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Sample records for 1-butene 2-methylpropene trans-2-butene

  1. Reaction rate and isomer-specific product branching ratios of C2H + C4H8: 1-butene, cis-2-butene, trans-2-butene, and isobutene at 79 K.

    PubMed

    Bouwman, Jordy; Fournier, Martin; Sims, Ian R; Leone, Stephen R; Wilson, Kevin R

    2013-06-20

    The reactions of C2H radicals with C4H8 isomers 1-butene, cis-2-butene, trans-2-butene, and isobutene are studied by laser photolysis-vacuum ultraviolet mass spectrometry in a Laval nozzle expansion at 79 K. Bimolecular-reaction rate constants are obtained by measuring the formation rate of the reaction product species as a function of the reactant density under pseudo-first-order conditions. The rate constants are (1.9 0.5) 10(-10), (1.7 0.5) 10(-10), (2.1 0.7) 10(-10), and (1.8 0.9) 10(-10) cm(3) s(-1) for the reaction of C2H with 1-butene, cis-2-butene, trans-2-butene, and isobutene, respectively. Bimolecular rate constants for 1-butene and isobutene compare well to values measured previously at 103 K using C2H chemiluminescence. Photoionization spectra of the reaction products are measured and fitted to ionization spectra of the contributing isomers. In conjunction with absolute-ionization cross sections, these fits provide isomer-resolved product branching fractions. The reaction between C2H and 1-butene yields (65 10)% C4H4 in the form of vinylacetylene and (35 10)% C5H6 in the form of 4-penten-1-yne. The cis-2-butene and trans-2-butene reactions yield solely 3-penten-1-yne, and no discrimination is made between cis- and trans-3-penten-1-yne. Last, the isobutene reaction yields (26 15)% 3-penten-1-yne, (35 15)% 2-methyl-1-buten-3-yne, and (39 15)% 4-methyl-3-penten-1-yne. The branching fractions reported for the C2H and butene reactions indicate that these reactions preferentially proceed via CH3 or C2H3 elimination rather than H-atom elimination. Within the experimental uncertainties, no evidence is found for the formation of cyclic species. PMID:23701666

  2. Metabolism of 2-Methylpropene (Isobutylene) by the Aerobic Bacterium Mycobacterium sp. Strain ELW1

    PubMed Central

    Kottegoda, Samanthi; Waligora, Elizabeth

    2015-01-01

    An aerobic bacterium (Mycobacterium sp. strain ELW1) that utilizes 2-methylpropene (isobutylene) as a sole source of carbon and energy was isolated and characterized. Strain ELW1 grew on 2-methylpropene (growth rate = 0.05 h−1) with a yield of 0.38 mg (dry weight) mg 2-methylpropene−1. Strain ELW1 also grew more slowly on both cis- and trans-2-butene but did not grow on any other C2 to C5 straight-chain, branched, or chlorinated alkenes tested. Resting 2-methylpropene-grown cells consumed ethene, propene, and 1-butene without a lag phase. Epoxyethane accumulated as the only detected product of ethene oxidation. Both alkene consumption and epoxyethane production were fully inhibited in cells exposed to 1-octyne, suggesting that alkene oxidation is initiated by an alkyne-sensitive, epoxide-generating monooxygenase. Kinetic analyses indicated that 1,2-epoxy-2-methylpropane is rapidly consumed during 2-methylpropene degradation, while 2-methyl-2-propen-1-ol is not a significant metabolite of 2-methylpropene catabolism. Degradation of 1,2-epoxy-2-methylpropane by 2-methylpropene-grown cells led to the accumulation and further degradation of 2-methyl-1,2-propanediol and 2-hydroxyisobutyrate, two sequential metabolites previously identified in the aerobic microbial metabolism of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA). Growth of strain ELW1 on 2-methylpropene, 1,2-epoxy-2-methylpropane, 2-methyl-1,2-propanediol, and 2-hydroxyisobutyrate was fully inhibited when cobalt ions were omitted from the growth medium, while growth on 3-hydroxybutyrate and other substrates was unaffected by the absence of added cobalt ions. Our results suggest that, like aerobic MTBE- and TBA-metabolizing bacteria, strain ELW1 utilizes a cobalt/cobalamin-dependent mutase to transform 2-hydroxyisobutyrate. Our results have been interpreted in terms of their impact on our understanding of the microbial metabolism of alkenes and ether oxygenates. PMID:25576605

  3. Interactions of Molecules with cis and trans Double Bonds: A Theoretical Study of cis- and trans-2-Butene.

    PubMed

    Zari?, Milana M; Bugarski, Branko; Kijev?anin, Mirjana Lj

    2016-01-01

    Noncovalent interactions of cis- and trans-2-butene, as the smallest model systems of molecules with cis and trans double bonds, were studied to find potential differences in interactions of these molecules. The study was performed using quantum chemical methods including very accurate CCSD(T)/CBS method. We studied parallel and displaced parallel interactions in 2-butene dimers, in butane dimers, and between 2-butene and saturated butane. The results show the trend that interactions of 2-butene with butane are the strongest, followed by interactions in butane dimers, whereas the interaction in 2-butene dimers are the weakest. The strongest calculated interaction energy is between trans-2-butene and butane, with a CCSD(T)/CBS energy of -2.80?kcal?mol(-1) . Interactions in cis-2-butene dimers are stronger than interactions in trans-2-butene dimers. Interestingly, some of the interactions involving 2-butene are as strong as interactions in a benzene dimer. These insights into interactions of cis- and trans-2-butene can improve understanding of the properties and processes that involve molecules with cis and trans double bonds, such as fatty acids and polymers. PMID:26541507

  4. Products of the reaction of hydroxyl radicals with trans-2-butene in the presence of oxygen and nitrogen dioxide

    NASA Astrophysics Data System (ADS)

    Martinez, Richard I.; Huie, Robert E.; Herron, John T.

    1980-06-01

    The reactions of hydroxy-substituted alkyl radicals, formed as secondary products in the reaction of ozone with trans-2-butene, have been identified in photoionization mass spectrometry studies, using acetaldehyde and nitrogen dioxide as free-radical scavengers. Products derived from 2-hydroxy-1-methylpropl in the absence of scavengers include 2,3-butanedione (diacetyl), 3-hydroxy-2-butanone (acetoin),and 2,3-butanediol. In the presence of added acetaldehyde or nitrogen dioxide, the formation of these products is suppressed. In addition, with added nitrogen dioxide, new products are formed which have been identified as a series of oxoalkyl and hydroxy-substituted-alkyl nitrates and peroxynitrates. These observations may have an important bearing on the chemistry of photochemical smog.

  5. The barrier to the methyl rotation in Cis-2-butene and its isomerization energy to Trans-2-butene, revisited.

    PubMed

    Matta, Chrif F; Sadjadi, Seyed Abdolreza; Braden, Dale A; Frenking, Gernot

    2016-01-01

    We respond to the two questions posed by Weinhold, Schleyer, and McKee (WSM) in their study of cis-2-butene (Weinhold et al., J Comput Chem 2014, 35, 1499), in which they solicit explanations for the relative conformational energies of this molecule in terms of the Quantum Theory of Atoms in Molecules (QTAIM). WSM requested answers to the questions: (1) why is cis-2-butene less stable than trans-2-butene despite the presence of a hydrogen-hydrogen (H?H) bond path in the former but not in the latter if the H?H bond path is stabilizing? (2) Why is the potential well of the conformational global minimum of cis-2-butene only 0.8 kcal/mol deep when the H?H bonding is stabilizing by 5 kcal/mol? Both questions raised by WSM are answered by considering the changes in the energies of all atoms as a function of the rotation of one of the two methyl groups from the minimum-energy structure, which exhibits the H?H bond path, to the transition state, which is devoid of this bond path. It is found that the stability gained by the H?H bonding interaction is cancelled by the destabilization of one of the ethylenic carbon atoms which, alone, destabilizes the system by as much as 5 kcal/mol in the global minimum conformation. Further, it is found that the 1.1 kcal/mol stability of trans-2-butene with respect to the cis-isomer is driven by the considerable destabilization of the ethylenic carbons by 11 kcal/mol, while the changes in the atomic energies of the other corresponding atoms in the two isomers account for the observed different stabilities. The error introduced into QTAIM atomic energies by neglecting the virials of the forces on the nuclei for partially optimized structures is discussed. 2015 Wiley Periodicals, Inc. PMID:26581645

  6. Direct observation of unstable intermediate species in the reaction of trans-2-butene on ferrierite zeolite by picosecond infrared laser spectroscopy.

    PubMed

    Noguchi, Hidenori; Yoda, Eisuke; Ishizawa, Naoko; Kondo, Junko N; Wada, Akihide; Kobayashi, Hisayoshi; Domen, Kazunari

    2005-09-15

    The reaction dynamics of trans-2-butene adsorbed to acidic hydroxyl groups on the surface of ferrierite zeolite is examined by time-resolved spectroscopy using a tunable infrared picosecond pulse laser system. The transient absorption spectra measured by a two-color pump-probe technique at 188-243 K reveal bleaching and hot bands of the OD stretching mode 2 ps after excitation. This vibrationally excited state relaxes within 20 ps at 188 K, while the bleaching band includes a long-lifetime component that lasts for more than 100 ps at 243 K. Thus, the OD (isotope-exchanged hydroxy groups) stretching band does not entirely recover in this period and is mirrored by an analogous weakening of the CH bending band of the adsorbed trans-2-butene. Simultaneously, three new bands in CH stretching region were observed at 3045, 3095, and 3130 cm(-1). This result suggests the presence of a short-lived intermediate formed by reaction between the acidic hydroxyl groups and adsorbed trans-2-butene. PMID:16853197

  7. Torsional analyses of trans-2-butene and propene cations: A comparative investigation of two prototypical ions with different degrees of symmetry

    NASA Astrophysics Data System (ADS)

    Burrill, A. B.; Johnson, P. M.

    2001-07-01

    The mass analyzed threshold ionization spectra of trans-2-butene and propene have been obtained using single-step vacuum ultraviolet excitation. The ionization potential for trans-2-butene is 73 6054 cm-1, while for propene it is 78 5874 cm-1. Both species have progressions of the low frequency, torsional, normal modes. Using the torsional normal mode and first overtone from a trans-2-butene cation the torsional barrier is determined to be approximately 453 cm-1, assuming a sinusoidal potential. Normal mode analysis indicates that all low frequency normal modes of the propene cation involve substantial internal motion of the vinyl component, and the spectrum shows a very anharmonic torsional mode progression. These factors complicate direct torsional barrier analysis from the experimental lines, but through the use of various ab initio methods the propene torsional barrier is determined to be approximately 429 cm-1. Due to the anharmonicity found in propene, the correlation corrected vibrational self-consistent field method in GAMESS was used to verify the assignments of the experimental lines. The torsional barriers for both cations are found to lie approximately 275-300 cm-1 below the barrier heights of the neutral species.

