND DEVELOPMENT (SHORT FORM) (APR 1984) The Government has the right to inspect and evaluate the work performed or being performed under

  15. Contract No. DE-AC02-07CH11358 Section F Contract Modification No. 0139

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    F Contract Modification No. 0139 i PART I SECTION F DELIVERIES OR PERFORMANCE TABLE OF CONTENTS PAGE NO. F.1 - PERIOD OF PERFORMANCE F-1 F.2 - AWARD TERM INCENTIVE (SPECIAL) F-1 F.3 - FAR 52.242-15 - STOP WORK ORDER (AUG 1989) - ALTERNATE I (APR 1984) F-4 F.4 - STOP WORK AND SHUTDOWN AUTHORITY F-5 F.5 - PRINCIPAL PLACE OF PERFORMANCE F-5 Contract No. DE-AC02-07CH11358 Section F Contract Modification No. 0139 F-1 PART I SECTION F - DELIVERIES OR PERFORMANCE F.1 - PERIOD OF PERFORMANCE (a) This

  16. Memorandum, CH2M HG Idaho, LLC, Request for Variance to Title 10 Code of Federal Regulations part 851, "Worker Safety and Health"

    Broader source: Energy.gov [DOE]

    CH2M HG Idaho, LLC, Request for Variance to Title 10 Code of Federal Regulations part 851, "Worker Safety and Health"

  17. Memorandum CH2M WG Idaho, LLC, Request for Variance to Title 10, Code of Federal Regulations Part 851, "Worker Safety and Health Program"

    Broader source: Energy.gov [DOE]

    Memorandum CH2M WG Idaho, LLC, Request for Variance to Title 10, Code of Federal Regulations Part 851, "Worker Safety and Health Program"

  18. Cooperative, Multicentered CH/ Interaction-Controlled Supramolecular Self-Assembly Processes

    SciTech Connect (OSTI)

    Li, Qing; Han, Chengbo; Horton, Scott R; Fuentes-Cabrera, Miguel A; Sumpter, Bobby G; Lu, Wenchang; Bernholc, J.; Maksymovych, Petro; Pan, Minghu

    2012-01-01

    Supramolecular self-assembly on well-defined surfaces provides access to a multitude of nanoscale architectures, including clusters of distinct symmetry and size. The driving forces underlying supramolecular structures generally involve both graphoepitaxy and weak directional nonconvalent interactions. Here we show that functionalizing a benzene molecule with an ethyne group introduces attractive interactions in a 2D geometry, which would otherwise be dominated by intermolecular repulsion. Furthermore, the attractive interactions enable supramolecular self-assembly, wherein a subtle balance between very weak CH/{pi} bonding and molecule-surface interactions produces a well-defined 'magic' dimension and chirality of supramolecular clusters. The nature of the process is corroborated by extensive scanning tunneling microscopy/spectroscopy (STM/S) measurements and ab initio calculations, which emphasize the cooperative, multicenter characters of the CH/{pi} interaction. This work points out new possibilities for chemical functionalization of {pi}-conjugated hydrocarbon molecules that may allow for the rational design of supramolecular clusters with a desired shape and size.

  19. CO2 and CH4 Fluxes across Polygon Geomorphic Types, Barrow, Alaska, 2006-2010

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Tweedie,Craig; Lara, Mark

    2014-09-17

    Carbon flux data are reported as Net Ecosystem Exchange (NEE), Gross Ecosystem Exchange (GEE), Ecosystem Respiration (ER), and Methane (CH4) flux. Measurements were made at 82 plots across various polygon geomorphic classes at research sites on the Barrow Environmental Observatory (BEO), the Biocomplexity Experiment site on the BEO, and the International Biological Program (IBP) site a little west of the BEO. This product is a compilation of data from 27 plots as presented in Lara et al. (2012), data from six plots presented in Olivas et al. (2010); and from 49 plots described in (Lara et al. 2014). Measurements were made during the peak of the growing seasons during 2006 to 2010. At each of the measurement plots (except Olivas et al., 2010) four different thicknesses of shade cloth were used to generate CO2 light response curves. Light response curves were used to normalize photosynthetically active radiation that is diurnally variable to a peak growing season average ~400 umolm-2sec-1. At the Olivas et al. (2010) plots, diurnal patterns were characterized by repeated sampling. CO2 measurements were made using a closed-chamber photosynthesis system and CH4 measurements were made using a photo-acoustic multi-gas analyzer. In addition, plot-level measurements for thaw depth (TD), water table depth (WTD), leaf area index (LAI), and normalized difference vegetation index (NDVI) are summarized by geomorphic polygon type.

  20. Class I methanol (CH{sub 3}OH) maser conditions near supernova remnants

    SciTech Connect (OSTI)

    McEwen, Bridget C.; Pihlstrm, Ylva M.; Sjouwerman, Lornt O.

    2014-10-01

    We present results from calculations of the physical conditions necessary for the occurrence of 36.169 (4{sub 1}-3{sub 0} E), 44.070 (7{sub 0}-6{sub 1} A {sup +}), 84.521 (5{sub 1}-4{sub 0} E), and 95.169 (8{sub 0}-7{sub 1} A {sup +}) GHz methanol (CH{sub 3}OH) maser emission lines near supernova remnants (SNRs), using the MOLPOP-CEP program. The calculations show that given a sufficient methanol abundance, methanol maser emission arises over a wide range of densities and temperatures, with optimal conditions at n ? 10{sup 4}-10{sup 6} cm{sup 3} and T > 60 K. The 36 GHz and 44 GHz transitions display more significant maser optical depths compared to the 84 GHz and 95 GHz transitions over the majority of physical conditions. It is also shown that line ratios are an important and applicable probe of the gas conditions. The line ratio changes are largely a result of the E-type transitions becoming quenched faster at increasing densities. The modeling results are discussed using recent observations of CH{sub 3}OH and hydroxyl (OH) masers near the SNRs G1.40.1, W28, and Sgr A East.

  1. CO2 and CH4 Fluxes across Polygon Geomorphic Types, Barrow, Alaska, 2006-2010

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Tweedie,Craig; Lara, Mark

    Carbon flux data are reported as Net Ecosystem Exchange (NEE), Gross Ecosystem Exchange (GEE), Ecosystem Respiration (ER), and Methane (CH4) flux. Measurements were made at 82 plots across various polygon geomorphic classes at research sites on the Barrow Environmental Observatory (BEO), the Biocomplexity Experiment site on the BEO, and the International Biological Program (IBP) site a little west of the BEO. This product is a compilation of data from 27 plots as presented in Lara et al. (2012), data from six plots presented in Olivas et al. (2010); and from 49 plots described in (Lara et al. 2014). Measurements were made during the peak of the growing seasons during 2006 to 2010. At each of the measurement plots (except Olivas et al., 2010) four different thicknesses of shade cloth were used to generate CO2 light response curves. Light response curves were used to normalize photosynthetically active radiation that is diurnally variable to a peak growing season average ~400 umolm-2sec-1. At the Olivas et al. (2010) plots, diurnal patterns were characterized by repeated sampling. CO2 measurements were made using a closed-chamber photosynthesis system and CH4 measurements were made using a photo-acoustic multi-gas analyzer. In addition, plot-level measurements for thaw depth (TD), water table depth (WTD), leaf area index (LAI), and normalized difference vegetation index (NDVI) are summarized by geomorphic polygon type.

  2. Kinetic and thermodynamic study of the reduction of 1,1-diphenylethylene by a thermally frustrated diethyl ether-BCF Lewis pair

    SciTech Connect (OSTI)

    Whittemore, Sean M.; Autrey, Thomas

    2015-02-01

    The reaction enthalpy and rate of reduction of 1,1-diphenylethylene (DPE) by the Frustrated Lewis pair formed between tris-pentafluorophenylborane (BCF) and diethyl ether (Et₂O) in dichloromethane have been determined by mixing calorimetry. At 50 °C and 13.6 atm hydrogen a 0.08 M solution of DPE is reduced to 1,1-diphenylethane in the presence of 1 equivalent BCF and 0.8 equivalents Et₂O in 40 minutes. NMR spectroscopy showed >99% conversion to the reduced product. The rate of conversion of the olefin to the alkane as monitored by the time dependent heat flow showed a linear dependence on the free Et₂O and BCF concentration. Integration of the heat flux provides a measure of the reaction enthalpy of ΔH ca. -116±4 kJ/mol for the reaction Ph₂C=CH₂+H2→Ph₂CHCH₃. The equilibrium constant for dative adduct formation, Et₂O+BCF↔Et₂O—BCF, was determined as a function of temperature by ¹⁹F NMR spectroscopy and provided an experimental measure of the enthalpy, ΔH = -54.6±3.3 kJ/mol⁻¹ and entropy, ΔS=-154±13 Jmol⁻¹ K⁻¹, for dative bond formation in DCM. Extrapolation of the van’t Hoff plot to 50 ºC provides Keq that is used to estimate the concentration of free BCF and Et₂O available to activate hydrogen. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.

  3. Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; Hensley, Jesse; Snowden-Swan, Lesley J.; Humbird, David; Schaidle, Joshua; Biddy, Mary

    2015-10-28

    This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economicmore » analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.« less

  4. Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates

    SciTech Connect (OSTI)

    Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; Hensley, Jesse; Snowden-Swan, Lesley J.; Humbird, David; Schaidle, Joshua; Biddy, Mary

    2015-10-28

    This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economic analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.

  5. Site Office Contracting Officer E-mail address Ames Site Office Jackie York Jacquelyn.york@ch.doe.gov

    National Nuclear Security Administration (NNSA)

    Site Office Contracting Officer E-mail address Ames Site Office Jackie York Jacquelyn.york@ch.doe.gov Argonne Site Office Jackie York Jacquelyn.york@ch.doe.gov Brookhaven Site Office Evelyn Landini Jennifer Hartmann elandini@bnl.gov jhartmann@bnl.gov Idaho Site Office Paul Allen allenph@id.doe.gov Kansas City Site Office Hilary Cole Hilary.Cole@nnsa.doe.gov Lawrence Livermore Site Office Jewell Lee Jewell.Lee@nnsa.doe.gov Los Alamos Site Office Barbara Romero Robert M. Poole

  6. CO2 and CH4 Surface Flux, Soil Profile Concentrations, and Stable Isotope Composition, Barrow, Alaska, 2012-2013

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Curtis, J.B.; Vaughn, L.S.; Torn, M.S.; Conrad, M.S.; Chafe, O.; Bill, M.

    2015-12-31

    In August-October 2012 and June-October 2013, co-located measurements were made of surface CH4 and CO2 flux, soil pore space concentrations and stable isotope compositions of CH4 and CO2, and subsurface temperature and soil moisture. Measurements were made in intensive study site 1 areas A, B, and C, and from the site 0 and AB transects, from high-centered, flat-centered, and low-centered polygons, from the center, edge, and trough of each polygon.

  7. Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Activation by Cytochrome P450 | Stanford Synchrotron Radiation Lightsource Iron(IV)hydroxide pKa and the Role of Thiolate Ligation in C-H Bond Activation by Cytochrome P450 Saturday, May 31, 2014 Cytochrome P450s (P450s) are a family of monooxygenase enzymes that are nearly ubiquitous in nature. P450s are often described as biological blowtorches due to their incredible oxidizing power:1 They can hydroxylate C-H bonds of about 98-100 kcal/mol. P450s are responsible for the phase I metabolism

  8. Contract No. DE-AC02-07CH11358 Section J Appendix G Contract Modification No. 0183

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Section J Appendix G Contract Modification No. 0183 ATTACHMENT J.7 Contract No. DE-AC02-07CH11358 J-G-1 APPENDIX G PURCHASING SYSTEM REQUIREMENTS Applicable to the Operation of AMES Laboratory Contract No. DE-AC02-07CH11358 Section J Appendix G Contract Modification No. 0183 Appendix G Purchasing System Requirements This Appendix and Clause 1.154, "Contractor Purchasing System," sets forth DOE requirements applicable to the Purchasing System established under the Contract for the

  9. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    SciTech Connect (OSTI)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has

  10. Final Report for DOE Project DE-FC07-99CH11010

    SciTech Connect (OSTI)

    Jed Randall; Robert Kean

    2003-10-22

    Department of Energy award number DE-FC07-99CH11010, Enhanced Utilization of Corn Based Biomaterials, supported a technology development program sponsored by Cargill Dow LLC from September 30, 1999 through June 30, 2003. The work involved fundamental scientific studies on poly lactic acid (PLA), a new environmentally benign plastic material from renewable resources. DOE funds supported academic research at the Colorado School of Mines and the National Renewable Energy Laboratory (NREL), and industry cost share was directed towards applied research into new product development utilizing the fundamental information generated by the academic partners. Under the arrangement of the grant, the fundamental information is published so that other companies can utilize it in evaluating the applicability of PLA in their own products. The overall project objective is to increase the utilization of PLA, a renewable resource based plastic, currently produced from fermented corn sugar.

  11. ChIP-seq Mapping of Distant-Acting Enhancers and Their In Vivo Activities

    SciTech Connect (OSTI)

    Visel, Axel; Pennacchio, Len A.

    2011-06-01

    The genomic location and function of most distant-acting transcriptional enhancers in the human genome remains unknown We performed ChIP-seq for various transcriptional coactivator proteins (such as p300) directly from different embryonic mouse tissues, identifying thousands of binding sitesTransgenic mouse experiments show that p300 and other co-activator peaks are highly predictive of genomic location AND tissue-specific activity patterns of distant-acting enhancersMost enhancers are active only in one or very few tissues Genomic location of tissue-specific p300 peaks correlates with tissue-specific expression of nearby genes Most binding sites are conserved, but the global degree of conservation varies between tissues

  12. Detection of class I methanol (CH{sub 3}OH) maser candidates in supernova remnants

    SciTech Connect (OSTI)

    Pihlstrm, Y. M.; Mesler, R. A.; McEwen, B. C.; Sjouwerman, L. O.; Frail, D. A.; Claussen, M. J.

    2014-04-01

    We have used the Karl G. Jansky Very Large Array to search for 36 GHz and 44 GHz methanol (CH{sub 3}OH) lines in a sample of 21 Galactic supernova remnants (SNRs). Mainly the regions of the SNRs with 1720 MHz OH masers were observed. Despite the limited spatial extent covered in our search, methanol masers were detected in both G1.40.1 and W28. Additional masers were found in Sgr A East. More than 40 masers were found in G1.40.1, which we deduce are due to interactions between the SNR and at least two separate molecular clouds. The six masers in W28 are associated with the molecular cloud that is also associated with the OH maser excitation. We discuss the possibility that the methanol maser may be more numerous in SNRs than the OH maser, but harder to detect due to observational constraints.

  13. Theoretical study on collision dynamics of H{sup +} + CH{sub 4} at low energies

    SciTech Connect (OSTI)

    Gao, Cong-Zhang; Wang, Jing; Wang, Feng

    2014-02-07

    In this work we make an investigation on collision dynamics of H{sup +} + CH{sub 4} at 30 eV by using time-dependent density functional theory coupled with molecular dynamics approach. All possible reactions are presented based on 9 incident orientations. The calculated fragment intensity is in nice agreement with experimental results. The mechanism of reaction transition for dissociation and proton exchange processes is explained by the intra-molecule energy transfer. However, the energy loss of the proton is in poor agreement with experimental results. The discrepancy is attributed to the mean-field treatment of potential surface. We also studied the dependence on initial velocity of both proton and methane. In addition, we find that for dynamical evolution a different self-interaction correction (SIC) may lead to different results, but with respect to the position of rainbow angle, average-density SIC seems to have reasonable correction.