  8. Production of stabilized Criegee intermediates and peroxides in the gas phase ozonolysis of alkenes: 1. Ethene, trans-2-butene, and 2,3-dimethyl-2-butene

    NASA Astrophysics Data System (ADS)

    Hasson, Alam S.; Orzechowska, Grazyna; Paulson, Suzanne E.

    2001-12-01

    Ozone-alkene reactions generate stabilized Criegee intermediates (of the form R1R2COO), which are believed to react with water molecules to form organic hydroperoxides, hydrogen peroxide and carboxylic acids. These reactions are thought to be significant sources of these environmentally important compounds, yet both the yields of stabilized Criegee intermediates and the branching ratios from their reaction with water are not well known. The formation of hydrogen peroxide and organic hydroperoxides was investigated in the gas phase ozonolysis of ethene, trans-2-butene, and 2,3-dimethyl-2-butene for relative humidities (RH) from 0 and 80% by gas chromatography with flame ionization detection and high-performance liquid chromatography with fluorescence detection. Additionally, yields of acetaldehyde and acetic acid from trans-2-butene and acetone from 2,3-dimethyl-2-butene were measured. The reactions of stabilized Criegee intermediates with water were found to proceed almost entirely via organic hydroperoxide or hydrogen peroxide formation with little acid formation. Stabilized Criegee intermediate yields of 0.39, 0.24, and 0.10 were obtained for ethene, trans-2-butene, and 2,3-dimethyl-2-butene, respectively.

  9. The Bond Dissociation Energies of 1-Butene

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

    1994-01-01

    The bond dissociation energies of 1-butene and several calibration systems are computed using the G2(MP2) approach. The agreement between the calibration systems and experiment is very good. The computed values for 1-butene are compared with calibration systems and the agreement between the computed results for 1-butene and the "rule of thumb" values from the smaller systems is remarkably good.

  10. Comparative metabolism and disposition of 1-chloro- and 3-chloro-2-methylpropene in rats and mice.

    PubMed

    Ghanayem, B I; Burka, L T

    1987-01-01

    A recent 2-year carcinogenicity study found that gavage administration of 3-chloro-2-methylpropene (CMP), containing 5% 1-chloro-2-methylpropene (dimethylvinyl chloride, DMVC), caused forestomach neoplasms in rats and mice. Similar chronic studies revealed that DMVC caused forestomach neoplasms in both rats and mice; neoplasms of the nasal and oral cavities were observed in rats but not in mice. In the current studies we have investigated the metabolic basis of these differences. Daily doses of 150 mg/kg of 2-[14C]DMVC or 2-[14C]CMP were administered to rats for 1, 2, or 4 consecutive days. One daily dose of 150 mg/kg of DMVC was administered to mice. Both DMVC and CMP were rapidly metabolized; however, CMP was cleared at a slightly lower rate. Rats exhaled approximately 25 and 10% of the DMVC and CMP as CO2, respectively. Mice exhaled 25% of the DMVC as CO2. Rats expired 30% of the administered DMVC unchanged in the 24 hr after dosing compared to only 7% of the administered CMP. Mice expired 5% of the administered DMVC in the same time period. This observation may explain the occurrence of tumors in the nasal and oral cavities of rats treated with DMVC but not in rats treated with CMP or in mice treated with DMVC in 2-year carcinogenicity studies. The 24-hr urinary excretion in rats was 35% of the administered DMVC compared to 58% of CMP. Mice excreted 47% of the administered DMVC in 24 hr in the urine. An unusual urinary metabolite of DMVC, 2-amino-6-methyl-4-thia-5-heptene-1,7-dioic acid, was identified.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2881764

  11. Isolation of 3-methyl-1-butene from a hydrocarbon stream

    SciTech Connect

    Drake, C.A.

    1986-12-16

    A process is described for recovering 3-methyl-1-butene from a hydrocarbon stream containing 3-methyl-1-butene and compounds which form azeotropes with 3-methyl-1-butene comprising extractive distillation of the hydrocarbon stream with a solvent mixture comprising dimethylformamide and sulfolane solvent mixture present in an amount ranging from about 0.1 to about 20 times the weight of the hydrocarbon stream. The dimethylformamide in the dimethylformamide/Sulfolane solvent mixture is present in an amount ranging from about 30 weight percent to about 70 weight percent based on the weight of the mixture. This separates insolubles containing the 3-methyl-l-butene as the overhead product stream from the bottoms product containing soluble compounds, the compounds that form azeotropes with 3-methyl-l-butene and the solvent mixture and thereafter recovering the 3-methyl-1-butene from the insolubles.

  12. Chronic inhalation toxicity and carcinogenicity studies of 3-chloro-2-methylpropene in BDF1 mice.

    PubMed

    Katagiri, T; Takeuchi, T; Mine, T; Noguchi, T; Nishizawa, T; Yamamoto, S; Okudaira, M; Matsushima, T

    2000-07-01

    Chronic toxicity and carcinogenicity studies of 3-chloro-2-methylpropene (CMP), which has been widely used as an insecticide and chemical intermediate, were carried out in BDF1 mice. CMP was administered to mice in groups of 50 male and 50 female mice by the inhalation route 5 days per week for 104 weeks at doses of 0, 50, 100 or 200 ppm. Male and female mice in the CMP-exposed groups had decreased body weight but no noticeable clinical signs when compared with the control group. Dose-related increases in the incidences of gastric mucosal hyperplasia and squamous cell papilloma were observed in both sexes, and squamous cell carcinoma was observed in only one male mouse in the 100 ppm group. An increased incidence of Harderian gland adenoma in female mice was also recognized. In the nasal cavity, eosinophilic exudate associated with atrophy of olfactory epithelia, respiratory metaplasia of olfactory epithelia and olfactory gland, and eosinophilic changes in respiratory and olfactory epithelia were increased in both sexes. PMID:10943079

  13. Forestomach lesions in rats and mice administered 3-chloro-2-methylpropene by gavage for two years.

    PubMed

    Chan, P C; Haseman, J K; Boorman, G A; Huff, J; Manus, A G; Cardy, R H

    1986-12-01

    The carcinogenicity of 3-chloro-2-methylpropene (CMP), a chemical intermediate and insecticide, was studied because of possible human exposure and because of its structural relationship to vinyl chloride and allyl chloride. CMP in corn oil was administered by gavage to groups of 50 male and 50 female Fischer 344/N rats at 0, 75, or 150 mg/kg body weight and to groups of 50 male and 50 female B6C3F1 mice at 0, 100, or 200 mg/kg body weight, 5 times a week for 103 weeks. The body weights of the two CMP treated groups of rats were 3-15% lower than the controls; the survival rates were similar. The body weights and survival rates of the CMP-exposed male and female mice were not different from the respective controls throughout the study. CMP administration resulted in dose-related increases in the incidence and severity of forestomach basal cell hyperplasia and the incidence of forestomach squamous cell papillomas in both sexes of rats and mice. In the two groups of CMP-exposed male mice the incidences of squamous cell carcinoma of the forestomach were also increased. Invasion or metastasis of the squamous cell carcinomas to other organs was observed in 2 male mice treated at 100 mg/kg and in 3 male mice and one female mouse treated at 200 mg/kg. The data show that CMP is a carcinogen for the forestomach in rats and mice and acts at the tissue site of contact and support genetic toxicity findings that CMP is a direct-acting alkylating agent. PMID:3779651

  14. Application of the margin of exposure (MoE) approach to substances in food that are genotoxic and carcinogenic - example: 1-methylcyclopropene and its impurities (1-chloro-2-methylpropene and 3-chloro-2-methylpropene).

    PubMed

    Renwick, Andrew; Leblanc, Jean-Charles; Setzer, R Woodrow

    2010-01-01

    The chlorinated impurities of 1-methylcyclopropene possess weak mutagenicity and are carcinogenic in rodent bioassays. Dose-response modelling of the data for 1-chloro-2-methylpropene gave a BMDL10 for nasal carcinomas in male rats of 11 mg/kg-bw/day (after correction for the 5 days/week dosage schedule). No human exposure data are available and theoretical estimates had to be used to calculate the MoE. The MoEs ranged from 40,000 to 100,000,000 depending on the assumptions used in the exposure estimation. PMID:19786060

  15. 21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Poly-1-butene resins and butene/ethylene...-butene resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers... produced by the catalytic polymerization of 1-butene liquid monomer. Butene/ethylene copolymers...

  16. 21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Poly-1-butene resins and butene/ethylene... Single and Repeated Use Food Contact Surfaces § 177.1570 Poly-1-butene resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers identified in this section may be...

  17. 21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Poly-1-butene resins and butene/ethylene...-butene resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers... produced by the catalytic polymerization of 1-butene liquid monomer. Butene/ethylene copolymers...

  18. 21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... their characteristic infrared spectra. (ii) Viscosity. Poly-1-butene resins and the butene/ethylene copolymers have an intrinsic viscosity 1.0 to 3.2 as determined by ASTM method D1601-78, “Standard Test Method for Dilute Solution Viscosity of Ethylene Polymers,” which is incorporated by reference....

  19. 21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... characteristic infrared spectra. (ii) Viscosity. Poly-1-butene resins and the butene/ethylene copolymers have an intrinsic viscosity 1.0 to 3.2 as determined by ASTM method D1601-78, “Standard Test Method for Dilute Solution Viscosity of Ethylene Polymers,” which is incorporated by reference. Copies may be obtained...

  20. Electron momentum spectroscopy of 1-butene: a theoretical analysis using molecular dynamics and molecular quantum similarity.

    PubMed

    Shojaei, S H Reza; Vandenbussche, Jelle; Deleuze, Michael S; Bultinck, Patrick

    2013-09-01

    The results of experimental studies of the valence electronic structure of 1-butene by means of electron momentum spectroscopy (EMS) have been reinterpreted on the basis of molecular dynamical simulations in conjunction with the classical MM3 force field. The computed atomic trajectories demonstrate the importance of thermally induced nuclear dynamics in the electronic neutral ground state, in the form of significant deviations from stationary points on the potential energy surface and considerable variations of the C-C-C-C dihedral angle. These motions are found to have a considerable influence on the computed spectral bands and outer-valence electron momentum distributions. Euclidean distances between spherically averaged electron momentum densities confirm that thermally induced nuclear motions need to be fully taken into account for a consistent interpretation of the results of EMS experiments on conformationally flexible molecules. PMID:23902590

  1. SAXS/WAXS studies of flow-induced crystallization of poly(1-butene) in uniaxial extensional flow

    NASA Astrophysics Data System (ADS)

    McCready, Erica; Burghardt, Wesley

    2013-03-01

    We report studies of flow-induced crystallization of poly(1-butene) in uniaxial extensional flow. Flow was produced using an SER extensional flow fixture housed in a custom built convection oven designed to provide x-ray access for in situ studies of polymer structure using synchrotron x-ray scattering techniques. Samples were loaded into the SER fixture, heated well into the melt, and then cooled to a temperature at which quiescent crystallization would be prohibitively slow. A short interval of uniaxial extensional flow was then applied, after which simultaneous wide- and small-angle x-ray scattering (SAXS and WAXS) patterns were collected to study the phase transformation kinetics and morphology of the subsequent accelerated crystallization. The impact of both deformation rate and total applied strain on the crystallization process were examined.

  2. SAXS/WAXS studies of flow-induced crystallization of poly(1-butene) in uniaxial extensional flow

    NASA Astrophysics Data System (ADS)

    McCready, Erica; Burghardt, Wesley

    2014-03-01

    We report studies of flow-induced crystallization of poly(1-butene) in uniaxial extensional flow. Flow was produced using an SER extensional flow fixture housed in a custom built convection oven designed to provide x-ray access for in situ studies of polymer structure using synchrotron x-ray scattering techniques. Samples were loaded into the SER fixture, heated well into the melt, and then cooled to a temperature at which quiescent crystallization would be prohibitively slow. A short interval of uniaxial extensional flow was then applied, after which simultaneous wide- and small-angle x-ray scattering (SAXS and WAXS) patterns were collected to study the phase transformation kinetics and morphology of the subsequent accelerated crystallization. The degree of crystallite orientation was generally found to decrease over the course of the crystallization. WAXS measurements yielded systematically higher degrees of crystallite orientation than SAXS. Both SAXS and WAXS gave generally consistent results for the extent of crystallization, although the SAXS invariant showed a decrease at long times that is not mirrored in the WAXS data. The impact of both deformation rate and total applied strain on the crystallization process were examined.

  3. Electrical conductivity and equation of state of liquid nitrogen, oxygen, benzene, and 1-butene shocked to 60 GPa

    SciTech Connect

    Hamilton, D.C.

    1986-10-08

    Measurements are reported for the electrical conductivity of liquid nitrogen (N/sub 2/), oxygen (O/sub 2/) and benzene (C/sub 6/H/sub 6/), and Hugoniot equation of state of liquid 1-butene (C/sub 4/H/sub 8/) under shock compressed conditions. The conductivity data span 7 x 10/sup -4/ to 7 x 10/sup 1/ ..cap omega../sup -1/cm/sup -1/ over a dynamic pressure range 18.1 to 61.5 GPa and are discussed in terms of amorphous semiconduction models which include such transport phenomena as hopping, percolation, pseudogaps, and metallization. Excellent agreement is found between the equation-of-state measurements, which span a dynamic pressure range 12.3 to 53.8 GPa, and Ree's calculated values which assume a 2-phase mixture consisting of molecular hydrogen and carbon in a dense diamond-like phase. There is a 2-1/2 fold increase in the thermal pressure contribution over a less dense, stoichiometrically equivalent liquid. 90 refs., 48 figs., 8 tabs.

  4. Evaluated kinetics of terminal and non-terminal addition of hydrogen atoms to 1-alkenes: a shock tube study of H + 1-butene.

    PubMed

    Manion, Jeffrey A; Awan, Iftikhar A

    2015-01-22

    Single-pulse shock tube methods have been used to thermally generate hydrogen atoms and investigate the kinetics of their addition reactions with 1-butene at temperatures of 880 to 1120 K and pressures of 145 to 245 kPa. Rate parameters for the unimolecular decomposition of 1-butene are also reported. Addition of H atoms to the ? bond of 1-butene results in displacement of either methyl or ethyl depending on whether addition occurs at the terminal or nonterminal position. Postshock monitoring of the initial alkene products has been used to determine the relative and absolute reaction rates. Absolute rate constants have been derived relative to the reference reaction of displacement of methyl from 1,3,5-trimethylbenzene (135TMB). With k(H + 135TMB ? m-xylene + CH3) = 6.7 10(13) exp(-3255/T) cm(3) mol(-1) s(-1), we find the following: k(H + 1-butene ? propene + CH3) = k10 = 3.93 10(13) exp(-1152 K/T) cm(3) mol(-1) s(-1), [880-1120 K; 145-245 kPa]; k(H + 1-butene ? ethene + C2H5) = k11 = 3.44 10(13) exp(-1971 K/T) cm(3) mol(-1) s(-1), [971-1120 K; 145-245 kPa]; k10/k11 = 10((0.0580.059)) exp [(818 141) K/T), 971-1120 K. Uncertainties (2?) in the absolute rate constants are about a factor of 1.5, while the relative rate constants should be accurate to within 15%. The displacement rate constants are shown to be very close to the high pressure limiting rate constants for addition of H, and the present measurements are the first direct determination of the branching ratio for 1-olefins at high temperatures. At 1000 K, addition to the terminal site is favored over the nonterminal position by a factor of 2.59 0.39, where the uncertainty is 2? and includes possible systematic errors. Combining the present results with evaluated data from the literature pertaining to temperatures of <440 K leads us to recommend the following: k?(H + 1-butene ? 2-butyl) = 1.05 10(9)T(1.40) exp(-366/T) cm(3) mol(-1) s(-1), [220-2000 K]; k?(H + 1-butene ? 1-butyl) = 9.02 10(8)T(1.40) exp(-1162/T) cm(3) mol(-1) s(-1) [220-2000 K]. Analogous rate constants for other unbranched 1-olefins should be very similar. Despite this, a factor of three discrepancy in the branching ratio for terminal and nonterminal addition is noted when comparing the present values with recommendations from a recent model of the important H + propene reaction. This difference is suggested to be well outside of the possible experimental errors of the present study or the expected differences with 1-butene. There thus appear to be inconsistencies in the current model for propene. In particular the addition branching ratio from that model should not be used as a reference value in extrapolations to other systems via rate rules or automated mechanism generation techniques. PMID:25517498

  5. The reaction of 3,4-epoxy-1-butene with deoxyguanosine and DNA in vitro: synthesis and characterization of the main adducts.

    PubMed

    Citti, L; Gervasi, P G; Turchi, G; Bellucci, G; Bianchini, R

    1984-01-01

    The reaction of guanosine with 3,4-epoxy-1-butene in acetic acid gives two main products of N-7 alkylation. After acidic hydrolysis the two aglycones have been isolated by h.p.l.c. and shown to be the regioisomeric 7-(2-hydroxy-3-buten-1-yl) guanine (I) and 7-(1-hydroxy-3-buten-2-yl) guanine (II), arising through nucleophilic attack by N-7 of the purine at the two oxirane carbons of 3,4-epoxy-1-butene. Spectral characteristics of both compounds are presented, including u.v., 1H-n.m.r. and mass spectra. Deoxyguanosine reacts with 3,4-epoxy-1-butene in 50% methanol-water at 37 degrees C to give the N-7 alkylated deoxynucleosides corresponding to I and II in a 59:41 ratio. The reaction rate depends on the nucleoside concentration, with second order rate constants at 37 degrees C of 1.6 X 10(-2) and 1.1 X 10(-2) h-1 M-1 for the formation of the two deoxynucleoside adduct corresponding to I and II, respectively. The same two compounds I and II in a similar (54:46) ratio have been identified after acidic or thermal hydrolysis of DNA which had been reacted with 3,4-epoxy-1-butene under similar conditions. The half life for the spontaneous depurination of I and II in the adducted DNA under physiological conditions (37 degrees C, pH 7.2) is 50 h. PMID:6690085

  6. Comparison of two-body and three-body decomposition of ethanedial, propanal, propenal, n-butane, 1-butene, and 1,3-butadiene

    NASA Astrophysics Data System (ADS)

    Chin, Chih-Hao; Lee, Shih-Huang

    2012-01-01

    We investigated two-body (binary) and three-body (triple) dissociations of ethanedial, propanal, propenal, n-butane, 1-butene, and 1,3-butadiene on the ground potential-energy surfaces using quantum-chemical and Rice-Ramsperger-Kassel-Marcus calculations; most attention is paid on the triple dissociation mechanisms. The triple dissociation includes elimination of a hydrogen molecule from a combination of two separate terminal hydrogen atoms; meanwhile, the rest part simultaneously decomposes to two stable fragments, e.g., C2H4, C2H2, or CO. Transition structures corresponding to the concerted triple dissociation were identified using the B3LYP/6-311G(d,p) level of theory and total energies were computed using the method CCSD(T)/6-311+G(3df, 2p). The forward barrier height of triple dissociation has a trend of ethanedial < propanal < propenal < n-butane < 1-butene < 1,3-butadiene, pertaining to the reaction enthalpy. Ratios of translational energies of three separate fragments could be estimated from the transition structure of triple dissociation. The synchronous concerted dissociation of propanal, propenal, and 1-butene leading to three different types of molecular fragments by breaking nonequivalent chemical bonds is rare. The triple dissociation of propanal, n-butane, 1-butene, and 1,3-butadiene were investigated for the first time. To outline a whole picture of dissociation mechanisms, some significant two-body dissociation channels were investigated for the calculations of product branching ratios. The triple dissociation plays an important role in the three carbonyl compounds, but plays a minor or negligible role in the three hydrocarbons.

  7. NTP Toxicology and Carcinogenesis Studies of Dimethylvinyl Chloride (1-Chloro-2-Methylpropene) (CAS No. 513-37-1) in F344/N Rats and B6C3F1 Mice (Gavage Studies).