  14. Near-infrared spectroscopy of CH{sub 2} by frequency modulated diode laser absorption

    SciTech Connect (OSTI)

    Marr, A.J.; Sears, T.J.; Chang, B.

    1998-09-01

    A diode laser spectrometer incorporating a multi-pass Herriott type cell and frequency modulation detection was used to record a previously unaccessed region of the near-infrared singlet{l_arrow}singlet absorption spectrum of methylene between 10thinsp000 cm{sup {minus}1} and 10thinsp600 cm{sup {minus}1}. With this spectrometer, signal-to-noise ratios close to the quantum noise limit have been attained. Identification of rovibronic transitions to five previously unobserved levels, K=1 {tilde a}(0,9,0), K=2thinsp{tilde b}(0,1,0), K=2thinsp{tilde a}(1,6,0), K=3thinsp{tilde b}(0,1,0) and K=3thinsp{tilde a}(0,10,0), was made. Despite the fact that the present spectra access levels within approximately 1300 cm{sup {minus}1} of the barrier to linearity, the spectrum is dense and perturbed, characteristics in common with spectra recorded in many previous studies at shorter wavelengths. Recent spectroscopic observations of halomethylenes [J. Mol. Spectrosc. {bold 188}, 68 (1998)] had suggested that the CH{sub 2} spectrum might become simpler at longer wavelengths, but this was not evident in the observed spectra. The mixed nature of the singlet states is evidenced by the assignment of rovibronic transitions to levels containing primarily {tilde a}thinsp{sup 1}A{sub 1} state character. The new measurements provide a stringent test for modern theoretical models for CH{sub 2} and will enable refinement of the electronic potential surfaces. {copyright} {ital 1998 American Institute of Physics.}

  15. Physical and chemical properties of dust produced in a N{sub 2}-CH{sub 4} RF plasma discharge

    SciTech Connect (OSTI)

    Ouni, F.; Alcouffe, G.; Szopa, C.; Carrasco, N.; Cernogora, G.; Adande, G.; Thissen, R.; Quirico, E.; Brissaud, O.; Schmitz-Afonso, I.; Laprevote, O.

    2008-09-07

    Titan's atmospheric chemistry is simulated using a Capacitively Coupled Plasma discharge produced in a N{sub 2}-CH{sub 4} mixture. The produced solid particles are analysed ex-situ. Chemical properties are deduced from: elemental composition, FTIR and LTQ-Orbitrap mass spectrometer. Optical properties are deduced from reflectivity in visible and IR range.

  16. Communication: Spectroscopic characterization of an alkyl substituted Criegee intermediate syn-CH{sub 3}CHOO through pure rotational transitions

    SciTech Connect (OSTI)

    Nakajima, Masakazu; Endo, Yasuki

    2014-01-07

    An alkyl-substituted Criegee intermediate syn-CH{sub 3}CHOO was detected in the gas phase through Fourier-transform microwave spectroscopy. Observed pure rotational transitions show a small splitting corresponding to the A/E components due to the threefold methyl internal rotation. The rotational constants and the barrier height of the hindered methyl rotation were determined to be A = 17?586.5295(15) MHz, B = 7133.4799(41) MHz, C = 5229.1704(40) MHz, and V{sub 3} = 837.1(17)cm{sup ?1}. High-level ab initio calculations which reproduce the experimentally determined values well indicate that the in-plane CH bond in the methyl moiety is trans to the CO bond, and other two protons are directed to the terminal oxygen atom for the most stable structure of syn-CH{sub 3}CHOO. The torsional barrier of the methyl top is fairly large in syn-CH{sub 3}CHOO, implying a significant interaction between the terminal oxygen and the protons of the methyl moiety, which may be responsible for the high production yields of the OH radical from energized alkyl-substituted Criegee intermediates.

  17. Rate constant and mechanism of the reaction between Cl and CH{sub 3}OCl at 295 K

    SciTech Connect (OSTI)

    Carl, S.A.; Roehl, C.M.; Moortgat, G.K.; Crowley, J.N.; Mueller, C.M.

    1996-10-24

    The reaction between Cl atoms and CH{sub 3}OCl was investigated at 295 K in both air and N{sub 2} bath gases at total pressures between 100 and 850 Torr by the relative rate method. The rate constant of the title reaction was found to be a factor 1.07{+-}0.02 (2{sigma}) greater than that of Cl+C{sub 2}H{sub 6} at room temperature and independent of pressure between 100 and 750 Torr. This yields a rate constant of (6.1{+-}0.6)x10{sup -11} cm{sup 3} molecule{sup -1} s{sup -1}. The products of the reaction were detected by FTIR and UV absorption spectroscopy. Analysis of Cl{sub 2} and HCl products allowed branching ratios of 0.2{+-}0.1 for HCl+CH{sub 2}OCl formation and 0.8{+-}0.2 for Cl{sub 2}+CH{sub 3}O formation to be determined. The high rate constant implies that reaction with Cl atoms is an important loss process for CH{sub 3}OCl in the polar stratosphere. 37 refs., 9 figs., 3 tabs.

  18. Accurate quantum dynamics calculations of vibrational spectrum of dideuteromethane CH{sub 2}D{sub 2}

    SciTech Connect (OSTI)

    Yu, Hua-Gen

    2015-05-21

    We report a rigorous variational study of the infrared (IR) vibrational spectra of both CH{sub 2}D{sub 2} and {sup 13}CH{sub 2}D{sub 2} isotopomers using an exact molecular Hamiltonian. Calculations are carried out using a recently developed multi-layer Lanczos algorithm based on the accurate refined Wang and Carrington potential energy surface of methane and the low-order truncated ab initio dipole moment surface of Yurchenko et al. [J. Mol. Spectrosc. 291, 69 (2013)]. All well converged 357 vibrational energy levels up to 6100 cm{sup ?1} of CH{sub 2}D{sub 2} are obtained, together with a comparison to previous calculations and 91 experimental bands available. The calculated frequencies are in excellent agreement with the experimental results and give a root-mean-square error of 0.67?cm{sup ?1}. In particular, we also compute the transition intensities from the vibrational ground state for both isotopomers. Based on the theoretical results, 20 experimental bands are suggested to be re-assigned. Surprisingly, an anomalous C isotopic effect is discovered in the n?{sub 5} modes of CH{sub 2}D{sub 2}. The predicted IR spectra provide useful information for understanding those unknown bands.

  19. Letter from DOE to URS | CH2M Oak Ridge LLC on Award Fee Determination for April to September 2015

    Broader source: Energy.gov [DOE]

    DOE's Oak Ridge Environmental Management Office told URS | CH2M Oak Ridge LLC (UCOR) in a letter that it had completed its evaluation of the company's performance for the award fee period of April to September 2015 and determined that UCOR earned a fee of more than $4.4 million for the period.

  20. Oxygenates du`jour...MTBE? Ethanol? ETBE?

    SciTech Connect (OSTI)

    Wolfe, R.

    1995-12-31

    There are many different liquids that contain oxygen which could be blended into gasoline. The ones that have been tried and make the most sense are in the alcohol (R-OH) and ether (R-O-R) chemical family. The alcohols considered are: methanol (MeOH), ethanol (EtOH), tertiary butyl alcohol (TBA). The ethers are: methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary amyl ethyl ether (TAEE), di-isopropyl ether (DIPE). Of the eight oxygenates listed above, the author describes the five that are still waiting for widespread marketing acceptance (methanol, TBA, TAME, TAEE, and DIPE). He then discusses the two most widely used oxygenates in the US, MTBE and ethanol, along with the up-and-coming ethanol ether, ETBE. Selected physical properties for all of these oxygenates can be found in Table 2 at the end of this paper. A figure shows a simplified alcohol/ether production flow chart for the oxygenates listed above and how they are interrelated.

  1. Effects of CO addition on the characteristics of laminar premixed CH{sub 4}/air opposed-jet flames

    SciTech Connect (OSTI)

    Wu, C.-Y. [Advanced Engine Research Center, Kao Yuan University, Kaohsiung County, 821 (China); Chao, Y.-C.; Chen, C.-P.; Ho, C.-T. [Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan, 701 (China); Cheng, T.S. [Department of Mechanical Engineering, Chung Hua University, Hsinchu, 300 (China)

    2009-02-15

    The effects of CO addition on the characteristics of premixed CH{sub 4}/air opposed-jet flames are investigated experimentally and numerically. Experimental measurements and numerical simulations of the flame front position, temperature, and velocity are performed in stoichiometric CH{sub 4}/CO/air opposed-jet flames with various CO contents in the fuel. Thermocouple is used for the determination of flame temperature, velocity measurement is made using particle image velocimetry (PIV), and the flame front position is measured by direct photograph as well as with laser-induced predissociative fluorescence (LIPF) of OH imaging techniques. The laminar burning velocity is calculated using the PREMIX code of Chemkin collection 3.5. The flame structures of the premixed stoichiometric CH{sub 4}/CO/air opposed-jet flames are simulated using the OPPDIF package with GRI-Mech 3.0 chemical kinetic mechanisms and detailed transport properties. The measured flame front position, temperature, and velocity of the stoichiometric CH{sub 4}/CO/air flames are closely predicted by the numerical calculations. Detailed analysis of the calculated chemical kinetic structures reveals that as the CO content in the fuel is increased from 0% to 80%, CO oxidation (R99) increases significantly and contributes to a significant level of heat-release rate. It is also shown that the laminar burning velocity reaches a maximum value (57.5 cm/s) at the condition of 80% of CO in the fuel. Based on the results of sensitivity analysis, the chemistry of CO consumption shifts to the dry oxidation kinetics when CO content is further increased over 80%. Comparison between the results of computed laminar burning velocity, flame temperature, CO consumption rate, and sensitivity analysis reveals that the effect of CO addition on the laminar burning velocity of the stoichiometric CH{sub 4}/CO/air flames is due mostly to the transition of the dominant chemical kinetic steps. (author)

  2. Evaluating Impacts of CO2 and CH4 Gas Intrusion into an Unconsolidated Aquifer: Fate of As and Cd

    SciTech Connect (OSTI)

    Lawter, Amanda R.; Qafoku, Nikolla; Shao, Hongbo; Bacon, Diana H.; Brown, Christopher F.

    2015-07-10

    Abstract The sequestration of carbon dioxide (CO2) in deep underground reservoirs has been identified as an important strategy to decrease atmospheric CO2 levels and mitigate global warming, but potential risks on overlying aquifers currently lack a complete evaluation. In addition to CO2, other gases such as methane (CH4) may be present in storage reservoirs. This paper explores for the first time the combined effect of leaking CO2 and CH4 gasses on the fate of major, minor and trace elements in an aquifer overlying a potential sequestration site. Emphasis is placed on the fate of arsenic (As) and cadmium (Cd) released from the sediments or present as soluble constituents in the leaking brine. Results from macroscopic batch and column experiments show that the presence of CH4 (at a concentration of 1 % in the mixture CO2/CH4) does not have a significant effect on solution pH or the concentrations of most major elements (such as Ca, Ba, and Mg). However, the concentrations of Mn, Mo, Si and Na are inconsistently affected by the presence of CH4 (i.e., in at least one sediment tested in this study). Cd is not released from the sediments and spiked Cd is mostly removed from the aqueous phase most likely via adsorption. The fate of sediment associated As [mainly sorbed arsenite or As(III) in minerals] and spiked As [i.e., As5+] is complex. Possible mechanisms that control the As behavior in this system are discussed in this paper. Results are significant for CO2 sequestration risk evaluation and site selection and demonstrate the importance of evaluating reservoir brine and gas stream composition during site selection to ensure the safest site is being chosen.

  3. Tracking the sources of polybrominated diphenyl ethers in birds: Foraging in waste management facilities results in higher DecaBDE exposure in males

    SciTech Connect (OSTI)

    Gentes, Marie-Line; Mazerolle, Marc J.; Giroux, Jean-François; Patenaude-Monette, Martin; and others

    2015-04-15

    Differences in feeding ecology are now recognized as major determinants of inter-individual variations in contaminant profiles of free-ranging animals, but exceedingly little attention has been devoted to the role of habitat use. Marked inter-individual variations and high levels of polybrominated diphenyl ethers (PBDEs) (e.g., DecaBDE) have previously been documented in ring-billed gulls (Larus delawarensis) breeding in a colony near Montreal (QC, Canada). However, the environmental sources of these compounds, and thus the reasons causing these large inter-individual variations remain unidentified. In the present study, we used GPS-based telemetry (±5 to 10 m precision) to track ring-billed gulls from this colony to reconstruct their movements at the landscape level. We related habitat use of individual gulls (n=76) to plasma concentrations (ng/g ww) and relative contributions (percentages) to Σ{sub 38}PBDEs of major congeners in the internationally restricted PentaBDE and current-use DecaBDE mixtures. Male gulls that visited waste management facilities (WMFs; i.e., landfills, wastewater treatment plants and related facilities; 25% of all GPS-tracked males) exhibited greater DecaBDE (concentrations and percentages) and lower PentaBDE (percentages) relative to those that did not. In contrast, no such relationships were found in females. Moreover, in males, DecaBDE (concentrations and percentages) increased with percentages of time spent in WMFs (i.e., ~5% of total foraging time), while PentaBDE (percentages) decreased. No relationships between percentages of time spent in other habitats (i.e., urban areas, agriculture fields, and St. Lawrence River) were found in either sex. These findings suggest that animals breeding in the vicinity of WMFs as well as mobile species that only use these sites for short stopovers to forage, could be at risk of enhanced DecaBDE exposure. - Highlights: • The study was conducted on breeding gulls with high levels of flame

  4. Polybrominated diphenyl ethers in e-waste: Level and transfer in a typical e-waste recycling site in Shanghai, Eastern China

    SciTech Connect (OSTI)

    Li, Yue; Duan, Yan-Ping, E-mail: duanyanping@tongji.edu.cn; Huang, Fan; Yang, Jing; Xiang, Nan; Meng, Xiang-Zhou; Chen, Ling

    2014-06-01

    Highlights: PBDEs were detected in the majority of e-waste. PBDEs were found in TVs made in China after 1990. The levels of ?PBDEs in e-waste made in Japan far exceed the threshold limit of RoHS. The inappropriate recycling and disposal of e-waste is an important source of PBDEs. - Abstract: Very few data for polybrominated diphenyl ethers (PBDEs) were available in the electronic waste (e-waste) as one of the most PBDEs emission source. This study reported concentrations of PBDEs in e-waste including printer, rice cooker, computer monitor, TV, electric iron and water dispenser, as well as dust from e-waste, e-waste dismantling workshop and surface soil from inside and outside of an e-waste recycling plant in Shanghai, Eastern China. The results showed that PBDEs were detected in the majority of e-waste, and the concentrations of ?PBDEs ranged from not detected to 175 g/kg, with a mean value of 10.8 g/kg. PBDEs were found in TVs made in China after 1990. The mean concentrations of ?PBDEs in e-waste made in Korea, Japan, Singapore and China were 1.84 g/kg, 20.5 g/kg, 0.91 g/kg, 4.48 g/kg, respectively. The levels of ?PBDEs in e-waste made in Japan far exceed the threshold limit of RoHS (1.00 g/kg). BDE-209 dominated in e-waste, accounting for over 93%. The compositional patterns of PBDEs congeners resembled the profile of Saytex 102E, indicating the source of deca-BDE. Among the samples of dust and surface soil from a typical e-waste recycling site, the highest concentrations of ?{sub 18}PBDEs and BDE-209 were found in dust in e-waste, ranging from 1960 to 340,710 ng/g and from 910 to 320,400 ng/g, which were 12 orders of magnitude higher than other samples. It suggested that PBDEs released from e-waste via dust, and then transferred to surrounding environment.