    PubMed

    1986-08-01

    Dimethylvinyl chloride is a clear colorless liquid, which, because of its volatility and flammability at room temperature, is a significant fire hazard. It has a boiling point of 68.1 degrees C (155 degrees F) and a density at 20 degrees C of 0.919 g/ml. Dimethylvinyl chloride is a byproduct in the production of 3-chloro-2-methylpropene by the chlorination of isobutene. It is not known to be produced in the United States for other than laboratory purposes. This chemical was nominated for toxicologic studies because of its reported presence in ambient air in the Baltimore area and was selected for toxicologic characterization because of its structural similarity to the known animal and human carcinogen, vinyl chloride monomer. Toxicology and carcinogenesis studies of dimethylvinyl chloride (96%-98% pure), a structural analog of vinyl chloride monomer, a known human carcinogen, by administered dimethylvinyl chloride in corn oil by gavage to groups of 50 male and 50 female F344/N rats and B6C3F1 mice at doses of 0, 100, or 200 mg/kg body weight 5 days per week for 102 or 103 weeks. The selection of these doses was based on results of 13-week studies, which included depression of body weight at doses of 500 mg/kg or above in rats as well as histopathologic changes intestinal epithelium, bone marrow, hepatocytes, and the testes at doses of 250 mg/kg and above; doses in mice were selected on the basis of histopathologic changes in lymphopoietic cells, liver, pancreatic islets, ovary, testis, and spleen, with changes being most prominent at doses of 500 mg/kg and above. In the 2-year studies, body weights of rats and mice given 100 mg/kg were comparable to those of the vehicle controls except for the last few weeks in mice when body weights were markedly lower than those for the vehicle controls. At 200 mg/kg, the mean body weights of rats and mice were progressively decreased relative to those of vehicle controls, with the significant departure from vehicle controls occurring somewhat earlier in males than in females. Survival of vehicle control rats and mice was comparable to historical values; however, survival of dosed male and female rats was significantly lower than that of vehicle controls, with the incidence of mortality being more severe at the high dose than at the low dose. There were no survivors in the high dose group of male rats after week 85 or in the high dose group of female rats after week 97. Survival was significantly lower among dosed male and female mice compared with vehicle controls. In the absence of toxicological findings that would explain the early deaths, it is assumed that the high incidence of tumors and chemical-related toxicity contributed to the decreased survival of dosed rats and mice. In rats, the severity and incidence of nonneoplastic lesions were minimal; these lesions included necrosis of the duodenum and epithelial hyperplasia at the sites of tumor formation--the nasal cavity, esophagus, and forestomach. In mice, the severity of nonneoplastic lesions was also minimal; the lesions included necrosis of the liver, bone marrow granulocytic hyperplasia, and inflammation of the nasal cavity (small number, females only.) Several types of neoplastic lesions occurred with significantly increased incidences in dosed animals as shown in the following table (see page 11 of Technical Report). Among rats, these lesions included malignant epithelial tumors of the nasal cavity and squamous cell tumors of the oral cavity, esophagus, and forestomach in males and females. The increased number of fibroadenomas of the mammary gland in female rats may have been related to dimethylvinyl chloride administration. The lack of a clear dose-response relationship for certain tumors in rats is considered to be related to the increased number of early deaths observed in the high dose groups. Among dosed mice, there were significantly increased incidences of squamous cell carcinomas of the forestomach (both sexes), squamous cell papillomas of the forestomach (males), and squamous cell carcinomas of the preputial gla preputial gland (males). The increased incidence of papillary adenomas of the harderian gland and alveolar/bronchiolar adenomas or carcinomas in female mice may have been related to administration of dimethylvinyl chloride. Limited metabolism studies of 14C-labeled dimethylvinyl chloride were conducted in male F344/N rats and B6C3F1 mice. Single doses of 150 mg/kg were administered to rats for 1, 2, or 4 consecutive days. About 25% of the administered doses was exhaled as carbon dioxide; this amount was independent of the number of doses administered. Another 25%-35% of the administered dose was exhaled; 96% of this parent was material. Approximately 35% and 6% were excreted in the urine and feces, respectively. The elimination half-life of radioactive label was 3-4 days for the liver and kidney, the two organs containing the greatest amounts of the administered dose. In mice, a much smaller fraction of the dose was exhaled and a larger proportion was excreted in urine compared with rats. Dimethylvinyl chloride was not mutagenic in four strains ofSalmonella typhimurium with or without metabolic activation, but it was mutagenic in the mouse lymphoma L5178Y/TK± assay in the absence of metabolic activation. Sister-chromatid exchanges were induced in Chinese hamster ovary cells with and without metabolic activation, but there was no increase in chromosomal aberrations. When fed to Drosophila, dimethylvinyl chloride induced significant increases in the frequencies of both sex-linked recessive lethal mutations and reciprocal translocations. Studies of the immunotoxicity of dimethylvinyl chloride were conducted in which female B6C3F1 mice received daily oral doses of 0, 50, 100, 200, or 400 mg dimethylvinyl chloride per kilogram body weight. Compound-related increases in susceptibility to bacterial infection and decreases in macrophage cytostasis were observed at all doses. At the highest dose, the decreased resistance to bacterial and viral challenge could be related to alterations in specific immune function. However, the increased mortality in rats and mice in the 2-year studies was not relatable to infectious processes. An audit of the experimental data was conducted for these2-year toxicology and carcinogenesis studies on dimethylvinyl chloride. No data discrepancies were found that influenced the final interpretations. Under the conditions of these 2-year gavage studies, there was clear evidence of carcinogenicity of dimethylvinyl chloride for both sexes of F344/N rats and B6C3F1 mice. This was based on increased incidences of neoplasms of the nasal cavity, oral cavity, esophagus, and forestomach of male and female F344/N rats. B6C3F1 mice showed increased incidences of squamous cell neoplasms of the forestomach in males and females and squamous cell carcinomas of the preputial gland in males. Synonym: 1-chloro-2-methylpropene PMID:12748737

  8. Determination of thermodynamic properties of isotactic poly(1-butene) at infinite dilution using density and inverse gas chromatography.

    PubMed

    Koz?owska, Marta Karolina; Doma?ska, Urszula; Lempert, Ma?gorzata; Rogalski, Marek

    2005-03-18

    The partial molar volumes, V1(M), and the molar volume of isotactic crystalline low-molecular-weight poly(1-butene), iPBu-1, V1, have been calculated from the measured density of {iPBu-1 + solvent (n-hexane, n-heptane, n-nonane, n-decane, p-xylene, cyclohexane and chloroform)} systems. Some of the thermodynamic quantities were also obtained for the iPBu-1 with eight hydrocarbons (n-octane, n-decane, n-undecane, n-dodecane, n-tridecane, o-xylene, m-xylene, p-xylene) by the method of inverse gas chromatography at various temperatures. The weight fraction activity coefficients of the solvent at infinite dilution, omega2(infinity) and the Flory-Huggins thermodynamic interaction parameters, chi21(infinity), between polymer and solvents were determined. The partial molar free energy, deltaG2(infinity), the partial molar heat of mixing, deltaH2(infinity), at infinite dilution and the polymer solubility parameter, delta1, were calculated. Additionally, the (solid + liquid) binary mixtures equilibria, SLE, of iPBu-1 with three hydrocarbons (n-octane, n-decane and m-xylene) were studied by a dynamic method. By performing these experiments over a large concentration range, the T-x phase diagrams of the polymer-solvent systems were constructed. The excess Gibbs energy models were used to describe the nonideal behaviour of the liquid phase. The omega2(infinity) were determined from the solubility measurements and were predicted by using the UNIFAC FV model. PMID:15830936

  9. Comparative kinetics of the 3-buten-1-ol and 1-butene reactions with OH radicals: a density functional theory/RRKM investigation.

    PubMed

    Peirone, Silvina; Nieto, Jorge D; Cometto, Pablo M; da Silva Barbosa, Thas; Bauerfeldt, Glauco Favilla; Arbilla, Graciela; Lane, Silvia I

    2015-04-01

    The compared kinetics of the reactions of unsaturated alcohols and alkenes with OH radicals is a topic of great interest from both the theoretical chemistry and the atmospheric chemistry points of view. The enhanced reactivity of an unsaturated alcohol, with respect to its alkene analogue, toward OH radicals has been previously demonstrated, at 298 K, by experimental and theoretical research. In this work, a new comparative investigation of such reactions is performed for 3-buten-1-ol and 1-butene. The model assumes that the overall kinetics is governed by the first OH addition steps of the mechanism. Calculations have been performed at the DFT level, employing the BHandHLYP functional and the cc-pVDZ and aug-cc-pVDZ basis sets, and the rate coefficients have been determined on the basis of the microcanonical variational transition state theory. The rate coefficients obtained for the OH reactions with 3-buten-1-ol (kOH(31BO)) and 1-butene (kOH(1B)) at 298.15 K are lower than the experimental rate coefficient available in the literature, showing deviations of 18% and 25%, respectively. Negative temperature dependence is verified for these rate coefficients. The kOH(31BO)/kOH(1B) ratios have also been investigated as a function of the temperature, suggesting that at room temperature the unsaturated alcohol reacts with the OH radicals faster than 1-butene, by a factor of 1.2, but at higher temperatures (400-500 K), the alkene should react faster, and that the stabilization of prebarrier complexes and saddle points due to hydrogen bonds is no longer an important factor to govern the reactivity of the unsaturated alcohol toward OH radicals, with respect to the alkene analogue. PMID:25785926

  10. In situ FTIR spectroscopy of 1-butene and 1,3-butadiene selective oxidation to maleic anhydride on V-P-O catalysts

    SciTech Connect

    Wenig, R.W.; Schrader, G.L.

    1987-03-26

    The selective oxidation of 1-butene and 1,3-butadiene was studied by transmission infrared spectroscopy. Vanadium-phosphorus-oxygen catalysts prepared by the reaction of V/sub 2/O/sub 5/ with H/sub 3/PO/sub 4/ in alcohol solution were used. Infrared spectra were collected in situ during the flow of 75 cm/sup 3/ of 1.5% hydrocarbon-in-air mixtures over catalysts having P-to-V ratios of 0.9, 1.0, and 1.1. Reaction temperatures from 300 to 400 /sup 0/C were investigated with 1-butene feeds, whereas the highly reactive 1,3-butadiene was studied only at 300 /sup 0/C. An adsorbed butadiene species, maleic acid, and maleic anhydride were observed during both olefin partial oxidation studies. Evidence was obtained for a second olefin species which had been previously observed for in situ n-butane selective oxidation studies. Concentrations of adsorbed species were found to vary with catalyst phosphorus loading, reaction temperature, and time of exposure to reaction conditions.