  5. Quercetin 3-O-methyl ether protects FL83B cells from copper induced oxidative stress through the PI3K/Akt and MAPK/Erk pathway

    SciTech Connect (OSTI)

    Tseng, Hsiao-Ling; Li, Chia-Jung; Huang, Lin-Huang; Chen, Chun-Yao; Tsai, Chun-Hao; Lin, Chun-Nan; Department of Biological Science and Technology, School of Medicine, China Medical University, Taichung, Taiwan ; Hsu, Hsue-Yin

    2012-10-01

    Quercetin is a bioflavonoid that exhibits several biological functions in vitro and in vivo. Quercetin 3-O-methyl ether (Q3) is a natural product reported to have pharmaceutical activities, including antioxidative and anticancer activities. However, little is known about the mechanism by which it protects cells from oxidative stress. This study was designed to investigate the mechanisms by which Q3 protects against Cu{sup 2+}-induced cytotoxicity. Exposure to Cu{sup 2+} resulted in the death of mouse liver FL83B cells, characterized by apparent apoptotic features, including DNA fragmentation and increased nuclear condensation. Q3 markedly suppressed Cu{sup 2+}-induced apoptosis and mitochondrial dysfunction, characterized by reduced mitochondrial membrane potential, caspase-3 activation, and PARP cleavage, in Cu{sup 2+}-exposed cells. The involvement of PI3K, Akt, Erk, FOXO3A, and Mn-superoxide dismutase (MnSOD) was shown to be critical to the survival of Q3-treated FL83B cells. The liver of both larval and adult zebrafish showed severe damage after exposure to Cu{sup 2+} at a concentration of 5 μM. Hepatic damage induced by Cu{sup 2+} was reduced by cotreatment with Q3. Survival of Cu{sup 2+}-exposed larval zebrafish was significantly increased by cotreatment with 15 μM Q3. Our results indicated that Cu{sup 2+}-induced apoptosis in FL83B cells occurred via the generation of ROS, upregulation and phosphorylation of Erk, overexpression of 14-3-3, inactivation of Akt, and the downregulation of FOXO3A and MnSOD. Hence, these results also demonstrated that Q3 plays a protective role against oxidative damage in zebrafish liver and remarked the potential of Q3 to be used as an antioxidant for hepatocytes. Highlights: ► Protective effects of Q3 on Cu{sup 2+}-induced oxidative stress in vitro and in vivo. ► Cu{sup 2+} induced apoptosis in FL83B cells via ROS and the activation of Erk. ► Q3 abolishes Cu{sup 2+}-induced apoptosis through the PI3K/Akt and MAPK

  6. Polyacetylene, (CH){sub x}, as an Emerging Material for Solar Cell Applications. Final Technical Report, March 19, 1979 - March 18, 1980

    DOE R&D Accomplishments [OSTI]

    Heeger, A. J.; MacDiarmid, A. G.

    1980-06-05

    Despite great theoretical and technological interest in polyacetylene, (CH){sub x}, the basic features of its band structure have not been unambiguously resolved. Since photoconductivity and optical absorption data have frequently been used to infer information on the band structure of semiconductors, such measurements were carried out on (CH){sub x}. The main results of an extensive study of the photoconductivity (..delta.. sigma{sub ph}) and absorption coefficient (..cap alpha..) in (CH){sub x} are presented. The absence of photoconductivity in cis-(CH){sub x}, despite the similarity in optical properties indicates that ..delta.. sigma/sub ph/ in trans-(CH){sub x} is induced by isomerization. It is found that isomerization generates states deep inside the gap that act as safe traps for minority carriers and thereby enhance the photoconductivity. Compensation of trans-(CH){sub x} with ammonia appears to decrease the number of safe traps, whereas acceptor doping increases their number. Thus, chemical doping can be used to control the photoconductive response. The energy of safe traps inside the gap is independent of the process used to generate them; indicative of an intrinsic localized defect level in trans-(CH){sub x}. A coherent picture based on the soliton model can explain these results, including the safe trapping.

  7. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    SciTech Connect (OSTI)

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan

    2008-02-04

    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  8. Mode specific dynamics of the H{sub 2} + CH{sub 3} → H + CH{sub 4} reaction studied using quasi-classical trajectory and eight-dimensional quantum dynamics methods

    SciTech Connect (OSTI)

    Wang, Yan; Li, Jun; Guo, Hua E-mail: hguo@unm.edu; Chen, Liuyang; Yang, Minghui E-mail: hguo@unm.edu; Lu, Yunpeng

    2015-10-21

    An eight-dimensional quantum dynamical model is proposed and applied to the title reaction. The reaction probabilities and integral cross sections have been determined for both the ground and excited vibrational states of the two reactants. The results indicate that the H{sub 2} stretching and CH{sub 3} umbrella modes, along with the translational energy, strongly promote the reactivity, while the CH{sub 3} symmetric stretching mode has a negligible effect. The observed mode specificity is confirmed by full-dimensional quasi-classical trajectory calculations. The mode specificity can be interpreted by the recently proposed sudden vector projection model, which attributes the enhancement effects of the reactant modes to their strong couplings with the reaction coordinate at the transition state.

  9. A Pyrrolyl-based Triazolophane: A Macrocyclic Receptor With CH and NH Donor Groups That Exhibits a Preference for Pyrophosphate Anions

    SciTech Connect (OSTI)

    Sessler, Jonathan L.; Cia, Jiajia; Gong, Han-Yuan; Yang, Xiauping; Arambula, Jonathan F.; Hay, Benjamin

    2010-01-01

    A pyrrolyl-based triazolophane, incorporating CH and NH donor groups, acts as a receptor for the pyrophosphate anion in chloroform solution. It shows selectivity for this trianion, followed by HSO{sub 4}{sup -} > H{sub 2}PO{sub 4}{sup -} > Cl{sup -} > Br{sup -} (all as the corresponding tetrabutylammonium salts), with NH-anion interactions being more important than CH-anion interactions. In the solid state, the receptor binds the pyrophosphate anion in a clip-like slot via NH and CH hydrogen bonds.

  10. Identification of genes directly regulated by the oncogene ZNF217using ChIP-chip assays.

    SciTech Connect (OSTI)

    Krig, S.R.; Jin, V.X.; Bieda, M.C.; O'geen, H.; Yaswen, P.; Green, R.; Farnham, P.J.

    2007-01-26

    It has been proposed that ZNF217, which is amplified at 20q13 in various tumors, plays a key role during neoplastic transformation. ZNF217 has been purified in complexes that contain repressor proteins such as CtBP2, suggesting that it acts as a transcriptional repressor. However, the function of ZNF217 has not been well characterized due to a lack of known target genes. Using a global chromatin immunoprecipitation (ChIP)-chip approach, we identified thousands of ZNF217 binding sites in three tumor cell lines (MCF7, SW480, and Ntera2). Further analysis of ZNF217 in Ntera2 cells showed that many promoters are bound by ZNF217 and CtBP2 and that a subset of these promoters are activated upon removal of ZNF217. Thus, our in vivo studies corroborate the in vitro biochemical analyses of ZNF217-containing complexes and support the hypothesis that ZNF217 functions as a transcriptional repressor. Gene ontology analysis showed that ZNF217 targets in Ntera2 cells are involved in organ development, suggesting that one function of ZNF217 may be to repress differentiation. Accordingly we show that differentiation of Ntera2 cells with retinoic acid led to down-regulation of ZNF217. Our identification of thousands of ZNF217 target genes will enable further studies of the consequences of aberrant expression of ZNF217 during neoplastic transformation.

  11. Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

    SciTech Connect (OSTI)

    Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.

    2010-03-16

    The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

  12. Airborne CH2O measurements over the North Atlantic during the 1997 NARE campaign: Instrument comparisons and distributions

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Fried, Alan; Lee, Yin -Nan; Frost, Greg; Wert, Bryan; Henry, Bruce; Drummond, James R.; Hubler, Gerd; Jobson, Tom

    2002-02-27

    Here, formaldehyde measurements from two independent instruments are compared with photochemical box model calculations. The measurements were made on the NOAA P-3 aircraft as part of the 1997 North Atlantic Regional Experiment (NARE 1997). After examining the possible reasons for the model-measurement discrepancy, we conclude that there are probably one or more additional unknown sources of CH2O in the North Atlantic troposphere.

  13. Solid-state organometallic chemistry of molecular metal oxide clusters: C-H activation by an iridium polyoxometalate

    SciTech Connect (OSTI)

    Siedle, A.R.; Newmark, R.A.; Brown-Wensley, K.A.; Skarjune, R.P.; Haddad, L.C.; Hodgson, K.O.; Roe, A.L.

    1988-09-01

    Hydrogenation of ((Ph/sub 3/P)/sub 2/Ir(C/sub 8/H/sub 12/))/sub 3/PW/sub 12/O/sub 40/ in a solid-gas reaction produces ((Ph/sub 3/P)/sub 2/IrH/sub 2/)/sub 3/PW/sub 12/O/sub 40/. EXAFS studies of the molybdenum analogue indicate the presence of isolated, lattice-stabilized (Ph/sub 3/P)/sub 2/IrH/sub 2//sup +/ ions. H/emdash/D exchange with CD/sub 3/CH/double bond/CH/sub 2/ occurs via a reversible C/emdash/H addition reaction that also produces ((Ph/sub 3/P)/sub 2/IrH(/pi/-C/sub 3/H/sub 5/))/sub 3/PW/sub 12/O/sub 40/ and scrambles the C/sub 3/D/sub 3/H/sub 3/ deuterium label. Exchange with toluene is selective and involves activation of aromatic but not aliphatic C-H bonds. Slow exchange with c-C/sub 6/D/sub 12/ also occurs.

  14. Structure, phase transitions, and isotope effects in [(CH3)4N]2PuCl6

    SciTech Connect (OSTI)

    Wilson, Richard E.

    2015-11-02

    The single crystal X-ray diffraction structure of [(CH3)4N]2PuCl6 is presented for the first time, resolving long standing confusion and speculation regarding the structure of this compound in the literature. A temperature dependent study of this compound shows that the structure of [(CH3)4N]2PuCl6 undergoes no fewer than two phase transitions between 100 and 360 K. The phase of [(CH3)4N]2PuCl6 at room temperature is Fd-3c a = 26.012(3) Å. At 360 K, the structure is in space group Fm-3m with a = 13.088(1) Å. The plutonium octahedra and tetramethylammonium cations undergo a rotative displacement and the degree of rotation varies with temperature, giving rise to the phase transition from Fm-3m to Fd-3c as the crystal is cooled. Synthesis and structural studies of the deuterated salt [(CD3)4N]2PuCl6 suggest that there is an isotopic effect associated with this phase transition as revealed by a changing transition temperature in the deuterated versus protonated compound indicating that the donor-acceptor interactions between the tetramethylammonium cations and the hexachloroplutonate anions are driving the phase transformation.

  15. Subtask 1.22 - Microbial Cycling of CH4, CO2, and N2O in a Wetlands Environment

    SciTech Connect (OSTI)

    Dingyi Ye; Bethany Kurz; Marc Kurz

    2008-12-31

    Soil microbial metabolic activities play an important role in determining CO{sub 2}, CH{sub 4}, and N{sub 2}O fluxes from terrestrial ecosystems. To verify and evaluate CO{sub 2} sequestration potential by wetland restoration in the Prairie Pothole Region (PPR), as well as to address concern over restoration effects on CH{sub 4} and N{sub 2}O emissions, laboratory and in situ microcosm studies on microbial cycling of CO{sub 2}, CH{sub 4}, and N{sub 2}O were initiated. In addition, to evaluate the feasibility of the use of remote sensing to detect soil gas flux from wetlands, a remote-sensing investigation was also conducted. Results of the laboratory microcosm study unequivocally proved that restoration of PPR wetlands does sequester atmospheric CO{sub 2}. Under the experimental conditions, the simulated restored wetlands did not promote neither N{sub 2}O nor CH{sub 4} fluxes. Application of ammonia enhanced both N{sub 2}O and CH{sub 4} emission, indicating that restoration of PPR wetlands may reduce both N{sub 2}O and CH{sub 4} emission by cutting N-fertilizer input. Enhancement of CO{sub 2} emission by the N-fertilizer was observed, and this observation revealed an overlooked fact that application of N-fertilizer may potentially increase CO{sub 2} emission. In addition, the CO{sub 2} results also demonstrate that wetland restoration sequesters atmospheric carbon not only by turning soil conditions from aerobic to anoxic, but also by cutting N-fertilizer input that may enhance CO{sub 2} flux. The investigation on microbial community structure and population dynamics showed that under the experimental conditions restoration of the PPR wetlands would not dramatically increase population sizes of those microorganisms that produce N{sub 2}O and CH{sub 4}. Results of the in situ study proved that restoration of the PPR wetland significantly reduced CO{sub 2} flux. Ammonia enhanced the greenhouse gas emission and linearly correlated to the CO{sub 2} flux within the

  16. Critical interpretation of CH and OH stretching regions for infrared spectra of methanol clusters (CH{sub 3}OH){sub n} (n = 25) using self-consistent-charge density functional tight-binding molecular dynamics simulations

    SciTech Connect (OSTI)

    Nishimura, Yoshifumi; Lee, Yuan-Pern; Irle, Stephan; Witek, Henryk A.

    2014-09-07

    Vibrational infrared (IR) spectra of gas-phase OH???O methanol clusters up to pentamer are simulated using self-consistent-charge density functional tight-binding method using two distinct methodologies: standard normal mode analysis and Fourier transform of the dipole time-correlation function. The twofold simulations aim at the direct critical assignment of the CH stretching region of the recently recorded experimental spectra [H.-L. Han, C. Camacho, H. A. Witek, and Y.-P. Lee, J. Chem. Phys. 134, 144309 (2011)]. Both approaches confirm the previous assignment (ibid.) of the CH stretching bands based on the B3LYP/ANO1 harmonic frequencies, showing that ?{sub 3}, ?{sub 9}, and ?{sub 2} CH stretching modes of the proton-accepting (PA) and proton-donating (PD) methanol monomers experience only small splittings upon the cluster formation. This finding is in sharp discord with the assignment based on anharmonic B3LYP/VPT2/ANO1 vibrational frequencies (ibid.), suggesting that some procedural faults, likely related to the breakdown of the perturbational vibrational treatment, led the anharmonic calculations astray. The IR spectra based on the Fourier transform of the dipole time-correlation function include new, previously unaccounted for physical factors such as non-zero temperature of the system and large amplitude motions of the clusters. The elevation of temperature results in a considerable non-homogeneous broadening of the observed IR signals, while the presence of large-amplitude motions (methyl group rotations and PA-PD flipping), somewhat surprisingly, does not introduce any new features in the spectrum.

  17. Final LDRD report : development of sample preparation methods for ChIPMA-based imaging mass spectrometry of tissue samples.

    SciTech Connect (OSTI)

    Maharrey, Sean P.; Highley, Aaron M.; Behrens, Richard, Jr.; Wiese-Smith, Deneille

    2007-12-01

    The objective of this short-term LDRD project was to acquire the tools needed to use our chemical imaging precision mass analyzer (ChIPMA) instrument to analyze tissue samples. This effort was an outgrowth of discussions with oncologists on the need to find the cellular origin of signals in mass spectra of serum samples, which provide biomarkers for ovarian cancer. The ultimate goal would be to collect chemical images of biopsy samples allowing the chemical images of diseased and nondiseased sections of a sample to be compared. The equipment needed to prepare tissue samples have been acquired and built. This equipment includes an cyro-ultramicrotome for preparing thin sections of samples and a coating unit. The coating unit uses an electrospray system to deposit small droplets of a UV-photo absorbing compound on the surface of the tissue samples. Both units are operational. The tissue sample must be coated with the organic compound to enable matrix assisted laser desorption/ionization (MALDI) and matrix enhanced secondary ion mass spectrometry (ME-SIMS) measurements with the ChIPMA instrument Initial plans to test the sample preparation using human tissue samples required development of administrative procedures beyond the scope of this LDRD. Hence, it was decided to make two types of measurements: (1) Testing the spatial resolution of ME-SIMS by preparing a substrate coated with a mixture of an organic matrix and a bio standard and etching a defined pattern in the coating using a liquid metal ion beam, and (2) preparing and imaging C. elegans worms. Difficulties arose in sectioning the C. elegans for analysis and funds and time to overcome these difficulties were not available in this project. The facilities are now available for preparing biological samples for analysis with the ChIPMA instrument. Some further investment of time and resources in sample preparation should make this a useful tool for chemical imaging applications.

  18. S-OO bond dissociation energies and enthalpies of formation of the thiomethyl peroxyl radicals CH{sub 3}S(O){sub n}OO (n=0,1,2)

    SciTech Connect (OSTI)

    Salta, Zoi; Kosmas, Agnie Mylona; Lesar, Antonija

    2014-10-06

    Optimized geometries, S-OO bond dissociation energies and enthalpies of formation for a series of thiomethyl peroxyl radicals are investigated using high level ab initio and density functional theory methods. The results show that the S-OO bond dissociation energy is largest in the methylsulfonyl peroxyl radical, CH{sub 3}S(O){sub 2}OO, which contains two sulfonic type oxygen atoms followed by the methylthiyl peroxyl radical, CH{sub 3}SOO. The methylsulfinyl peroxyl radical, CH{sub 3}S(O)OO, which contains only one sulfonic type oxygen shows the least stability with regard to dissociation to CH{sub 3}S(O)+O{sub 2}. This stabilization trend is nicely reflected in the variations of the S-OO bond distance which is found to be shortest in CH{sub 3}S(O){sub 2}OO and longest in CH{sub 3}S(O)OO.

  19. li Aone+amth arfumionto itu%illti&% p?e~6a'&ionofthoChOmiQo

    Office of Legacy Management (LM)

    li Aone+amth arfumionto itu%illti&% p?e~6a'&ionofthoChOmiQo SinaL report, pattisulerly dfh, raqmot b dto evaluation. 8. A eixdtoirth~atension primarily to inauro havlrg Chealeo &&able . fbroowultationonWtj0 ~itoevaluation~rkforthet&wto Bsddw Timoveoy ?lant, but 980 to keep Chemioo avsilable for dmelopm~t ark on the alternate oatbanatie mtoolaw leaoh proosa80 DIECDBfiIOH Be are requesting anamndcmntto o&end CoatmotAT(W&-1489 with the Chmaloal Qonstruobloon Cor;orhlon.

  20. Study of x-ray radiant characteristics and thermal radiation redistribution in CH foam filling cylindrical cavities

    SciTech Connect (OSTI)

    Shang Wanli; Zhu Tuo; Song Tianming; Zhang Wenhai; Zhao Yang; Xiong Gang; Zhang Jiyan; Yang Jiamin

    2011-04-15

    Experiments are presented, which demonstrate the properties of x-ray radiation and redistribution of radiant thermal energy in high Z cylindrical cavities filled with low Z CH foam. Time integrated spectra records were obtained by a calibrated space-resolved transmission grating spectrometer. The x-ray radiation became weaker in intensity and was changed to a softer near-Planckian radiation light after a 1500 {mu}m long transport in the foam filling cavity. The experimental redistribution of the radiant thermal energy was plotted and compared to the numerical results of a simplified model. Good agreements have been achieved.

  1. Silver-mordenite for radiologic gas capture from complex streams. Dual catalytic CH3I decomposition and I confinement

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Nenoff, Tina M.; Rodriguez, Mark A.; Soelberg, Nick R.; Chapman, Karena W.

    2014-05-09

    The selective capture of radiological iodine (129I) is a persistent concern for safe nuclear energy. In these nuclear fuel reprocessing scenarios, the gas streams to be treated are extremely complex, containing several distinct iodine-containing molecules amongst a large variety of other species. Silver-containing mordenite (MOR) is a longstanding benchmark for radioiodine capture, reacting with molecular iodine (I2) to form AgI. However the mechanisms for organoiodine capture is not well understood. Here we investigate the capture of methyl iodide from complex mixed gas streams by combining chemical analysis of the effluent gas stream with in depth characterization of the recovered sorbent.more » Tools applied include infrared spectroscopy, thermogravimetric analysis with mass spectrometry, micro X-ray fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. Moreover, the MOR zeolite catalyzes decomposition of the methyl iodide through formation of surface methoxy species (SMS), which subsequently reacts with water in the mixed gas stream to form methanol, and with methanol to form dimethyl ether, which are both detected downstream in the effluent. The liberated iodine reacts with Ag in the MOR pore to the form subnanometer AgI clusters, smaller than the MOR pores, suggesting that the iodine is both physically and chemically confined within the zeolite.« less

  2. Silver-Mordenite for Radiologic Gas Capture from Complex Streams: Dual Catalytic CH3I Decomposition and I Confinement

    SciTech Connect (OSTI)

    Tina M. Nenoff; Mark Rodriguez; Nick Soelberg; Karena W. Chapman

    2014-12-01

    The effective capture and storage of radiological iodine (129I) remains a strong concern for safe nuclear waste storage and safe nuclear energy. Silver-containing mordenite (MOR) is a longstanding benchmark for iodine capture. In nuclear fuel reprocessing scenarios, complex gas streams will be present and the need for high selectivity of all iodine containing compounds is of the utmost importance for safety and the environment. In particular, a molecular level understanding of the sorption of organic iodine compounds is not well understood. Here we probe the structure and distribution of methyl iodide sorbed by silver-containing MOR using a combination of crystallographic and materials characterization techniques including: infrared spectroscopy, thermogravimetric analysis with mass spectrometry, Micro-X-ray Fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. The iodine is captured inside the MOR pore in the form of AgI nanoparticles, that is consistent with the pores sizes of the MOR, indicating that the molecule is both physically and chemically captured in the Ag-MOR. The organic component is surface catalyzed by the zeolite via the formation of Surface Methoxy Species (SMS) that result in downstream organics of dimethyl ether and methanol formation.

  3. Department of Justice: CH2M Hill Hanford Group Inc. Admits Criminal Conduct, Parent Company Agrees to Cooperate in Ongoing Investigation and Pay $18.5 Million to Resolve Civil and Criminal Allegations

    Broader source: Energy.gov [DOE]

    The Justice Department, in conjunction with the U.S. Attorney’s Office for the Eastern District of Washington, announced today that Colorado-based CH2M Hill Hanford Group Inc. (CHG) and its parent company, CH2M Hill Companies Ltd. (CH2M Hill) have agreed that CHG committed federal criminal violations, defrauding the public by engaging in years of widespread time card fraud.

  4. Survey of the high resolution infrared spectrum of methane ({sup 12}CH{sub 4} and {sup 13}CH{sub 4}): Partial vibrational assignment extended towards 12000 cm{sup ?1}

    SciTech Connect (OSTI)

    Ulenikov, O. N.; Bekhtereva, E. S.; Albert, S.; Bauerecker, S.; Niederer, H. M.; Quack, M.

    2014-12-21

    We have recorded the complete infrared spectrum of methane {sup 12}CH{sub 4} and its second most abundant isotopomer {sup 13}CH{sub 4} extending from the fundamental range starting at 1000 cm{sup ?1} up to the overtone region near 12000 cm{sup ?1} in the near infrared at the limit towards the visible range, at temperatures of about 80 K and also at 298 K with Doppler limited resolution in the gas phase by means of interferometric Fourier transform spectroscopy using the Bruker IFS 125 HR prototype (ZP 2001) of the ETH Zrich laboratory. This provides the so far most complete data set on methane spectra in this range at high resolution. In the present work we report in particular those results, where the partial rovibrational analysis allows for the direct assignment of pure (J = 0) vibrational levels including high excitation. These results substantially extend the accurate knowledge of vibrational band centers to higher energies and provide a benchmark for both the comparison with theoretical results on the one hand and atmospheric spectroscopy on the other hand. We also present a simple effective Hamiltonian analysis, which is discussed in terms of vibrational level assignments and {sup 13}C isotope effects.

  5. Full-dimensional and reduced-dimensional calculations of initial state-selected reaction probabilities studying the H + CH{sub 4} ? H{sub 2} + CH{sub 3} reaction on a neural network PES

    SciTech Connect (OSTI)

    Welsch, Ralph Manthe, Uwe

    2015-02-14

    Initial state-selected reaction probabilities of the H + CH{sub 4} ? H{sub 2} + CH{sub 3} reaction are calculated in full and reduced dimensionality on a recent neural network potential [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. The quantum dynamics calculation employs the quantum transition state concept and the multi-layer multi-configurational time-dependent Hartree approach and rigorously studies the reaction for vanishing total angular momentum (J = 0). The calculations investigate the accuracy of the neutral network potential and study the effect resulting from a reduced-dimensional treatment. Very good agreement is found between the present results obtained on the neural network potential and previous results obtained on a Shepard interpolated potential energy surface. The reduced-dimensional calculations only consider motion in eight degrees of freedom and retain the C{sub 3v} symmetry of the methyl fragment. Considering reaction starting from the vibrational ground state of methane, the reaction probabilities calculated in reduced dimensionality are moderately shifted in energy compared to the full-dimensional ones but otherwise agree rather well. Similar agreement is also found if reaction probabilities averaged over similar types of vibrational excitation of the methane reactant are considered. In contrast, significant differences between reduced and full-dimensional results are found for reaction probabilities starting specifically from symmetric stretching, asymmetric (f{sub 2}-symmetric) stretching, or e-symmetric bending excited states of methane.

  6. Communication: Imaging the effects of the antisymmetric-stretching excitation in the O({sup 3}P) + CH{sub 4}(v{sub 3} = 1) reaction

    SciTech Connect (OSTI)

    Pan, Huilin [Institute of Atomic and Molecular Sciences (IAMS), Academia Sinica, P. O. Box 23-166, Taipei 10617, Taiwan (China) [Institute of Atomic and Molecular Sciences (IAMS), Academia Sinica, P. O. Box 23-166, Taipei 10617, Taiwan (China); State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China); Liu, Kopin, E-mail: kliu@po.iams.sinica.edu.tw [Institute of Atomic and Molecular Sciences (IAMS), Academia Sinica, P. O. Box 23-166, Taipei 10617, Taiwan (China)] [Institute of Atomic and Molecular Sciences (IAMS), Academia Sinica, P. O. Box 23-166, Taipei 10617, Taiwan (China)

    2014-05-21

    Effects of one-quantum excitation of the antisymmetric-stretching mode of CH{sub 4}(v{sub 3} = 1) on the O({sup 3}P) + CH{sub 4} reaction were studied in a crossed-beam, ion-imaging experiment. In the post-threshold region, we found that (1) the product state distributions are dominated by the CH{sub 3}(0{sub 0}) + OH(v{sup ?} = 1) pair, (2) the product angular distributions extend toward sideways from the backward dominance of the ground-state reaction, and (3) vibrational excitation exerts a positive effect on reactivity, but translational energy is more efficient in promoting the rate of this central-barrier reaction. All major findings agree reasonably well with recent theoretical results. Some remaining questions are pointed out.

  7. Unusual defect physics in CH{sub 3}NH{sub 3}PbI{sub 3} perovskite solar cell absorber

    SciTech Connect (OSTI)

    Yin, Wan-Jian Shi, Tingting; Yan, Yanfa

    2014-02-10

    Thin-film solar cells based on Methylammonium triiodideplumbate (CH{sub 3}NH{sub 3}PbI{sub 3}) halide perovskites have recently shown remarkable performance. First-principle calculations show that CH{sub 3}NH{sub 3}PbI{sub 3} has unusual defect physics: (i) Different from common p-type thin-film solar cell absorbers, it exhibits flexible conductivity from good p-type, intrinsic to good n-type depending on the growth conditions; (ii) Dominant intrinsic defects create only shallow levels, which partially explain the long electron-hole diffusion length and high open-circuit voltage in solar cell. The unusual defect properties can be attributed to the strong Pb lone-pair s orbital and I p orbital antibonding coupling and the high ionicity of CH{sub 3}NH{sub 3}PbI{sub 3}.

  8. Efficient photo-dissociation of CH{sub 4} and H{sub 2}CO molecules with optimized ultra-short laser pulses

    SciTech Connect (OSTI)

    Rasti, S.; Irani, E.; Sadighi-Bonabi, R.

    2015-11-15

    The fragmentation dynamics of CH{sub 4} and H{sub 2}CO molecules have been studied with ultra-short pulses at laser intensityof up to 10{sup 15}Wcm{sup −2}. Three dimensional molecular dynamics calculations for finding the optimized laser pulses are presented based on time-dependent density functional theory and quantum optimal control theory. A comparison of the results for orientation dependence in the ionization process shows that the electron distribution for CH{sub 4} is more isotropic than H{sub 2}CO molecule. Total conversion yields of up to 70% at an orientation angle of 30{sup o} for CH{sub 4} and 65% at 90{sup 0} for H{sub 2}CO are achieved which lead to enhancement of dissociation probability.

  9. Observation of hydroxymethyl hydroperoxide in a reaction system containing CH{sub 2}OO and water vapor through pure rotational spectroscopy

    SciTech Connect (OSTI)

    Nakajima, Masakazu; Endo, Yasuki

    2015-10-28

    Pure rotational transitions of hydroxymethyl hydroperoxide (HMHP) were observed in the discharged plasma of a CH{sub 2}I{sub 2}/O{sub 2}/water gas mixture, where the water complex with the simplest Criegee intermediate CH{sub 2}OO has been identified [M. Nakajima and Y. Endo, J. Chem. Phys. 140, 134302 (2014)]. Isotope experiments using heavy water support that the currently observed HMHP molecule was produced by the reaction of CH{sub 2}OO with water vapor. The observed species was identified as the most stable conformer with the help of quantum chemical calculations. We also clarified that productions of formic acid and dioxirane are promoted by the existence of water vapor in the discharged reaction system.