  11. Effects of Deposition Plasma Power on Properties of Low Dielectric-Constant Plasma Polymer Films Deposited Using Hexamethyldisiloxane and 3,3-Dimethyl-1-butene Precursors

    NASA Astrophysics Data System (ADS)

    Lee, Sungwoo; Woo, Jihyung; Nam, Eunkyoung; Jung, Donggeun; Yang, Jaeyoung; Chae, Heeyeop; Kim, Hyoungsub

    2009-10-01

    We investigated the effects of deposition plasma power on the properties of plasma polymer films deposited by plasma-enhanced chemical vapor deposition using a mixture of hexamethyldisiloxane and 3,3-dimethyl-1-butene as the precursor, which are referred to as plasma polymerized hexamethyldisiloxane:3,3-dimethyl-1-butene (PPHMDSO:DMB) films. As the deposition plasma power was increased from 15 to 60 W, the relative dielectric constants k of PPHMDSO:DMB films, increased from 2.67 to 3.19. After annealing at 450 °C, the films deposited at a deposition plasma power of 15-60 W showed k values of 2.27-2.64. With increased deposition plasma power, the as-deposited and annealed films showed increased values of hardness and Young's modulus. For as-deposited films, deposited at a plasma power of 15-60 W, the films showed a hardness of 0.13-2.0 GPa, and a modulus of 2.25-17.27 GPa. Annealed films, deposited at a plasma power of 15-60 W, showed a hardness of 0.05-2.07 GPa and a modulus of 1.66-14.4 GPa. The change in the k value and hardness of plasma polymer films as a function of deposition plasma power was correlated with fourier transform infrared (FT-IR) absorption peaks of C-Hx, Si-CH3, and Si-O related groups. The as-deposited and annealed PPHMDSO:DMB films showed decreased intensities of C-Hx and Si-CH3 peaks as the deposition plasma power increased. The reduction in the dielectric constant after annealing is mainly due to hydrocarbon removal in the film. Deconvolution of Si-CH3 bending peaks of PPHMDSO:DMB films was performed to relate mechanical properties to chemical structures. The relative oxygen content in the O-Si-(CH3)x structure is analyzed in detail. Improvements in hardness and modulus of our films are attributed to an increased amount of O3Si-(CH3) in the Si-CH3 structure.

  12. Conformationally disordered crystals and their influence on material properties: The cases of isotactic polypropylene, isotactic poly(1-butene), and poly(L-lactic acid)

    NASA Astrophysics Data System (ADS)

    Cocca, Mariacristina; Androsch, Ren; Righetti, Maria Cristina; Malinconico, Mario; Di Lorenzo, Maria Laura

    2014-12-01

    This article provides a comprehensive review of the physical properties of the conformationally disordered (condis) structures of isotactic polypropylene (iPP), isotactic poly(1-butene) (iPB-1) and poly(L-lactic acid) (PLLA), in comparison with the respective more stable crystalline forms. The aim of this review is to define the influence of the condis modifications on the thermal and mechanical properties of these materials. The condis structures of the three polymers are metastable and spontaneously transform into the more stable crystalline structures upon annealing above a critical temperature. The transition from the mesophase to the more stable crystalline structure becomes possible when the chains have sufficient mobility to allow rearrangements of chain conformations. A rigid amorphous fraction develops during solidification of iPP, iPB-1 and PLLA. Crystallization of iPB-1 and PLLA into the more stable forms leads to a larger coupling of the amorphous and crystalline chain segments, compared to the conformationally disordered arrangements, which results in a higher fraction of rigid amorphous chain segments. The difference in chain packing, together with the varied mobility of the coupled amorphous chain portions, affects both the initial resistance to the tensile strain and the large strain properties. All the three stable crystalline forms have a higher Young's modulus compared to the condis mesophases, and can sustain lower deformation under mechanical stimuli.

  13. AlCl3-Promoted Facile E-to-Z Isomerization Route to (Z)-2-Methyl-1-buten-1,4-ylidene Synthons for Highly Efficient and Selective (Z)-Isoprenoid Synthesis

    PubMed Central

    Wang, Guangwei; Negishi, Ei-ichi

    2013-01-01

    Zr-catalyzed methylalumination of 3-butyn-1-ols followed by AlCl3-promoted stereoisomerization at 50 °C for 6 h provides 4-iodo-3-methyl-3-buten-1-ols 2b and 6 of ≥98 Z configuration in 87 and 67% yields, respectively. (Z)-1,4-Diiodo-2-methyl-1-butene (1b) obtainable by iodination of 2b is a valuable synthon for efficient and selective syntheses of (Z)-alkene containing isoprenoids. PMID:24307863

  14. Modeling chemical growth processes in Titan's atmosphere 2. Theoretical study of reactions between C 2H and ethene, propene, 1-butene, 2-butene, isobutene, trimethylethene, and tetramethylethene

    NASA Astrophysics Data System (ADS)

    Woon, David E.; Park, Jin-Young

    2009-08-01

    Barrierless reactions between unsaturated hydrocarbons and the ethynyl radical (C 2H) can contribute to the growth of organic particulates in the haze-forming regions of Titan's atmosphere as well as in the gas giants and in the interstellar medium. We employed a combination of quantum chemistry and statistical rate theories to characterize reactions between ground state C 2H and seven alkenes of the general structure RRCdbnd CRR containing up to six carbons. The alkenes included ethene (C 2H 4); propene (C 3H 6); 1-butene, 2-butene, and isobutene (C 4H 8); trimethylethene (C 5H 10); and tetramethylethene (C 6H 12). Density functional theory calculations at the B3LYP/6-31 + G ∗∗ level were used to characterize the adducts, isomers, products, and the intervening transition states for the addition-elimination reactions of all seven species. A multiple-well treatment was then employed to determine the outcome distributions for the range of temperatures and pressures relevant to Titan's atmosphere, the interstellar medium, and the outer atmospheres of the gas giants. Finally, trajectory calculations using an ROMP2 potential energy surface were used to calculate kinetic rates for the ethene + C 2H reaction, where the agreement between the computed and measured values is very good. At low pressure and temperature, vinyl acetylene is a dominant product of several of the reactions, and all of the reactions yield at least one dominant product with both a double and a triple C sbnd C bond.

  15. MoO sub 3 catalysts promoted by MnMoO sub 4 I. Synthesis, characterization, and selectivity in oxidation of 1-butene and 1,3-butadiene to maleic anhydride

    SciTech Connect

    Ozkan, U.; Gill, R.C.; Smith, M.R. )

    1989-03-01

    MoO{sub 3} catalysts impregnated with MnMoO{sub 4} are active for the selective oxidation of C{sub 4} hydrocarbons to maleic anhydride. Presence of MnMoO{sub 4} creates a significant promoter effect in catalytic behavior of MoO{sub 3}. The pure phases and the impregnated catalysts have been characterized during various stages of their life history using characterization techniques such as X-ray diffraction, laser Raman spectroscopy, scanning electron microscopy, and BET surface area measurements, and their catalytic activity and selectivity in selective oxidation of 1-butene and 1,3-butadiene to maleic anhydride have been studied.

  16. MoO sub 3 catalysts promoted by MnMoO sub 4. II. Effect of O sub 2 concentration and temperature in selective oxidation of 1-butene to maleic anhydride

    SciTech Connect

    Gill, R.C.; Ozkan, U.S. )

    1990-04-01

    In a previous paper, the authors have reported the results of a study where they focused their attention on catalytic activity and selectivity of pure MoO{sub 3} and attempted to modify its catalytic behavior by bringing its surfaces into close contact with MnMoO{sub 4}. While their characterization experiments revealed the two-phase nature of the MnMoO{sub 4}/MoO{sub 3} catalyst, the activity studies showed a pronounced promoter effect in selective oxidation of both 1-butene and 1,3-butadiene to maleic anhydride, suggesting a possible synergy between the two phases. This note presents the results of their selective oxidation studies where the effect of temperature and oxygen partial pressure on catalytic behavior of the pure phases (MoO{sub 3} and MnMoO{sub 4}) as well as the two phase catalyst (MnMoO{sub 4}/MoO{sub 3}) has been investigated in conversion of 1-butene to maleic anhydride. All catalysts were characterized in detail using BET surface area measurement, x-ray diffraction, scanning electron microscopy, energy dispersive x-ray analysis, laser Raman spectroscopy and Raman microprobe techniques.

  17. Hydrogenolysis and homologation of 3,3-dimethyl-1-butene on Ru/SiO{sub 2} catalyst: Implications for the mechanism of carbon-carbon bond formation and cleavage on metal surfaces

    SciTech Connect

    Toyir, J.; Leconte, M.; Niccolai, G.P.; Basset, J.M.

    1995-04-01

    The reactions of 3,3-dimethyl-1-butene (neohexene) with hydrogen in the presence of zero-valent ruthenium metal particles supported on silica are reported. The predominant reaction is the hydrogenation of neohexene to neohexane. Simultaneous but slower homologation and hydrogenolysis reactions are reported. The homologation and hydrogenolysis reactions run at approximately equal rates, suggesting a mechanistic link between the two processes. The relative quantities of C{sub 1}-C{sub 5} and C{sub 7} products and the variation of these quantities with respect to varying temperature, neohexene/hydrogen ratio, and contact time are reported. The distribution of the primary products, neopentane, isobutene, and methane for hydrogenolysis and 2,2-dimethyl pentane, 2,2,3-trimethyl butane, and 4,4-dimethyl-1-pentene for homologation is discussed in terms of current thought on the mechanism of homologation and hydrogenolysis of alkanes. The most likely and strongly indicated mechanism for the hydrogenolysis of neohexene involves the deinsertion of a methylidene fragment from a ruthenium-neohexyl intermediate which is also an intermediate in the hydrogenation of neohexene. The distribution of C{sub 7} homologation products does not allow one to distinguish between a simple insertion mechanism and a mechanism passing through a metallacyclic intermediate. 19 refs., 10 figs.

  18. Selective oxidation of n-butane and butenes over vanadium-containing catalysts

    SciTech Connect

    Nieto, J.M.L.; Concepcion, P.; Dejoz, A.; Knoezinger, H.; Melo, F.; Vazquez, M.I.