  10. Effect of CH stretching excitation on the reaction dynamics of F + CHD{sub 3} → DF + CHD{sub 2}

    SciTech Connect (OSTI)

    Yang, Jiayue; Zhang, Dong; Chen, Zhen; Jiang, Bo; Blauert, Florian; Dai, Dongxu; Wu, Guorong E-mail: xmyang@dicp.ac.cn; Zhang, Donghui; Yang, Xueming E-mail: xmyang@dicp.ac.cn

    2015-07-28

    The vibrationally excited reaction of F + CHD{sub 3}(ν{sub 1} = 1) → DF + CHD{sub 2} at a collision energy of 9.0 kcal/mol is investigated using the crossed-beams and time-sliced velocity map imaging techniques. Detailed and quantitative information of the CH stretching excitation effects on the reactivity and dynamics of the title reaction is extracted with the help of an accurate determination of the fraction of the excited CHD{sub 3} reagent in the crossed-beam region. It is found that all vibrational states of the CHD{sub 2} products observed in the ground-state reaction, which mainly involve the excitation of the umbrella mode of the CHD{sub 2} products, are severely suppressed by the CH stretching excitation. However, there are four additional vibrational states of the CHD{sub 2} products appearing in the excited-state reaction which are not presented in the ground-state reaction. These vibrational states either have the CH stretching excitation retained or involve one quantum excitation in the CH stretching and the excitation of the umbrella mode. Including all observed vibrational states, the overall cross section of the excited-state reaction is estimated to be 66.6% of that of the ground-state one. Experimental results also show that when the energy of CH stretching excitation is released during the reaction, it is deposited almost exclusively as the rovibrational energy of the DF products, with little portion in the translational degree of freedom. For vibrational states of the CHD{sub 2} products observed in both ground- and excited-state reactions, the CH stretching excitation greatly suppresses the forward scattered products, causing a noticeable change in the product angular distributions.

  11. ELECTRON IRRADIATION OF KUIPER BELT SURFACE ICES: TERNARY N{sub 2}-CH{sub 4}-CO MIXTURES AS A CASE STUDY

    SciTech Connect (OSTI)

    Kim, Y. S.; Kaiser, R. I.

    2012-10-10

    The space weathering of icy Kuiper Belt Objects was investigated in this case study by exposing methane (CH{sub 4}) and carbon monoxide (CO) doped nitrogen (N{sub 2}) ices at 10 K to ionizing radiation in the form of energetic electrons. Online and in situ Fourier transform infrared spectroscopy was utilized to monitor the radiation-induced chemical processing of these ices. Along with isocyanic acid (HNCO), the products could be mainly derived from those formed in irradiated binary ices of the N{sub 2}-CH{sub 4} and CO-CH{sub 4} systems: nitrogen-bearing products were found in the form of hydrogen cyanide (HCN), hydrogen isocyanide (HNC), diazomethane (CH{sub 2}N{sub 2}), and its radical fragment (HCN{sub 2}); oxygen-bearing products were of acetaldehyde (CH{sub 3}CHO), formyl radical (HCO), and formaldehyde (H{sub 2}CO). As in the pure ices, the methyl radical (CH{sub 3}) and ethane (C{sub 2}H{sub 6}) were also detected, as were carbon dioxide (CO{sub 2}) and the azide radical (N{sub 3}). Based on the temporal evolution of the newly formed products, kinetic reaction schemes were then developed to fit the temporal profiles of the newly formed species, resulting in numerical sets of rate constants. The current study highlights important constraints on the preferential formation of isocyanic acid (HNCO) over hydrogen cyanide (HCN) and hydrogen isocyanide (HNC), thus guiding the astrobiological and chemical evolution of those distant bodies.

  12. Complete Phase I Tests As Described in the Multi-lab Test Plan for the Evaluation of CH3I Adsorption on AgZ

    SciTech Connect (OSTI)

    Bruffey, S. H.; Jubin, R. T.

    2014-09-30

    Silver-exchanged mordenite (AgZ) has been identified as a potential sorbent for iodine present in the off-gas streams of a used nuclear fuel reprocessing facility. In such a facility, both elemental and organic forms of iodine are released from the dissolver in gaseous form. These species of iodine must be captured with high efficiency for a facility to avoid radioactive iodine release above regulatory limits in the gaseous effluent of the plant. Studies completed at Idaho National Laboratory (INL) examined the adsorption of organic iodine in the form of CH3I by AgZ. Upon breakthrough of the feed gas through the sorbent bed, elemental iodine was observed in the effluent stream, despite the fact that the only source of iodine in the system was the CH3I in the feed gas.1 This behavior does not appear to have been reported previously nor has it been independently confirmed. Thus, as a result of these prior studies, multiple knowledge gaps relating to the adsorption of CH3I by AgZ were identified, and a multi-lab test plan, including Oak Ridge National Laboratory (ORNL), INL, Pacific Northwest National Laboratory (PNNL), and Sandia National Laboratories, was formulated to address each in a systematic way.2 For this report, the scope of work for ORNL was further narrowed to three thin-bed experiments that would characterize CH3I adsorption onto AgZ in the presence of water, NO, and NO2. Completion of these three-thin bed experiments demonstrated that organic iodine in the form of CH3I was adsorbed by reduced silver mordenite (Ag0Z) to a 50% higher loading than that of I2 when adsorbed from a dry air stream. Adsorption curves suggest different adsorption mechanisms for I2 and CH3I. In the presence of NO and NO2 gas, the loading of CH3I onto Ag0Z is suppressed and may be reversible. Further, the presence of NO and NO2 gas appears to oxidize CH3I to I2; this is indicated by an adsorption curve similar to that of I2 on Ag0Z. Finally, the loss of organic iodine loading

  13. Microstructures and properties of CH{sub 3}NH{sub 3}PbI{sub 3?x}Cl{sub x} hybrid solar cells

    SciTech Connect (OSTI)

    Suzuki, Kohei E-mail: oku@mat.usp.ac.jp; Suzuki, Atsushi E-mail: oku@mat.usp.ac.jp; Zushi, Masahito E-mail: oku@mat.usp.ac.jp; Oku, Takeo E-mail: oku@mat.usp.ac.jp

    2015-02-27

    Halide-perovskite CH{sub 3}NH{sub 3}PbI{sub 3} was produced on mesoporous TiO{sub 2} layer by spin-coating a precursor solution of PbCl{sub 2} and CH{sub 3}NH{sub 3}I in dimethylformamide. The role of the annealing process and chlorine (Cl) doping for the perovskite-phase formation was investigated. It was found that crystallization of the perovskite materials was stimulated by the annealing process, and that longer annealing time is necessary for the Cl-doped perovskite compared with that of non-doped perovskite phase.

  14. FCC LPG olefinicity and branching enhanced by octane catalysts

    SciTech Connect (OSTI)

    Keyworth, D.A.; Reid, T.A.; Kreider, K.R.; Yatsu, C.A.

    1989-05-29

    Refiners are increasingly recognizing the downstream opportunities for fluid catalytic cracking LPG olefins for the production of methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE, if the ethanol subsidy is extended to the production of ETBE), and as petrochemical feedstocks. Some of new gasoline FCC octane-enhancing catalysts can support those opportunities because their low non-framework alumina (low NFA) preserve both LPG olefinicity and promote branching of the LPG streams from the FCCU. The combined effect results in more isobutane for alkylate feed, more propylene in the propane/propylene stream, and more isobutene - which makes the addition of an MTBE unit very enticing.

  15. Review of the findings of the Ignik Sikumi CO2-CH4 gas hydrate exchange field trial

    SciTech Connect (OSTI)

    Anderson, Brian J.; Boswell, Ray; Collett, Tim S.; Farrell, Helen; Ohtsuka, Satoshi; White, Mark D.

    2014-08-01

    The Ignik Sikumi Gas Hydrate Exchange Field Trial was conducted by ConocoPhillips in partnership with the U.S. Department of Energy, the Japan Oil, Gas, and Metals National Corporation, and the U.S. Geological Survey within the Prudhoe Bay Unit on the Alaska North Slope (ANS) during 2011 and 2012. The 2011 field program included drilling the vertical test well and performing extensive wireline logging through a thick section of gas-hydrate-bearing sand reservoirs that provided substantial new insight into the nature of ANS gas hydrate occurrences. The 2012 field program involved an extended, scientific field trial conducted within a single vertical well (“huff-and-puff” design) through three primary operational phases: 1) injection of a gaseous phase mixture of CO2, N2, and chemical tracers; 2) flowback conducted at down-hole pressures above the stability threshold for native CH4-hydrate, and 3) extended (30-days) flowback at pressures below the stability threshold of native CH4-hydrate. Ignik Sikumi represents the first field investigation of gas hydrate response to chemical injection, and the longest-duration field reservoir response experiment yet conducted. Full descriptions of the operations and data collected have been fully reported by ConocoPhillips and are available to the science community. The 2011 field program indicated the presence of free water within the gas hydrate reservoir, a finding with significant implications to the design of the exchange trial – most notably the use of a mixed gas injectant. While this decision resulted in a complex chemical environment within the reservoir that greatly tests current experimental and modeling capabilities – without such a mixture, it is apparent that injection could not have been achieved. While interpretation of the field data are continuing, the primary scientific findings and implications of the program are: 1) gas hydrate destabilizing is self-limiting, dispelling any notion of the potential for

  16. Low Surface Recombination Velocity in Solution-Grown CH3NH3PbBr3 Perovskite Single Crystal

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Yang, Ye; Yan, Yong; Yang, Mengjin; Choi, Sukgeun; Zhu, Kai; Luter, Joseph M.; Beard, Matthew C.

    2015-08-06

    Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH3NH3PbBr3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4±0.1 103 cm s-1, B2–3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggests that the planar grain sizemore » for the perovskite thin films should be larger thanB30 mm to avoid the influence of surface recombination on the effective carrier lifetime.« less

  17. Time-Resolved Quantitative Measurement of OH HO2 and CH2O in Fuel Oxidation Reactions by High Resolution IR Absorption Spectroscopy.

    SciTech Connect (OSTI)

    Huang, Haifeng; Rotavera, Brandon; Taatjes, Craig A.

    2014-08-01

    Combined with a Herriott-type multi-pass slow flow reactor, high-resolution differential direct absorption spectroscopy has been used to probe, in situ and quantitatively, hydroxyl (OH), hydroperoxy (HO 2 ) and formaldehyde (CH 2 O) molecules in fuel oxidation reactions in the reactor, with a time resolution of about 1 micro-second. While OH and CH 2 O are probed in the mid-infrared (MIR) region near 2870nm and 3574nm respectively, HO 2 can be probed in both regions: near-infrared (NIR) at 1509nm and MIR at 2870nm. Typical sensitivities are on the order of 10 10 - 10 11 molecule cm -3 for OH at 2870nm, 10 11 molecule cm -3 for HO 2 at 1509nm, and 10 11 molecule cm -3 for CH 2 O at 3574nm. Measurements of multiple important intermediates (OH and HO 2 ) and product (CH 2 O) facilitate to understand and further validate chemical mechanisms of fuel oxidation chemistry.

  18. Effects of support on bifunctional methanol oxidation pathways catalyzed by polyoxometallate keggin clusters

    SciTech Connect (OSTI)

    Liu, Haichao; Iglesia, Enrique

    2003-12-26

    H5PV2Mo10O40 polyoxometallate Keggin clusters supported on ZrO2, TiO2, SiO2, and Al2O3 are effective catalysts for CH3OH oxidation reactions to form HCHO, methyl formate (MF), and dimethoxymethane (DMM). Rates and selectivities and the structure of supported clusters depend on the surface properties of the oxide supports. Raman spectroscopy showed that Keggin structures remained essentially intact on ZrO2, TiO2, and SiO2 after treatment in air at 553 K, but decomposed to MoOx and VOx oligomers on Al2O3. Accessible protons per Keggin unit (KU) were measured during CH3OH oxidation by titration with 2,6-di-tert-butyl pyridine. For similar KU surface densities (0.28 0.37 KU/nm2), the number of accessible protons was larger on SiO2 than on ZrO2 and TiO2 and much smaller on Al2O3 supports, even though residual dimethyl ether (DME) synthesis rates after titrant saturation indicated that the fractional dispersion of KU was similar on the first three supports. These effects of support on structure and on H+ accessibility reflect varying extents of interaction between polyoxometallate clusters and supports. Rates of CH3OH oxidative dehydrogenation per KU were higher on ZrO2 and TiO2 than on SiO2 at similar KU surface densities (0.28 0.37 KU/nm2) and dispersion, indicating that redox properties of Keggin clusters depend on the identity of the support used to disperse them. ZrO2 and TiO2 supports appear to enhance the reducibility of anchored polyoxometallate clusters. Rates were much lower on Al2O3, because structural degradation led to less reactive MoOx and VOx domains. CH3OH reactions involve primary oxidation to form HCHO and subsequent secondary reactions to form DMM and MF. These reactions involve HCHO CH3OH acetalization steps leading to methoxymethanol (CH3OCH2OH) or hemiacetal intermediates, which condense with CH3OH on acid sites to form DMM or dehydrogenate to form MF. COx formation rates are much lower than those of other reactions, and DME forms in parallel

  19. Phase stabilities of pyrite-related MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te): A systematic DFT study

    SciTech Connect (OSTI)

    Bachhuber, Frederik; Krach, Alexander; Furtner, Andrea; Söhnel, Tilo; Peter, Philipp; Rothballer, Jan; Weihrich, Richard

    2015-03-15

    Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine their stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS{sub 2}). - Highlights: • Study of compositional stability of MTCh vs. M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} compounds. • Study of structural stability of known and novel MTCh compounds. • Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS{sub 2}.

  20. Gas-phase photodissociation of CH{sub 3}COCN at 308 nm by time-resolved Fourier-transform infrared emission spectroscopy

    SciTech Connect (OSTI)

    Yeh, Yu-Ying; Chao, Meng-Hsuan; Tsai, Po-Yu; Chang, Yuan-Bin; Tsai, Ming-Tsang; Lin, King-Chuen

    2012-01-28

    By using time-resolved Fourier-transform infrared emission spectroscopy, the fragments of HCN(v= 1, 2) and CO(v= 1-3) are detected in one-photon dissociation of acetyl cyanide (CH{sub 3}COCN) at 308 nm. The S{sub 1}(A'), {sup 1}(n{sub O}, {pi}*{sub CO}) state at 308 nm has a radiative lifetime of 0.46 {+-} 0.01 {mu}s, long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of Ar collision-induced internal conversion is estimated to be (1-7) x 10{sup -12} cm{sup 3} molecule{sup -1} s{sup -1}. The measurements of O{sub 2} dependence exclude the production possibility of these fragments via intersystem crossing. The high-resolution spectra of HCN and CO are analyzed to determine the ro-vibrational energy deposition of 81 {+-} 7 and 32 {+-} 3 kJ/mol, respectively. With the aid of ab initio calculations, a two-body dissociation on the energetic ground state is favored leading to HCN + CH{sub 2}CO, in which the CH{sub 2}CO moiety may further undergo secondary dissociation to release CO. The production of CO{sub 2} in the reaction with O{sub 2} confirms existence of CH{sub 2} and a secondary reaction product of CO. The HNC fragment is identified but cannot be assigned, as restricted to a poor signal-to-noise ratio. Because of insufficient excitation energy at 308 nm, the CN and CH{sub 3} fragments that dominate the dissociation products at 193 nm are not detected.

  1. THE SOURCES OF HCN AND CH{sub 3}OH AND THE ROTATIONAL TEMPERATURE IN COMET 103P/HARTLEY 2 FROM TIME-RESOLVED MILLIMETER SPECTROSCOPY

    SciTech Connect (OSTI)

    Drahus, Michal; Jewitt, David; Guilbert-Lepoutre, Aurelie; Waniak, Waclaw; Sievers, Albrecht

    2012-09-01

    One of the least understood properties of comets is the compositional structure of their nuclei, which can either be homogeneous or heterogeneous. The nucleus structure can be conveniently studied at millimeter wavelengths, using velocity-resolved spectral time series of the emission lines, obtained simultaneously for multiple molecules as the body rotates. Using this technique, we investigated the sources of CH{sub 3}OH and HCN in comet 103P/Hartley 2, the target of NASA's EPOXI mission, which had an exceptionally favorable apparition in late 2010. Our monitoring with the IRAM 30 m telescope shows short-term variability of the spectral lines caused by nucleus rotation. The varying production rates generate changes in brightness by a factor of four for HCN and by a factor of two for CH{sub 3}OH, and they are remarkably well correlated in time. With the addition of the velocity information from the line profiles, we identify the main sources of outgassing: two jets, oppositely directed in a radial sense, and icy grains, injected into the coma primarily through one of the jets. The mixing ratio of CH{sub 3}OH and HCN is dramatically different in the two jets, which evidently shows large-scale chemical heterogeneity of the nucleus. We propose a network of identities linking the two jets with morphological features reported elsewhere and postulate that the chemical heterogeneity may result from thermal evolution. The model-dependent average production rates are 3.5 Multiplication-Sign 10{sup 26} molecules s{sup -1} for CH{sub 3}OH and 1.25 Multiplication-Sign 10{sup 25} molecules s{sup -1} for HCN, and their ratio of 28 is rather high but not abnormal. The rotational temperature from CH{sub 3}OH varied strongly, presumably due to nucleus rotation, with the average value being 47 K.

  2. Infrared spectroscopic and modeling studies of H{sub 2}/CH{sub 4} microwave plasma gas phase from low to high pressure and power

    SciTech Connect (OSTI)

    Rond, C. Lombardi, G.; Gicquel, A.; Hamann, S.; Rpcke, J.; Wartel, M.

    2014-09-07

    InfraRed Tunable Diode Laser Absorption Spectroscopy technique has been implemented in a H{sub 2}/CH{sub 4} Micro-Wave (MW frequency f?=?2.45 GHz) plasma reactor dedicated to diamond deposition under high pressure and high power conditions. Parametric studies such as a function of MW power, pressure, and admixtures of methane have been carried out on a wide range of experimental conditions: the pressure up to 270 mbar and the MW power up to 4?kW. These conditions allow high purity Chemical Vapor Deposition diamond deposition at high growth rates. Line integrated absorption measurements have been performed in order to monitor hydrocarbon species, i.e., CH{sub 3}, CH{sub 4}, C{sub 2}H{sub 2}, C{sub 2}H{sub 4}, and C{sub 2}H{sub 6}. The densities of the stable detected species were found to vary in the range of 10{sup 12}10{sup 17} molecules cm{sup ?3}, while the methyl radical CH{sub 3} (precursor of diamond growth under these conditions) measured into the plasma bulk was found up to 10{sup 14} molecules cm{sup ?3}. The experimental densities have been compared to those provided by 1D-radial thermochemical model for low power and low pressure conditions (up to 100 mbar/2?kW). These densities have been axially integrated. Experimental measurements under high pressure and power conditions confirm a strong increase of the degree of dissociation of the precursor, CH{sub 4}, associated to an increase of the C{sub 2}H{sub 2} density, the most abundant reaction product in the plasma.

  3. Crystal structure of dioxobis(benzhydroxamato)molybdenum(VI) with propionic acid MoO2(C6H5CONHO)2 x 2/3 CH3CH2COOH

    SciTech Connect (OSTI)

    Makhmudova, N.K.; Sharipov, Kh.T.; Kohdashova, T.S.; Porai-Koshits, M.A.; Ibragimov, B.T.

    1987-04-01

    An x-ray structural investigation of the structure of MoO2 (C6H5CONHO)2 x 2/3 CH3CH2COOH (I) has been carried out (diffractometer, Cu K/sub /, least-squares method in the anisotropic approximation to R = 0.053). The crystallographic data are: a = 17.290(2), c = 11.140(2) A, rho(exp) = 1.53, rho(calc) = 1.562(1) g/cmT, space group P61, Z = 6. The crystals of I were built up from monomeric complex molecules of MoO2 (C6H5CONHO)2, which are joined to one another by a system of hydrogen bonds to form a loose three-dimensional skeleton with large channel-like openings. The presence of solvent molecules in I (which were not detected by the analysis of the electron density) is indicated by the band of the stretching vibration of the carbonyl group nu(C=O) of propionic acid at nu = 1720 cm in the IR spectrum of I. The analysis of the derivatogram of I and the comparison of the values of the density of the crystal (calculated and experimental) indicate that the MoO2(BHA)2:PA ratio is equal to 1:2/3. An ordinary distorted octahedral environment of Mo(VI) consisting of oxygen atoms has been established. The geometric characteristics of the cis-molybdenyl grouping are as follows: Mo-O(1) = 1.701(4), Mo-O(2) = 1.679(6) A, and the OMoO angle equals 104.3(3). The magnitude of the effect of the influence of the double bonds in the two independent chelate rings is equal to 0.137 and 0.244 A. The complex molecules of MoO2 (BHA)2 are joined to one another by H bonds, which link the neighboring complexes in helical chains around 61 axes and bind these chains in a three-dimensional framework. The set of H bonds and the arrangement of the chelate rings and phenyl rings result in the formation of channels of types A and B. X-ray powder diffraction analysis showed that the channels of type A are randomly occupied by the molecules of propionic acid (PA).

  4. Synthesis and crystal structure of (NH{sub 4}){sub 3}[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2}[UO{sub 2}(CH{sub 3}COO)(NCS){sub 2}(H{sub 2}O)

    SciTech Connect (OSTI)

    Serezhkina, L. B.; Peresypkina, E. V.; Virovets, A. V.; Karasev, M. O.

    2010-01-15

    Single crystals of the compound (NH{sub 4}){sub 3}[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2}[UO{sub 2}(CH{sub 3}COO)(NCS){sub 2}(H{sub 2}O)] (I) are synthesized, and their structure is investigated using X-ray diffraction. Compound I crystallizes in the monoclinic system with the unit cell parameters a = 18.3414(6) A, b = 16.3858(7) A, c = 12.4183(5) A, {beta} = 92.992(1){sup o}, space group C2/c, Z = 4, V = 3727.1(3) A{sup 3}, and R = 0.0253. The uranium-containing structural units of crystals I are mononuclear complexes of two types with an island structure, i.e., the [UO{sub 2}(CH{sub 3}COO){sub 3}]{sup -} anionic complexes belonging to the crystal-chemical group (AB{sub 3}{sup 01} = UO{sub 2}{sup 2+}, B{sup 01} = CH{sub 3}COO{sup -}) of the uranyl complexes and the [UO{sub 2}(CH{sub 3}COO)(NCS){sub 2}(H{sub 2}O)]{sup -} anionic complexes belonging to the crystal-chemical group AB{sup 01}M{sub 3}{sup 1} (A = UO{sub 2}{sup 2+}, B{sup 01} = CH{sub 3}COO{sup -}, M{sup 1} = NCS{sup -} or H{sub 2}O).

  5. High Temperature, Low Relative Humidity, Polymer-type Membranes Based on Disulfonated Poly(arylene ether) Block and Random Copolymers Optionally Incorporating Protonic Conducting Layered Water insoluble Zirconium Fillers

    SciTech Connect (OSTI)

    McGrath, James E.; Baird, Donald G.

    2010-06-03

    Our research group has been engaged in the past few years in the synthesis of biphenol based partially disulfonated poly(arylene ether sulfone) random copolymers as potential PEMs. This series of polymers are named as BPSH-xx, where BP stands for biphenol, S stands for sulfonated, H stands for acidified and xx represents the degree of disulfonation. All of these sulfonated copolymers phase separate to form nano scale hydrophilic and hydrophobic morphological domains. The hydrophilic phase containing the sulfonic acid moieties causes the copolymer to absorb water. Water confined in hydrophilic pores in concert with the sulfonic acid groups serve the critical function of proton (ion) conduction and water transport in these systems. Both Nafion and BPSH show high proton conductivity at fully hydrated conditions. However proton transport is especially limited at low hydration level for the BPSH random copolymer. It has been observed that the diffusion coefficients of both water and protons change with the water content of the pore. This change in proton and water transport mechanisms with hydration level has been attributed to the solvation of the acid groups and the amount of bound and bulk-like water within a pore. At low hydration levels most of the water is tightly associated with sulfonic groups and has a low diffusion coefficient. This tends to encourage isolated domain morphology. Thus, although there may be significant concentrations of protons, the transport is limited by the discontinuous morphological structure. Hence the challenge lies in how to modify the chemistry of the polymers to obtain significant protonic conductivity at low hydration levels. This may be possible if one can alter the chemical structure to synthesize nanophase separated ion containing block copolymers. Unlike the BPSH copolymers, where the sulfonic acid groups are randomly distributed along the chain, the multiblock copolymers will feature an ordered sequence of hydrophilic and

  6. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbons via Indirect Liquefaction. Thermochemical Research Pathway to High-Octane Gasoline Blendstock Through Methanol/Dimethyl Ether Intermediates

    SciTech Connect (OSTI)

    Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; Hensley, Jesse; Schaidle, Josh; Biddy, Mary; Humbird, David; Snowden-Swan, Lesley J.; Ross, Jeff; Sexton, Danielle; Yap, Raymond; Lukas, John

    2015-03-01

    This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s (BETO’s) efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from lignocellulosic biomass feedstocks. The research funded by BETO is designed to advance the state of technology of biomass feedstock supply and logistics, conversion, and overall system sustainability. It is expected that these research improvements will be made within the 2022 timeframe. As part of their involvement in this research and development effort, the National Renewable Energy Laboratory and the Pacific Northwest National Laboratory investigate the economics of conversion pathways through the development of conceptual biorefinery process models and techno-economic analysis models. This report describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas or syngas via indirect gasification, gas cleanup, catalytic conversion of syngas to methanol intermediate, methanol dehydration to dimethyl ether (DME), and catalytic conversion of DME to high-octane, gasoline-range hydrocarbon blendstock product. The conversion process configuration leverages technologies previously advanced by research funded by BETO and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via reforming of tars and other hydrocarbons is one of the key technology advancements realized as part of this prior research and 2012 demonstrations. The process described in this report evaluates a new technology area for the downstream utilization of clean biomass-derived syngas for the production of high-octane hydrocarbon products through methanol and DME intermediates. In this process, methanol undergoes dehydration to

  7. Photocatalytic CO{sub 2} reduction by CH{sub 4} over montmorillonite modified TiO{sub 2} nanocomposites in a continuous monolith photoreactor

    SciTech Connect (OSTI)

    Tahir, Muhammad; Tahir, Beenish

    2015-03-15

    Highlights: TiO{sub 2}/MMT supported monolith photo-reactor was tested for CO{sub 2} reduction with CH{sub 4}. MMT inhibited crystal growth and enhanced TiO{sub 2} photo-activity in monolith reactor. CO{sub 2} was reduced by CH{sub 4} to CO, CH{sub 3}OH, C{sub 2}H{sub 6}, C{sub 3}H{sub 6} and C{sub 3}H{sub 8} in a monolith reactor. CO yield over TiO{sub 2}/MMT was 237.5 ?mol g-catal.{sup ?1} h{sup ?1}, a 2.52 fold than TiO{sub 2}. Stability test revealed TiO{sub 2}/MMT partially lost photo-activity in reused cyclic runs. - Abstract: In this study, the performance of montmorillonite (MMT) modified TiO{sub 2} nanocomposites for photocatalytic CO{sub 2} reduction with CH{sub 4} in a continuous monolith photoreactor has been investigated. The MMT modified TiO{sub 2} nanocomposites were dip-coated over monolith channels and were characterized by XRD, SEM, TEM, XPS, N{sub 2}-adsorptiondesorption and UVvis spectroscopy. The MMT produced anatase phase of TiO{sub 2} and reduced TiO{sub 2} crystallite size from 19 nm to 13 nm. CO was the major reduction product with a yield rate of 237.5 ?mol g-catal.{sup ?1} h{sup ?1} over 10 wt.% MMT-loaded TiO{sub 2} at 100 C, and CO{sub 2}/CH{sub 4} feed ratio 1.0. The photoactivity of MMT-loaded TiO{sub 2} monolithic catalyst was 2.52 times higher than bare TiO{sub 2}. Likewise, low concentrations of C{sub 2}H{sub 6}, CH{sub 3}OH, C{sub 3}H{sub 6} and C{sub 3}H{sub 8} were detected in the products mixture. These results inferred MMT modified TiO{sub 2} and monolith photoreactor were beneficial for enhancing photocatalysis process with appreciable productivity. The stability test revealed photoactivity of MMT-loaded TiO{sub 2} nanocomposites partially diminished in recycle runs.

  8. The European land and inland water CO2, CO, CH4 and N2O balance between 2001 and 2005

    SciTech Connect (OSTI)

    Luyassaert, S; Abril, G; Andres, Robert Joseph; Bastviken, D; Bellassen, V; Bergamaschi, P; Bousquet, P; Chevallier, F; Ciais, P.; Dechow, R; Erb, K-H; Etiope, G; Fortems-Cheiney, A; Grassi, G; Hartmann, J; Jung, M.; Lathiere, J; Lohila, A; Mayorga, E; Moosdorf, N; Njakou, D; Otto, J; Papale, D.; Peters, W; Peylin, P; Raymond, Peter A; Rodenbeck, C; Saarnio, S; Schulze, E.-D.; Szopa, S; Thompson, R; Verkerk, P; Vuichard, N; Wang, R; Wattenbach, M; Zaehle, S

    2012-01-01

    Globally, terrestrial ecosystems have absorbed about 30% of anthropogenic greenhouse gas emissions over the period 2000-2007 and inter-hemispheric gradients indicate that a significant fraction of terrestrial carbon sequestration must be north of the Equator. We present a compilation of the CO{sub 2}, CO, CH{sub 4} and N{sub 2}O balances of Europe following a dual constraint approach in which (1) a land-based balance derived mainly from ecosystem carbon inventories and (2) a land-based balance derived from flux measurements are compared to (3) the atmospheric data-based balance derived from inversions constrained by measurements of atmospheric GHG (greenhouse gas) concentrations. Good agreement between the GHG balances based on fluxes (1294 {+-} 545 Tg C in CO{sub 2}-eq yr{sup -1}), inventories (1299 {+-} 200 Tg C in CO{sub 2}-eq yr{sup -1}) and inversions (1210 {+-} 405 Tg C in CO{sub 2}-eq yr{sup -1}) increases our confidence that the processes underlying the European GHG budget are well understood and reasonably sampled. However, the uncertainty remains large and largely lacks formal estimates. Given that European net land to atmosphere exchanges are determined by a few dominant fluxes, the uncertainty of these key components needs to be formally estimated before efforts could be made to reduce the overall uncertainty. The net land-to-atmosphere flux is a net source for CO{sub 2}, CO, CH{sub 4} and N{sub 2}O, because the anthropogenic emissions by far exceed the biogenic sink strength. The dual-constraint approach confirmed that the European biogenic sink removes as much as 205 {+-} 72 Tg C yr{sup -1} from fossil fuel burning from the atmosphere. However, This C is being sequestered in both terrestrial and inland aquatic ecosystems. If the C-cost for ecosystem management is taken into account, the net uptake of ecosystems is estimated to decrease by 45% but still indicates substantial C-sequestration. However, when the balance is extended from CO{sub 2} towards

  9. The role of the transition state in polyatomic reactions: Initial state-selected reaction probabilities of the H + CH{sub 4} ? H{sub 2} + CH{sub 3} reaction

    SciTech Connect (OSTI)

    Welsch, Ralph Manthe, Uwe

    2014-11-07

    Full-dimensional calculations of initial state-selected reaction probabilities on an accurate ab initio potential energy surface (PES) have been communicated recently [R. Welsch and U. Manthe, J. Chem. Phys. 141, 051102 (2014)]. These calculations use the quantum transition state concept, the multi-layer multi-configurational time-dependent Hartree approach, and graphics processing units to speed up the potential evaluation. Here further results of these calculations and an extended analysis are presented. State-selected reaction probabilities are given for many initial ro-vibrational states. The role of the vibrational states of the activated complex is analyzed in detail. It is found that rotationally cold methane mainly reacts via the ground state of the activated complex while rotationally excited methane mostly reacts via HHCH{sub 3}-bending excited states of the activated complex. Analyzing the different contributions to the reactivity of the vibrationally states of methane, a complex pattern is found. Comparison with initial state-selected reaction probabilities computed on the semi-empirical Jordan-Gilbert PES reveals the dependence of the results on the specific PES.