    2000-01-01

    The oxidative dehydrogenation (OXDH) of n-butane, 1-butene, and trans-2-butene on different vanadia catalysts has been compared. MgO, alumina, and Mg-Al mixed oxides with Mg/(Al + Mg) ratios of 0.25 and 0.75 were used as supports. The catalytic data indicate that the higher the acid character of catalysts the lower is both the selectivity to C{sub 4}-olefins from n-butane and the selectivity to butadiene from both 1-butene or trans-2-butene. Thus, OXDH reactions are mainly observed from n-butane and butenes on basic catalysts. The different catalytic performance of both types of catalysts is a consequence of the isomerization of olefins on acid sites, which appears to be a competitive reaction with the selective way, i.e., the oxydehydrogenation process by a redox mechanism. Infrared spectroscopy data of 1-butene adsorbed on supported vanadium oxide catalysts suggest the presence of different adsorbed species. O-containing species (carbonyl and alkoxide species) are observed on catalysts with acid sites while adsorbed butadiene species are observed on catalysts with basic sites. According to these results a reaction network for the oxydehydrogenation of n-butane is proposed with parallel and consecutive reactions.

  19. FT-IR studies on light olefin skeletal isomerization catalysis: II. The interaction of C4 olefins and alcohols with HZSM5 zeolite

    SciTech Connect

    Trombetta, M.; Busca, G.; Rossini, S.

    1997-06-01

    The catalytic activity of the zeolite HZSM5 in n-butene conversion was investigated under conditions similar to those of a commercial process for skeletal isomerization. The catalyst was found to be very active in n-butene conversion, but selectivity to isobutene was low due to a predominance of cracking, coking, and oligomerization side reactions. The interaction of 1-butene, cis-2-butene, trans-2-butene, isobutene, sec-butanol, and tert-butanol was also investigated by FT-IR spectroscopy in the temperature range 150-673 K. 47 refs., 9 figs., 2 tabs.

  20. Sum frequency generation vibrational spectroscopy of 1,3-butadiene hydrogenation on 4 nm Pt@SiO2, Pd@SiO2, and Rh@SiO2 core-shell catalysts.

    PubMed

    Krier, James M; Michalak, William D; Cai, Xiaojun; Carl, Lindsay; Komvopoulos, Kyriakos; Somorjai, Gabor A

    2015-01-14

    1,3-Butadiene (1,3-BD) hydrogenation was performed on 4 nm Pt, Pd, and Rh nanoparticles (NPs) encapsulated in SiO2 shells at 20, 60, and 100 C. The core-shells were grown around polyvinylpyrrolidone (PVP) coated NPs (Stber encapsulation) prepared by colloidal synthesis. Sum frequency generation (SFG) vibrational spectroscopy was performed to correlate surface intermediates observed in situ with reaction selectivity. It is shown that calcination is effective in removing PVP, and the SFG signal can be generated from the metal surface. Using SFG, it is possible to compare the surface vibrational spectrum of Pt@SiO2 (1,3-BD is hydrogenated through multiple paths and produces butane, 1-butene, and cis/trans-2-butene) to Pd@SiO2 (1,3-BD favors one path and produces 1-butene and cis/trans-2-butene). In contrast to Pt@SiO2 and Pd@SiO2, SFG and kinetic experiments of Rh@SiO2 show a permanent accumulation of organic material. PMID:25272243

  1. Processing-structure-property studies of: (I) submicron polymeric fibers produced by electrospinning and (II) films of linear low density polyethylenes as influenced by the short chain branch length in copolymers of ethylene/1-butene, ethylene/1-hexene and ethylene/1-octene synthesized by a single site metallocene catalyst

    NASA Astrophysics Data System (ADS)

    Gupta, Pankaj

    The overall theme of the research discussed in this dissertation has been to explore processing-structure-property relationships for submicron polymeric fibers produced by electrospinning (Part I) and to ascertain whether or not the length of the short chain branch has any effect on the physical properties of films of linear low-density polyethylenes (LLDPEs) (Part II). The research efforts discussed in Part I of this dissertation relate to some fundamental as well as more applied investigations involving electrospinning. These include investigating the effects of solution rheology on fiber formation and developing novel methodologies to fabricate polymeric mats comprising of high specific surface submicron fibers of more than one polymer, high chemical resistant substrates produced by in situ photo crosslinking during electrospinning, superparamagnetic flexible substrates by electrospinning a solution of an elastomeric polymer containing ferrite nanoparticles of Mn-Zn-Ni and substrates for filtration applications. Bicomponent electrospinning of poly(vinyl chloride)-polyurethane and poly(vinylidiene fluoride)-polyurethane was successfully performed. In addition, filtration properties of single and bicomponent electrospun mats of polyacrylonitrile and polystyrene were investigated. Results indicated lower aerosol penetration or higher filtration efficiencies of the filters based on submicron electrospun fibers in comparison to the conventional filter materials. In addition, Part II of this dissertation explores whether or not the length of the short chain branch affects the physical properties of blown and compression molded films of LLDPEs that were synthesized by a single site metallocene catalyst. Here, three resins based on copolymers of ethylene/1-butene, ethylene/1-hexene, and ethylene/1-octene were utilized that were very similar in terms of their molecular weight and distribution, melt rheology, density, crystallinity and short chain branching content and its distribution. Interestingly, at higher deformation rates (ca. 1m/s), the breaking, tear and impact strengths of films based on ethylene/1-hexene and ethylene/1-octene were found to be superior than those based on ethylene/1-butene. (Abstract shortened by UMI.)

  2. Reactions of OH with Butene Isomers. Measurements of the Overall Rates and a Theoretical Study

    SciTech Connect

    Vasu, Subith; Huynh, Lam; Davidson, David F.; Hanson, Ronald K.; Golden, David

    2011-03-09

    Reactions of hydroxyl (OH) radicals with 1-butene (k1), trans-2-butene (k2), and cis-2-butene (k3) were studied behind reflected shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH3)3-CO-OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R1(5) line of the OH A-X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C5 oxidation mechanism, and rate constants for the reaction of OH with butene isomers were extracted by matching modeled and measured OH concentration time histories. We present the first high-temperature measurement of OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both 1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of OH with 1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study.

  3. Mesophases in polyethylene, polypropylene, and poly(1-butene)

    SciTech Connect

    Androsch, Rene J; Di Lorenzo, Maria; Schick, Christoph; Wunderlich, Bernhard {nmn}

    2010-01-01

    This paper contains new views about the amorphous and partially ordered phases of the three polymers listed in the title. The discussion is based on information on structure, thermodynamic stability, and large-amplitude molecular motion. Polyethylene is the basic backbone of all alkene polymers, and the other two are the first members of the vinyl polymers which have stereospecifically placed alkyl side chains. Their multiphase structures consist of metastable crystals, mesophases, and surrounding rigid and mobile amorphous fractions. All these phases have sizes ranging from micrometer dimensions down to nanometers. Besides the phase structures, information about the molecular coupling between the phases must be considered. Depending on temperature, the polymer phases can vary from solid (rigid) to liquid (mobile). New knowledge is also gained by cross-comparison of the title polymers. The experimental information was gained from (a) various forms of slow, fast, and temperature-modulated thermal analysis to identify equilibrium and non-equilibrium states, (b) measurement of structure and morphology at various length scales, and (c) tracing of the large-amplitude molecular motion, the kinetics of order/disorder changes, and the liquid/solid transitions (glass transitions). It is shown that much more needs to be known about the various phases and their coupling to characterize a given polymer and to fine-tune its properties for a given application.

  4. Raman spectroscopy and dioxygen adsorption on Cs-loaded zeolite catalysts for butene isomerization.

    PubMed

    Li, Junhui; Davis, Robert J

    2005-04-21

    Cesium-exchanged zeolite X was impregnated with cesium acetate (Cs(Ac)/CsX) or cesium carbonate (Cs(2)CO(3)/CsX) and subsequently calcined to yield a basic catalyst. The Raman spectra of calcined Cs(Ac)/CsX and Cs(2)CO(3)/CsX exhibited a new peak at 1036 cm(-1) associated with the occluded species. No evidence for cesium peroxide or superoxide was observed. The occluded cesium species in both samples is proposed to be an oxycarbonate, which is a metastable intermediate between cesium carbonate and cesium oxide. The isomerization of 1-butene to cis- and trans-2-butene was catalyzed by cesium-loaded zeolite X. Although CO(2) readily poisoned the active base sites for catalysis, pretreatment of a basic zeolite with O(2) at 373 K did not. Co-feeding O(2) with 1-butene at 373 K, however, completely deactivated the base sites. Analysis of the reactor effluent at 473 K and the IR spectrum of the catalyst indicated the formation of carbon dioxide, which irreversibly adsorbed on the basic sites of the catalyst. Deactivation of basic catalysts by O(2) is proposed to occur through a low temperature oxidation of 1-butene to carbon dioxide, which strongly adsorbs on the active sites. PMID:16851814

  5. [Os{sub 2}(CO){sub 8}({mu}{sub 2}-{eta}{sup 1},{eta}{sup 1}-propene)] and related complexes as vibrational models for alkenes chemisorbed on single-crystal metal surfaces

    SciTech Connect

    Anson, C.E.; Sheppard, N.; Bender, B.R.; Norton, J.R.

    1999-01-27

    The FTIR spectra of [Os{sub 2}(CO){sub 8}({mu}{sub 2}-{eta}{sup 1},{eta}{sup 1}-C{sub 2}H{sub 3}CH{sub 3})] and of its methyl-d{sub 3} and d{sub 6} isotopologues have been measured and assigned. Comparison of these vibrational data with previously published EELS and RAIRS studies of propene chemisorbed on Pt(111) and Ni(111) at low temperatures indicates that, on these surfaces, the propene species are chemisorbed via a ({mu}{sub 2}-P{eta}{sup 1},{eta}{sup 1}-C{sub 2}H{sub 3}CH{sub 3}) bonding mode. However, differences in the intensity patterns between the spectra of the adsorbed species compared with that of the model compound imply additional twisting or tilting with respect to the surface. Assignment of the FTIR spectra of the corresponding 1-butene and trans-2-butene complexes [Os{sub 2}(CO){sub 8}({mu}{sub 2}-{eta}{sup 1},{eta}{sup 1}-C{sub 2}H{sub 3}C{sub 2}H{sub 5})] and [Os{sub 2}(CO){sub 8}({mu}{sub 2}{eta}{sup 1},{eta}{sup 1}-CH{sub 3}C{sub 2}H{sub 2}CH{sub 3})] indicates similar bonding modes for chemisorbed 1-butene and trans-2-butene on Pt(111). Infrared data for the mononuclear propene complex [Os(CO){sub 4}({eta}{sup 2}-C{sub 2}H{sub 3}CH{sub 3})], on the other hand, are in good agreement with published EEL data for propene on Ru(0001) and Rh(111), indicating that at low temperatures on these surfaces, propene is chemisorbed as a methyl-substituted metallacyclopropane-like species. These bonding modes are analogous to those established for low-temperature ethene chemisorption on these surfaces.