  10. Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Wang, Yun; Huang, Jingsong; Sumpter, Bobby G.; Zhang, Haimin; Liu, Porun; Yang, Huagui; Zhao, Huijun

    2014-12-19

    Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms,more » which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.« less

  11. Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3

    SciTech Connect (OSTI)

    Wang, Yun; Huang, Jingsong; Sumpter, Bobby G; Zhang, Haimin; Liu, Porun; Yang, Huagui; Zhao, Huijun

    2015-01-01

    Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms, which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.

  12. Intermolecular potential energy surface and thermophysical properties of the CH{sub 4}N{sub 2} system

    SciTech Connect (OSTI)

    Hellmann, Robert Bich, Eckard; Vogel, Eckhard; Vesovic, Velisa

    2014-12-14

    A five-dimensional potential energy surface (PES) for the interaction of a rigid methane molecule with a rigid nitrogen molecule was determined from quantum-chemical ab initio calculations. The counterpoise-corrected supermolecular approach at the CCSD(T) level of theory was utilized to compute a total of 743 points on the PES. The interaction energies were calculated using basis sets of up to quadruple-zeta quality with bond functions and were extrapolated to the complete basis set limit. An analytical site-site potential function with nine sites for methane and five sites for nitrogen was fitted to the interaction energies. The PES was validated by calculating the cross second virial coefficient as well as the shear viscosity and binary diffusion coefficient in the dilute-gas limit for CH{sub 4}N{sub 2} mixtures. An improved PES was obtained by adjusting a single parameter of the analytical potential function in such a way that quantitative agreement with the most accurate experimental values of the cross second virial coefficient was achieved. The transport property values obtained with the adjusted PES are in good agreement with the best experimental data.

  13. Thermogravimetric Analysis of Modified Hematite by Methane (CH{sub 4}) for Chemical-Looping Combustion: A Global Kinetics Mechanism

    SciTech Connect (OSTI)

    Monazam, Esmail R.; Breault, Ronald W.; Siriwardane, Ranjani; Miller, Duane D.

    2013-10-01

    Iron oxide (Fe{sub 2}O{sub 3}) or in its natural form (hematite) is a potential material to capture CO{sub 2} through the chemical-looping combustion (CLC) process. It is known that magnesium (Mg) is an effective methyl cleaving catalyst and as such it has been combined with hematite to assess any possible enhancement to the kinetic rate for the reduction of Fe{sub 2}O{sub 3} with methane. Therefore, in order to evaluate its effectiveness as a hematite additive, the behaviors of Mg-modified hematite samples (hematite 5% Mg(OH){sub 2}) have been analyzed with regard to assessing any enhancement to the kinetic rate process. The Mg-modified hematite was prepared by hydrothermal synthesis. The reactivity experiments were conducted in a thermogravimetric analyzer (TGA) using continuous stream of CH{sub 4} (5, 10, and 20%) at temperatures ranging from 700 to 825 {degrees}C over ten reduction cycles. The mass spectroscopy analysis of product gas indicated the presence of CO{sub 2}, H{sub 2}O, H{sub 2} and CO in the gaseous product. The kinetic data at reduction step obtained by isothermal experiments could be well fitted by two parallel rate equations. The modified hematite samples showed higher reactivity as compared to unmodified hematite samples during reduction at all investigated temperatures.

  14. The efficiency limit of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite solar cells

    SciTech Connect (OSTI)

    Sha, Wei E. I.; Ren, Xingang; Chen, Luzhou; Choy, Wallace C. H.

    2015-06-01

    With the consideration of photon recycling effect, the efficiency limit of methylammonium lead iodide (CH{sub 3}NH{sub 3}PbI{sub 3}) perovskite solar cells is predicted by a detailed balance model. To obtain convincing predictions, both AM 1.5 spectrum of Sun and experimentally measured complex refractive index of perovskite material are employed in the detailed balance model. The roles of light trapping and angular restriction in improving the maximal output power of thin-film perovskite solar cells are also clarified. The efficiency limit of perovskite cells (without the angular restriction) is about 31%, which approaches to Shockley-Queisser limit (33%) achievable by gallium arsenide (GaAs) cells. Moreover, the Shockley-Queisser limit could be reached with a 200 nm-thick perovskite solar cell, through integrating a wavelength-dependent angular-restriction design with a textured light-trapping structure. Additionally, the influence of the trap-assisted nonradiative recombination on the device efficiency is investigated. The work is fundamentally important to high-performance perovskite photovoltaics.

  15. The complete, temperature resolved experimental spectrum of methanol (CH{sub 3}OH) between 560 and 654 GHz

    SciTech Connect (OSTI)

    Fortman, Sarah M.; Neese, Christopher F.; De Lucia, Frank C.

    2014-02-20

    The complete spectrum of methanol (CH{sub 3}OH) has been characterized over a range of astrophysically significant temperatures in the 560.4-654.0 GHz spectral region. Absolute intensity calibration and analysis of 166 experimental spectra recorded over a slow 248-398 K temperature ramp provide a means for the simulation of the complete spectrum of methanol as a function of temperature. These results include contributions from v{sub t} = 3 and other higher states that are difficult to model via quantum mechanical (QM) techniques. They also contain contributions from the {sup 13}C isotopologue in terrestrial abundance. In contrast to our earlier work on semi-rigid species, such as ethyl cyanide and vinyl cyanide, significant intensity differences between these experimental values and those calculated by QM methods were found for many of the lines. Analysis of these differences shows the difficulty of the calculation of dipole matrix elements in the context of the internal rotation of the methanol molecule. These results are used to both provide catalogs in the usual line frequency, linestrength, and lower state energy format, as well as in a frequency point-by-point catalog that is particularly well suited for the characterization of blended lines.

  16. Evaluation of the new cosmos sensor CH-01 for the detection of methane, in terms of selectivity and long-term stability

    SciTech Connect (OSTI)

    Massok, P.; Bertrand, D.

    1996-12-31

    For the last few years, Gaz de France has been interested in natural gas detection, which could become an additional service for its customers. Since these detectors would be linked to a shut-off valve, included in the new smart gas meter Dialogaz, they have to be reliable. That is why Gaz de France defined a protocol to evaluate sensors in terms of sensitivity to methane, selectivity to other gases and long-term stability. In the Gaz de France Research Centre laboratories, several commercialized sensors have already been tested among them the sensor CH-01, manufactured and distributed by New Cosmos Electric Co. Ltd, and distributed in Europe by Schlumberger Industries Gas Division, under the name CH-M.

  17. Intermolecular C?H bond activation of benzene and pyridines by a vanadium(III) alkylidene including a stepwise conversion of benzene to a vanadium-benzyne complex

    SciTech Connect (OSTI)

    Andino, Jos G.; Kilgore, Uriah J.; Pink, Maren; Ozarowski, Andrew; Krzystek, J.; Telser, Joshua; Baik, Mu-Hyun; Mindiola, Daniel J.

    2012-01-20

    Breaking of the carbon-hydrogen bond of benzene and pyridine is observed with (PNP)V(CH{sub 2}tBu){sub 2} (1), and in the case of benzene, the formation of an intermediate benzyne complex (C) is proposed, and indirect proof of its intermediacy is provided by identification of (PNP)VO({eta}{sup 2}-C{sub 6}H{sub 4}) in combination with DFT calculations.

  18. Airborne CH2O measurements over the North Atlantic during the 1997 NARE campaign: Instrument comparisons and distributions

    SciTech Connect (OSTI)

    Fried, Alan; Lee, Yin -Nan; Frost, Greg; Wert, Bryan; Henry, Bruce; Drummond, James R.; Hubler, Gerd; Jobson, Tom

    2002-02-27

    Here, formaldehyde measurements from two independent instruments are compared with photochemical box model calculations. The measurements were made on the NOAA P-3 aircraft as part of the 1997 North Atlantic Regional Experiment (NARE 1997). After examining the possible reasons for the model-measurement discrepancy, we conclude that there are probably one or more additional unknown sources of CH2O in the North Atlantic troposphere.

  19. Electron-hole diffusion lengths >175 μm in solution-grown CH3NH3PbI3 single crystals

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Dong, Qingfeng; Fang, Yanjun; Shao, Yuchuan; Mulligan, Padhraic; Qiu, Jie; Cao, Lei; Huang, Jinsong

    2015-02-27

    Long, balanced electron and hole diffusion lengths greater than 100 nanometers in the polycrystalline organolead trihalide compound CH3NH3PbI3 are critical for highly efficient perovskite solar cells. We found that the diffusion lengths in CH3NH3PbI3 single crystals grown by a solution-growth method can exceed 175 micrometers under 1 sun (100 mW cm–2) illumination and exceed 3 millimeters under weak light for both electrons and holes. The internal quantum efficiencies approach 100% in 3-millimeter-thick single-crystal perovskite solar cells under weak light. These long diffusion lengths result from greater carrier mobility, longer lifetime, and much smaller trap densities in the single crystals thanmore » in polycrystalline thin films. As a result, the long carrier diffusion lengths enabled the use of CH3NH3PbI3 in radiation sensing and energy harvesting through the gammavoltaic effect, with an efficiency of 3.9% measured with an intense cesium-137 source.« less

  20. Alternative current conduction mechanisms of organic-inorganic compound [N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4}

    SciTech Connect (OSTI)

    Ben Bechir, M. Karoui, K.; Guidara, K.; Ben Rhaiem, A.; Tabellout, M.

    2014-04-21

    [N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4} has been studied by X-ray powder diffraction patterns, differential scanning calorimetry (DSC), and impedance spectroscopy. The [N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4} hybrid compound is crystallized at room temperature (T ? 300?K) in the orthorhombic system with Pnma space group. Five phase transitions (T{sub 1}?=?255?K, T{sub 2}?=?282?K, T{sub 3}?=?302?K, T{sub 4}?=?320?K, and T{sub 5}?=?346?K) have been proved by DSC measurements. The electrical technique was measured in the 10{sup ?1}-10{sup 7}?Hz frequency range and 233363?K temperature interval. The frequency dependence of alternative current (AC) conductivity is interpreted in terms of Jonscher's law. The AC electrical conduction in [N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4} is analyzed by different processes, which can be attributed to several models: the correlated barrier hopping model in phase I, the overlapping large polaron tunneling model in phase II, the quantum mechanical tunneling model in phase IV, and the non-overlapping small polaron tunneling model in phases III, V, and VI. The conduction mechanism is studied with the help of Elliot's theory, and the Elliot's parameters are determined.

  1. Alternative current conduction mechanisms of organic-inorganic compound [N(CH{sub 3}){sub 3}H]{sub 2}CuCl{sub 4}

    SciTech Connect (OSTI)

    Ben Bechir, M. Karoui, K.; Guidara, K.; Ben Rhaiem, A.; Tabellout, M.

    2014-05-28

    The [N(CH{sub 3}){sub 3}H]{sub 2}CuCl{sub 4} single crystal has been analyzed by X-ray powder diffraction patterns, differential scanning calorimetry (DSC), and electrical impedance spectroscopy. [N(CH{sub 3}){sub 3}H]{sub 2}CuCl{sub 4} crystallizes at room temperature in the monoclinic system with P2{sub 1}/{sub C} space group. Three phase transitions at T{sub 1}?=?226?K, T{sub 2}?=?264?K, and T{sub 3}?=?297?K have been evidenced by DSC measurements. The electrical technique was measured in the 10{sup ?1}10{sup 7}?Hz frequency range and 203313?K temperature intervals. The frequency dependence of alternative current (AC) conductivity is interpreted in terms of Jonscher's law (developed). The AC electrical conduction in [N(CH{sub 3}){sub 3}H]{sub 2}CuCl{sub 4} compound is studied by two processes which can be attributed to a hopping transport mechanism: the correlated barrier hopping model in phases I, II, and III, the non-overlapping small polaron tunneling model in phase IV. The conduction mechanism is interpreted with the help of Elliot's theory, and the Elliot's parameters are found.

  2. Dissociative adsorption of CH{sub 3}X (X = Br and Cl) on a silicon(100) surface revisited by density functional theory

    SciTech Connect (OSTI)

    Wang, Chen-Guang; Huang, Kai E-mail: wji@ruc.edu.cn; Ji, Wei E-mail: wji@ruc.edu.cn

    2014-11-07

    During the dissociative adsorption on a solid surface, the substrate usually participates in a passive manner to accommodate fragments produced upon the cleavage of the internal bond(s) of a (transient) molecular adsorbate. This simple picture, however, neglects the flexibility of surface atoms. Here, we report a Density Functional Theory study to revisit our early studies of the dissociative adsorption of CH{sub 3}X (X = Br and Cl) on Si(100). We have identified a new reaction pathway, which involves a flip of a silicon dimer; this new pathway agrees better with experiments. For our main exemplar of CH{sub 3}Br, insights have been gained using a simple model that involves a three-atom reactive center, Br-C-Si. When the silicon dimer flips, the interaction between C and Si in the Br-C-Si center is enhanced, evident in the increased energy-split of the frontier orbitals. We also examine how the dissociation dynamics of CH{sub 3}Br is altered on a heterodimer (Si-Al, Si-P, and Si-Ge) in a Si(100) surface. In each case, we conclude, on the basis of computed reaction pathways, that no heterodimer flipping is involved before the system transverses the transition state to dissociative adsorption.