  6. Laboratory spectroscopic analyses of electron irradiated alkanes and alkenes in solar system ices

    NASA Astrophysics Data System (ADS)

    Hand, K. P.; Carlson, R. W.

    2012-03-01

    We report results from laboratory experiments of 10 keV electron irradiation of thin ice films of water and short-chain hydrocarbons at 10-8 Torr and temperatures ranging from 70-100 K. Hydrocarbon mixtures include water with C3H8, C3H6, C4H10 (butane and isobutane), and C4H8, (1-butene and cis/trans-2-butene). The double bonds of the alkenes in our initial mixtures were rapidly destroyed or converted to single carbon bonds, covalent bonds with hydrogen, bonds with -OH (hydroxyl), bonds with oxygen (C-O), or double bonds with oxygen (carbonyl). Spectra resulting from irradiation of alkane and alkene ices are largely indistinguishable; the initial differences in film composition are destroyed and the resulting mixture includes long-chain, branched aliphatics, aldehydes, ketones, esters, and alcohols. Methane was observed as a product during radiolysis but CO was largely absent. We find that while some of the carbon is oxidized and lost to CO2 formation, some carbon is sequestered into highly refractory, long-chain aliphatic compounds that remain as a thin residue even after the ice film has been raised to standard temperature and pressure. We conclude that the high availability of hydrogen in our experiments leads to the formation of the formyl radical which then serves as the precursor for formaldehyde and polymerization of longer hydrocarbon chains.

  7. Characterization of volatile organic compounds in smoke at municipal structural fires.

    PubMed

    Austin, C C; Wang, D; Ecobichon, D J; Dussault, G

    2001-07-20

    The objective of this study was to characterize volatile organic compounds (VOCs) found at municipal structural fires in order to identify sources of long-term health risks to firefighters, which may be contributing factors in heart disease and cancer. Firefighters collected air into evacuated Summa canisters inside burning buildings at nine municipal structural fires under conditions where they judged that at least some firefighters might remove their self-contained breathing apparatus masks. Volatile organic compounds were identified and quantified for 144 target compounds using cryogenic preconcentration and gas chromatography/mass spectral detection (GC/MSD) methodology operating in selected ion monitoring mode. Samples were also analyzed in SCAN mode and examined for the appearance of substances that were not present in the instrument standard calibration mixture. The spectra of municipal structural fires were surprisingly similar and remarkable for their simplicity, which was largely due to the dominating presence of benzene along with toluene and naphthalene. Propene and 1,3-butadiene were found in all of the fires, and styrene and other alkyl-substituted benzene compounds were frequently identified. Similar "fingerprints" of the same 14 substances (propene, benzene, xylenes, 1-butene/2-methylpropene, toluene, propane, 1,2-butadiene, 2-methylbutane, ethylbenzene, naphthalene, styrene, cyclopentene, 1-methylcyclopentene, isopropylbenzene) previously identified at experimental fires burning various solid combustible materials were also found at municipal structural fires, accounting for 76.8% of the total VOCs measured. Statistically significant positive correlations were found between increasing levels of benzene and levels of propene, the xylenes, toluene, 1-butene/2-methylpropene, 1,3-butadiene, and naphthalene. Given the toxicity/carcinogenicity of those VOCs that were found in the highest concentrations, particularly benzene, 1,3-butadiene, and styrene, further investigation of VOC exposures of firefighters is warranted. Benzene, or its metabolic product s-phenylmercapturic acid in urine, was identified as a suitable chemical marker for firefighter exposure to combustion products. PMID:11482799

  8. Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes. Progress report, April 1, 1988--March 31, 1989

    SciTech Connect

    Norton, J.R.

    1989-01-01

    We have obtained a neutron diffraction data set for Os{sub 2}(CO){sub 8}({mu}-C{sub 2}H{sub 4}). While the structure is still being solved, it is already clear that the hybridization at both of the ethylene carbons is sp{sup 3}. Our first interpretation of our liquid crystal NMR results had suggested a very acute H-C-H angle. We have also obtained {sup 13}C liquid crystal data for Os{sub 2}(CO){sub 8}({mu}-C{sub 2}H{sub 4}). Liquid crystal NMR ({sup 13}C as well as {sup 1}H) spectra have been obtained for Os(CO){sub 4}(C{sub 2}H{sub 4}) and its solution structure determined, in order to test our methodology on a molecule with a rigid structure. The normal modes of Os(CO){sub 4}({mu}-C{sub 2}H{sub 4}) and its deuterated and {sup 13}C-labelled isotopomers have been completely assigned. A partial vibrational analysis of Os{sub 2}(CO){sub 8}({mu}-propene), Os{sub 2}(CO){sub 8}(trans-2-butene), and Os{sub 2}(CO){sub 8}(1-butene) has been completed. We have prepared Os(CO){sub 4}({mu}-CH{sub 2}CH{sub 2}CH{sub 2}) and its 3,3-dideuterio analog. In the course of this work the reaction of Na{sub 2}Os(CO){sub 4} with a number of 1,3-propanediol derivatives has been examined. 1,3-Propanediol ditosylate afforded much better yields of the osmacycle than did either the ditriflate or diiodide. 2,2-Dideutero-1,3-propanediol ditosylate was used to prepare the deuterium-labelled osmacyclobutane.

  9. Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes

    SciTech Connect

    Norton, J.R.

    1989-01-01

    We have obtained a neutron diffraction data set for Os{sub 2}(CO){sub 8}({mu}-C{sub 2}H{sub 4}). While the structure is still being solved, it is already clear that the hybridization at both of the ethylene carbons is sp{sup 3}. Our first interpretation of our liquid crystal NMR results had suggested a very acute H-C-H angle. We have also obtained {sup 13}C liquid crystal data for Os{sub 2}(CO){sub 8}({mu}-C{sub 2}H{sub 4}). Liquid crystal NMR ({sup 13}C as well as {sup 1}H) spectra have been obtained for Os(CO){sub 4}(C{sub 2}H{sub 4}) and its solution structure determined, in order to test our methodology on a molecule with a rigid structure. The normal modes of Os(CO){sub 4}({mu}-C{sub 2}H{sub 4}) and its deuterated and {sup 13}C-labelled isotopomers have been completely assigned. A partial vibrational analysis of Os{sub 2}(CO){sub 8}({mu}-propene), Os{sub 2}(CO){sub 8}(trans-2-butene), and Os{sub 2}(CO){sub 8}(1-butene) has been completed. We have prepared Os(CO){sub 4}({mu}-CH{sub 2}CH{sub 2}CH{sub 2}) and its 3,3-dideuterio analog. In the course of this work the reaction of Na{sub 2}Os(CO){sub 4} with a number of 1,3-propanediol derivatives has been examined. 1,3-Propanediol ditosylate afforded much better yields of the osmacycle than did either the ditriflate or diiodide. 2,2-Dideutero-1,3-propanediol ditosylate was used to prepare the deuterium-labelled osmacyclobutane.

  10. Kinetics of hydrogen abstraction reactions of butene isomers by OH radical

    SciTech Connect

    Sun, Hongyan; Law, Chung K.

    2010-11-26

    The rate coefficients of H-abstraction reactions of butene isomers by the OH radical were determined by both canonical variational transition-state theory and transition-state theory, with potential energy surfaces calculated at the CCSD(T)/6-311++G(d,p)//BH&HLYP/6-311G(d,p) level and CCSD(T)/6-311++G(d,p)//BH&HLYP/cc-pVTZ level and quantum mechanical tunneling effect corrected by either the small-curvature tunneling method or the Eckart method. While 1-butene contains allylic, vinylic, and alkyl hydrogens that can be abstracted to form different butene radicals, results reveal that s-allylic H-abstraction channels have low and broad energy barriers, and they are the most dominant channels which can occur via direct and indirect H-abstraction channels. For the indirect H-abstraction s-allylic channel, the reaction can proceed via forming two van der Waals prereactive complexes with energies that are 2.7-2.8 kcal mol-1 lower than that of the entrance channel at 0 K. Assuming that neither mixing nor crossover occurs between different reaction pathways, the overall rate coefficient was calculated by summing the rate coefficients of the s-allyic, methyl, and vinyl H-abstraction paths and found to agree well with the experimentally measured OH disappearance rate. Furthermore, the rate coefficients of p-allylic H abstraction of cis-2-butene, trans-2-butene, and isobutene by the OH radical were also determined at 300-1500 K, with results analyzed and compared with available experimental data.

  11. Reactions of volatile organic compounds in the atmosphere: Ozone-alkene reactions

    NASA Astrophysics Data System (ADS)

    Fenske, Jill Denise

    2000-08-01

    Photochemical smog cannot form without sunlight, nitrogen oxides, and volatile organic compounds (VOC). This dissertation addresses several different aspects of VOC chemistry in the atmosphere. Aside from ambient levels of VOC outdoors, VOC are also present at moderate concentrations indoors. Many studies have measured indoor air concentrations of VOC, but only one considered the effects of human breath. The major VOC in the breath of healthy individuals are isoprene (12-580 ppb), acetone (1.2-1800 ppb), ethanol (13-1000 ppb), methanol (160-2000 ppb), and other alcohols. Human emissions of VOC are negligible on a regional (less than 4%) and global scale (less than 0.3%). However, in indoor air, under fairly crowded situations, human emissions of VOC may dominate other sources of VOC. An important class of VOC in the atmosphere is alkenes, due to their high reactivity. The ozone reaction with alkenes forms OH radicals, a powerful oxidizing agent in the troposphere. OH radical formation yields from the ozonolysis of several cycloalkenes were measured using small amounts of fast-reacting aromatics and aliphatic ethers to trace OH formation. The values are 0.62 +/- 0.15, 0.54 +/- 0.13, 0.36 +/- 0.08, and 0.91 +/- 0.20 for cyclopentene, cyclohexene, cycloheptene and 1-methylcyclohexene, respectively. Density functional theory calculations at the B3LYP/6-31 G(d,p) level are presented to aid in understanding the trends observed. The pressure dependence of OH radical yields may lend insight into the formation mechanism. We have made the first study of the pressure dependence of the OH radical yield for ethene, propene, 1-butene, trans-2-butene, and 2,3-dimethyl-2- butene over the range 20-760 Torr, and trans -3-hexene, and cyclopentene over the range 200-760 Torr. The OH yields from ozonolysis of ethene and propene were pressure dependent, while the other compounds had OH yields that were independent of pressure. Ozone-alkene reactions form vibrationally excited carbonyl oxide intermediates (of the form R1R2COO), some of which, once thermalized, are thought to react with SO2, H2O, NOx, aldehydes and alcohols. Several studies using relative rate techniques and ab initio calculations have resulted in estimates for the rate coefficients of reactions of the thermalized biradicals. The ranges of measured and estimated rate coefficients span two to six orders of magnitude, depending on the reaction partner. Using an atmospheric pressure flow reactor, we have made the first absolute rate coefficient determination for the decomposition of and reaction with acetaldehyde of thermalized CH3CHOO from trans-2-butene ozonolysis. The measurement results are: kdec = 76 s-1 and kald = 1.0 10-12 cm 3molec-1s-1.