  3. Electron-hole diffusion lengths >175 μm in solution-grown CH3NH3PbI3 single crystals

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Dong, Qingfeng; Fang, Yanjun; Shao, Yuchuan; Mulligan, Padhraic; Qiu, Jie; Cao, Lei; Huang, Jinsong

    2015-02-27

    Long, balanced electron and hole diffusion lengths greater than 100 nanometers in the polycrystalline organolead trihalide compound CH3NH3PbI3 are critical for highly efficient perovskite solar cells. We found that the diffusion lengths in CH3NH3PbI3 single crystals grown by a solution-growth method can exceed 175 micrometers under 1 sun (100 mW cm–2) illumination and exceed 3 millimeters under weak light for both electrons and holes. The internal quantum efficiencies approach 100% in 3-millimeter-thick single-crystal perovskite solar cells under weak light. These long diffusion lengths result from greater carrier mobility, longer lifetime, and much smaller trap densities in the single crystals thanmore »in polycrystalline thin films. As a result, the long carrier diffusion lengths enabled the use of CH3NH3PbI3 in radiation sensing and energy harvesting through the gammavoltaic effect, with an efficiency of 3.9% measured with an intense cesium-137 source.« less

  4. CW EC-QCL-based sensor for simultaneous detection of H2O, HDO, N2O and CH4 using multi-pass absorption spectroscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Yu, Yajun; Sanchez, Nancy P.; Griffin, Robert J.; Tittel, Frank K.

    2016-05-03

    A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H2O, HDO, N2O and CH4 using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm-1 operating at similar to 7.8 mu m was scanned covering four neighboring absorption lines, for H2O at 1281.161 cm-1, HDO at 1281.455 cm-1, N2O at 1281.53 cm-1 and CH4 at 1281.61 cm-1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonic detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviationmore » analysis indicated that minimum detection limits of 1.77 ppmv for H2O, 3.92 ppbv for HDO, 1.43 ppbv for N2O, and 2.2 ppbv for CH4 were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. In conclusion, experimental measurements of ambient air are also reported.« less

  5. U.S. Oxygenate Production

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    By: Product Area May-15 Jun-15 Jul-15 Aug-15 Sep-15 Oct-15 View History Fuel Ethanol 29,666 29,684 30,256 29,621 28,543 30,139 1981-2015 Methyl Tertiary Butyl Ether (MTBE) 1,634...

  6. Status and Impacts of State MTBE Bans

    Reports and Publications (EIA)

    2003-01-01

    This paper describes legislation passed in 16 states banning or restricting the use of methyl tertiary butyl ether (MTBE) in gasoline. Analysis of the status and impact of these state MTBE bans is provided concerning the supply and potential price changes of gasoline.

  7. Motor Gasoline Outlook and State MTBE Bans

    Reports and Publications (EIA)

    2003-01-01

    The U.S. is beginning the summer 2003 driving season with lower gasoline inventories and higher prices than last year. Recovery from this tight gasoline market could be made more difficult by impending state bans on the blending of methyl tertiary butyl ether (MTBE) into gasoline that are scheduled to begin later this year.

  8. Impact of Renewable Fuels Standard/MTBE Provisions of S. 1766

    Reports and Publications (EIA)

    2002-01-01

    This service report addresses the Renewable Fuels Standard (RFS)/methyl tertiary butyl ether (MTBE) provisions of S. 1766. The 'S. 1766' Case reflects provisions of S. 1766 including a renewable fuels standard (RFS) reaching five billion gallons by 2012, a complete phase-out of MTBE within four years, and the option for states to waive the oxygen requirement for reformulated gasoline (RFG).

  9. Eliminating MTBE in Gasoline in 2006

    Reports and Publications (EIA)

    2006-01-01

    A review of the market implications resulting from the rapid change from methyl tertiary butyl ether (MTBE) to ethanol-blended reformulated gasoline (RFG) on the East Coast and in Texas. Strains in ethanol supply and distribution will increase the potential for price volatility in these regions this summer.

  10. Acute alteration of cardiac ECG, action potential, I{sub Kr} and the human ether-a-go-go-related gene (hERG) K{sup +} channel by PCB 126 and PCB 77

    SciTech Connect (OSTI)

    Park, Mi-Hyeong; Park, Won Sun; Jo, Su-Hyun

    2012-07-01

    Polychlorinated biphenyls (PCBs) have been known as serious persistent organic pollutants (POPs), causing developmental delays and motor dysfunction. We have investigated the effects of two PCB congeners, 3,3′,4,4′-tetrachlorobiphenyl (PCB 77) and 3,3′,4,4′,5-pentachlorobiphenyl (PCB 126) on ECG, action potential, and the rapidly activating delayed rectifier K{sup +} current (I{sub Kr}) of guinea pigs' hearts, and hERG K{sup +} current expressed in Xenopus oocytes. PCB 126 shortened the corrected QT interval (QTc) of ECG and decreased the action potential duration at 90% (APD{sub 90}), and 50% of repolarization (APD{sub 50}) (P < 0.05) without changing the action potential duration at 20% (APD{sub 20}). PCB 77 decreased APD{sub 20} (P < 0.05) without affecting QTc, APD{sub 90}, and APD{sub 50}. The PCB 126 increased the I{sub Kr} in guinea-pig ventricular myocytes held at 36 °C and hERG K{sup +} current amplitude at the end of the voltage steps in voltage-dependent mode (P < 0.05); however, PCB 77 did not change the hERG K{sup +} current amplitude. The PCB 77 increased the diastolic Ca{sup 2+} and decreased Ca{sup 2+} transient amplitude (P < 0.05), however PCB 126 did not change. The results suggest that PCB 126 shortened the QTc and decreased the APD{sub 90} possibly by increasing I{sub Kr}, while PCB 77 decreased the APD{sub 20} possibly by other modulation related with intracellular Ca{sup 2+}. The present data indicate that the environmental toxicants, PCBs, can acutely affect cardiac electrophysiology including ECG, action potential, intracellular Ca{sup 2+}, and channel activity, resulting in toxic effects on the cardiac function in view of the possible accumulation of the PCBs in human body. -- Highlights: ► PCBs are known as serious environmental pollutants and developmental disruptors. ► PCB 126 shortened QT interval of ECG and action potential duration. ► PCB 126 increased human ether-a-go-go-related K{sup +} current and I{sub Kr}. ► PCB

  11. Ultrafast dynamics of strong-field dissociative ionization ofCH2Br2 probed by femtosecond soft x-ray transient absorptionspectroscopy

    SciTech Connect (OSTI)

    Loh, Zhi-Heng; Leone, Stephen R.

    2008-01-15

    Femtosecond time-resolved soft x-ray transient absorption spectroscopy based on a high-order harmonic generation source is used to investigate the dissociative ionization of CH{sub 2}Br{sub 2} induced by 800 nm strong-field irradiation. At moderate peak intensities (2.0 x 10{sup 14} W/cm{sup 2}), strong-field ionization is accompanied by ultrafast C-Br bond dissociation, producing both neutral Br ({sup 2}P{sub 3/2}) and Br* ({sup 2}P{sub 1/2}) atoms together with the CH{sub 2}Br{sup +} fragment ion. The measured rise times for Br and Br* are 130 {+-} 22 fs and 74 {+-} 10 fs, respectively. The atomic bromine quantum state distribution shows that the Br/Br* population ratio is 8.1 {+-} 3.8 and that the Br {sup 2}P{sub 3/2} state is not aligned. The observed product distribution and the timescales of the photofragment appearances suggest that multiple field-dressed potential energy surfaces are involved in the dissociative ionization process. In addition, the transient absorption spectrum of CH{sub 2}Br{sub 2}{sup +} suggests that the alignment of the molecule relative to the polarization axis of the strong-field ionizing pulse determines the electronic symmetry of the resulting ion; alignment of the Br-Br, H-H, and C{sub 2} axis of the molecule along the polarization axis results in the production of the ion {tilde X}({sup 2}B{sub 2}), {tilde B}({sup 2}B{sub 1}) and {tilde C}({sup 2}A{sub 1}) states, respectively. At higher peak intensities (6.2 x 10{sup 14} W/cm{sup 2}), CH{sub 2}Br{sub 2}{sup +} undergoes sequential ionization to form the metastable CH{sub 2}Br{sub 2}{sup 2+} dication. These results demonstrate the potential of core-level probing with high-order harmonic transient absorption spectroscopy for studying ultrafast molecular dynamics.

  12. Development of alternative fuels from coal derived syngas. Topical report: Task 2.2, Demonstration of a one-step slurry-phase process for the production of dimethyl ether/methanol mixtures at the LaPorte Alternative Fuels Development Unit

    SciTech Connect (OSTI)

    Not Available

    1993-06-01

    This report documents engineering, modification, and operations efforts of demonstration of dimethyl-ether/methanol coproduction in a slurry-phase reactor, carried out in a 2-ft diameter bubble column reactor. Equipment modifications made it possible to remove the product DME and by-product CO{sub 2} from the reactor effluent. Coproduction of dimethyl-ether (DME) and methanol (MeOH) was accomplished in the slurry reactor by physically mixing two different catalysts. The catalyst used to produce MeOH from syngas was manufactured by BASF (type S3-86); the catalyst used to convert MeOH to DME was Catapal {gamma}-alumina. Ratio of MeOH to DME catalysts determined the selectivity towards DME. The demonstration sought to study effect of cocatalyst ratio on product selectivity. Three different proportions of DME catalyst were examined: 0, 6.6, and 19.3 wt % alumina. At each catalyst proportion, the plant was operated at two different gas space velocities. Some process variables were maintained at fixed conditions; most important variables included: reactor temperature (482F), reactor pressure (750 psig), and reactor feed gas composition (35% H{sub 2}, 51% CO,13% CO{sub 2} 1% other, nominal-molar basis).

  13. CH Packaging Program Guidance

    SciTech Connect (OSTI)

    None, None

    2008-09-11

    The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the pplication." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the U.S. Department of Energy (DOE) or the Waste Isolation Pilot Plant (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations (CFR) §71.8. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required. In accordance with 10 CFR Part 71, certificate holders, packaging users, and contractors or subcontractors who use, design, fabricate, test, maintain, or modify the packaging shall post copies of (1) 10 CFR Part 21 regulations, (2) Section 206 of the Energy Reorganization Act of 1974, and (3) NRC Form 3, Notice to Employees. These documents must be posted in a conspicuous location where the activities subject to these regulations are conducted. This document provides the instructions to be followed to operate, maintain, and test the TRUPACT-II and HalfPACT packaging. The intent of these instructions is to standardize operations. All users will follow these instructions or equivalent instructions that assure operations are safe and meet the requirements of the SARPs.

  14. CH Packaging Program Guidance

    SciTech Connect (OSTI)

    None, None

    2007-12-13

    The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the U.S. Department of Energy (DOE) or the Waste Isolation Pilot Plant (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations (CFR) §71.8. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required.In accordance with 10 CFR Part 71, certificate holders, packaging users, and contractors or subcontractors who use, design, fabricate, test, maintain, or modify the packaging shall post copies of (1) 10 CFR Part 21 regulations, (2) Section 206 of the Energy Reorganization Act of 1974, and (3) NRC Form 3, Notice to Employees. These documents must be posted in a conspicuous location where the activities subject to these regulations are conducted.

  15. CH Packaging Program Guidance

    SciTech Connect (OSTI)

    None, None

    2006-04-25

    The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package TransporterModel II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the U.S. Department of Energy (DOE) or the Waste Isolation Pilot Plant| (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations(CFR) §71.8. Any time a user suspects or has indications that the conditions ofapproval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required.In accordance with 10 CFR Part 71, certificate holders, packaging users, and contractors or subcontractors who use, design, fabricate, test, maintain, or modify the packaging shall post copies of (1) 10 CFR Part 21 regulations, (2) Section 206 of the Energy Reorganization Act of 1974, and (3) NRC Form 3, Notice to Employees. These documents must be posted in a conspicuous location where the activities subject to these regulations are conducted.

  16. CH Packaging Program Guidance

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2005-02-28

    The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the Waste Isolation Pilot Plant (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations (CFR) §71.8. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required.

  17. CH Packaging Program Guidance

    SciTech Connect (OSTI)

    None, None

    2009-06-01

    The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and U.S. Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: "each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application." They further state: "each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application." Chapter 9.0 of the SARP charges the U.S. Department of Energy (DOE) or the Waste Isolation Pilot Plant (WIPP) management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with Title 10 Code of Federal Regulations (CFR) §71.8. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. The CBFO will evaluate the issue and notify the NRC if required. In accordance with 10 CFR Part 71, certificate holders, packaging users, and contractors or subcontractors who use, design, fabricate, test, maintain, or modify the packaging shall post copies of (1) 10 CFR Part 21 regulations, (2) Section 206 of the Energy Reorganization Act of 1974, and (3) NRC Form 3, Notice to Employees. These documents must be posted in a conspicuous location where the activities subject to these regulations are conducted. This document provides the instructions to be followed to operate, maintain, and test the TRUPACT-II and HalfPACT packaging. The intent of these instructions is to standardize operations. All users will follow these instructions or equivalent instructions that assure operations are safe and meet the requirements of the SARPs.

  18. Pub-3000: CH45

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    C. Transporting Hazardous Materials Work Process D. Berkeley Lab Chemical Management System (Chemical Inventory) Work Process E. Chemical Hazard Descriptions Work Process F....

  19. CH Packaging Program Guidance

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2003-04-30

    The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT shipping package, and directly related components. This document complies with the minimum requirements as specified in the TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event of a conflict between this document and the SARP or C of C, the C of C shall govern. The C of Cs state: ''each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application.'' They further state: ''each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application.'' Chapter 9.0 of the SARP charges the WIPP management and operating (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with 10 CFR 71.11. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. CBFO will evaluate the issue and notify the NRC if required. This document provides the instructions to be followed to operate, maintain, and test the TRUPACT-II and HalfPACT packaging. The intent of these instructions is to standardize operations. All users will follow these instructions or equivalent instructions that assure operations are safe and meet the requirements of the SARPs.

  20. CH Packaging Program Guidance

    SciTech Connect (OSTI)

    Washington TRU Solutions LLC

    2002-03-04

    The purpose of this document is to provide the technical requirements for preparation for use, operation, inspection, and maintenance of a Transuranic Package Transporter Model II (TRUPACT-II), a HalfPACT Shipping Package, and directly related components. This document complies with the minimum requirements as specified in TRUPACT-II Safety Analysis Report for Packaging (SARP), HalfPACT SARP, and Nuclear Regulatory Commission (NRC) Certificates of Compliance (C of C) 9218 and 9279, respectively. In the event there is a conflict between this document and the SARP or C of C, the SARP and/or C of C shall govern. C of Cs state: ''each package must be prepared for shipment and operated in accordance with the procedures described in Chapter 7.0, Operating Procedures, of the application.'' They further state: ''each package must be tested and maintained in accordance with the procedures described in Chapter 8.0, Acceptance Tests and Maintenance Program of the Application.'' Chapter 9.0 of the SAR P charges the WIPP Management and Operation (M&O) contractor with assuring packaging is used in accordance with the requirements of the C of C. Because the packaging is NRC-approved, users need to be familiar with 10 CFR 71.11. Any time a user suspects or has indications that the conditions of approval in the C of C were not met, the Carlsbad Field Office (CBFO) shall be notified immediately. CBFO will evaluate the issue and notify the NRC if required. This document details the instructions to be followed to operate, maintain, and test the TRUPACT-II and HalfPACT packaging. The intent of these instructions is to standardize these operations. All users will follow these instructions or equivalent instructions that assure operations are safe and meet the requirements of the SARPs.