  12. Effects of biomass burning on summertime nonmethane hydrocarbon concentrations in the Canadian wetlands

    NASA Technical Reports Server (NTRS)

    Blake, D. R.; Smith, T. W., Jr.; Chen, T.-Y.; Whipple, W. J.; Rowland, F. S.

    1994-01-01

    Approximately 900 whole air samples were collected and assayed for selected C2-C10 hydrocarbons and seven halocarbons during the 5-week Arctic Boundary Layer Expedition (ABLE) 3B conducted in eastern Canadian wetland areas. In more than half of the 46 vertical profiles flown, enhanced nonmethane hydrocarbon (NMHC) concentrations attributable to plumes from Canadian forest fires were observed. Urban plumes, also enhanced in many NMHCs, were separately identified by their high correlation with elevated levels of perchloroethene. Emission factors relative to ethane were determined for 21 hydrocarbons released from Canadian biomass burning. Using these data for ethane, ethyne, propane, n-butane, and carbon monoxide enhancements from the literature, global emissions of these four NMHCs were estimated. Because of its very short atmospheric lifetime and its below detection limit background mixing ratio, 1,3-butadiene is an excellent indicator of recent combustion. No statistically significant emissions of nitrous oxide, isoprene, or CFC 12 were observed in the biomass-burning plumes encountered during ABLE 3B. The presence of the short-lived biogenically emitted isoprene at altitudes as high as 3000 m implies that mixing within the planetary boundary layer (PBL) was rapid. Although background levels of the longer-lived NMHCs in this Canadian region increase during the fire season, isoprene still dominated local hydroxyl radical photochemistry within the PBL except in the immediate vicinity of active fires. The average biomass-burning emission ratios for hydrocarbons from an active fire sampled within minutes of combustion were, relative to ethane, ethene, 2.45; ethyne 0.57; propane, 0.25; propene, 0.73; propyne, 0.06; n-butane, 0.09; i-butane, 0.01; 1-butene, 0.14; cis-2-butene, 0.02; trans-2-butene, 0.03; i-butylene, 0.07; 1,3-butadiene, 0.12; n-pentane, 0.05; i-pentane, 0.03; 1-pentene, 0.06; n-hexane, 0.05; 1-hexene, 0.07; benzene, 0.37; toluene, 0.16.

  13. Fluid inclusion volatile analysis by gas chromatography with photoionization/micro-thermal conductivity detectors: Applications to magmatic MoS sub 2 and other H sub 2 O-CO sub 2 and H sub 2 O-CH sub 4 fluids

    SciTech Connect

    Bray, C.J.; Spooner, E.T.C. )

    1992-01-01

    Eighteen fluid inclusion volatile peaks have been detected and identified from 1-2 g samples (quartz) by gas chromatography using heated on-line crushing, helium carrier gas, a single porous polymer column, two temperature programmed conditions for separate sample aliquots, micro-thermal conductivity (TCD) and photoionization detectors (PID), and off-line digital peak processing. In order of retention time these volatile peaks are: N{sub 2}, Ar, CO, CH{sub 4}, CO{sub 2}, C{sub 2}H{sub 4}, C{sub 2}H{sub 6}, C{sub 2}H{sub 2}, COS, C{sub 3}H{sub 6}, C{sub 3}H{sub 8}, C{sub 3}H{sub 4} (propyne), H{sub 2}O, SO{sub 2} {plus minus} iso-C{sub 4}H{sub 10} {plus minus} C{sub 4}H{sub 8} (1-butene) {plus minus} CH{sub 3}SH, C{sub 4}H{sub 8} (iso-butylene), ( ) C{sub 4}H{sub 6} (1,3 butadiene), and {plus minus} n-C{sub 4}H{sub 10} {plus minus}C{sub 4}H{sub 8} (trans-2-butene). H{sub 2}O is analyzed directly. O{sub 2} can be analyzed cryogenically between N{sub 2} and Ar, but has not been detected in natural samples to date in this study. Initial inclusion volatile analyses of fluids of interpreted magmatic origin from the Cretaceous Boss Mtn. monzogranite stock-related MoS{sub 2} deposit, central British Columbia of 97 mol% H{sub 2}O, 3% CO{sub 2}, 140-150 ppm N{sub 2}, and 16-39 ppm CH{sub 4} are reasonable in comparison with high temperature volcanic gas analyses from four, active calc-alkaline volcanoes, e.g., the H{sub 2}O contents of volcanic gases from the White Island (New Zealand), Mount St. Helens (Washington, USA), Merapi (Bali, Indonesia), and Momotombo (Nicaragua) volcanoes are 88-95%, > 90%, 88-95% and 93%, respectively; CO{sub 2} contents are 3-10%, 1-10%, 3-8%, and 3.5%. It appears that low, but significant concentrations of alkanes, alkenes, and alkynes have been detected in magmatically derived fluids.

  14. KINETIC ANALYSIS OF THE ALKYLATION REACTION OF ISOBUTANE WITH 1-BUTENE ON A SOLID ACID CATALYST IN GAS, LIQUID, AND SUPERCRITICAL REACTION MEDIA. (R826694C669)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  15. Transferable Potentials for Phase Equilibria. 4. United-Atom Description of Linear and Branched Alkenes and Alkylbenzenes

    SciTech Connect

    WICK,COLLIN D.; MARTIN,MARCUS G.; SIEPMANN,J. ILJA

    2000-07-12

    The Transferable Potentials for Phase Equilibria-United Atom (TraPPE-UA) force field for hydrocarbons is extended to alkenes and alkylbenzenes by introducing the following pseudo-atoms: CH{sub 2}(sp{sup 2}), CH(sp{sup 2}), CH(aro), R-C(aro) for the link to aliphatic side chains, and C(aro) for the link of two benzene rings. In this united-atom force field, the nonbonded interactions of the hydrocarbon pseudo-atoms are solely governed by Lennard-Jones 12-6 potentials, and the Lennard-Jones well depth and size parameters for the new pseudo-atoms were determined by fitting to the single-component vapor-liquid phase equilibria of a few selected model compounds. Configurational-bias Monte Carlo simulations in the NVT version of the Gibbs ensemble were carried out to calculate the single-component vapor-liquid coexistence curves for ethene, propene, 1-butene, trans- and cis-2-butene. 2-methylpropene, 1,5-hexadiene, 1-octene, benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene, o-, m-, and p-xylene, and naphthalene. The phase diagrams for the binary mixtures of (supercritical) ethene/n-heptane and benzene/n-pentane were determined from simulations in the NpT Gibbs ensemble. Although the TraPPE-UA force field is rather simple and makes use of relatively few different pseudo-atoms, its performance, as judged by comparisons to other popular force fields and available experimental data, is very satisfactory.

  16. Biogenic Emissions of Light Alkenes from a Coniferous Forest

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Turnipseed, A. A.; Martinez, L.; Shen, S.; De Gouw, J. A.; Warneke, C.; Koss, A.; Lerner, B. M.; Miller, B. R.; Smith, J. N.; Guenther, A. B.

    2014-12-01

    Alkenes are reactive hydrocarbons that play important roles in the photochemical production of tropospheric ozone and in the formation of secondary organic aerosols. The light alkenes (C2-C4) originate from both biogenic and anthropogenic sources and include C2H4 (ethene), C3H6 (propene) and C4H8 (1-butene, 2-butene, 2-methylpropene). Light alkenes are used widely as chemical feedstocks because their double bond makes them versatile for industrial reactions. Their biogenic sources are poorly characterized, with most global emissions estimates relying on laboratory-based studies; net ecosystem emissions have been measured at only one site thus far. Here we report net ecosystem fluxes of light alkenes and isoprene from a semi-arid ponderosa pine forest in the Rocky Mountains of Colorado, USA. Canopy scale fluxes were measured using relaxed eddy accumulation (REA) techniques on the 28-meter NCAR tower in the Manitou Experimental Forest Observatory. Updrafts and downdrafts were determined by sonic anemometry and segregated into 'up' and 'down' reservoirs over the course of an hour. Samples were then measured on two separate automated gas chromatographs (GCs). The first GC measured light hydrocarbons (C2-C6 alkanes and C2-C5 alkenes) by flame ionization detection (FID). The second GC measured halocarbons (methyl chloride, CFC-12, and HCFC-22) by electron capture detection (ECD). Additional air measurements from the top of the tower included hydrocarbons and their oxidation products by Proton Transfer Reaction Mass Spectrometry (PTR-MS). Three field intensives were conducted during the summer of 2014. The REA flux measurements showed that ethene, propene and the butene emissions have significant diurnal cycles, with maximum emissions at midday. The light alkenes contribute significantly to the overall biogenic source of reactive hydrocarbons and have a temporal variability that may be associated with physical and biological parameters. These ecosystem scale measurements will be compared with estimates used in global emissions models.

  17. Production of hydrogen peroxide and organic peroxides in the gas phase reactions of ozone with natural alkenes

    SciTech Connect

    Simonaitis, R.; Olszyna, K.J.; Meagher, J.F.

    1991-01-01

    The formation of H{sub 2}O{sub 2} and organic peroxides in the reaction of O{sub 3} with trans-2-butene and naturally occurring alkenes has been studied using a 31 m{sup 3} reaction chamber. H{sub 2}O{sub 2} and organic peroxides were found to be products of the O{sub 3} reaction with trans-2-butene, isoprene, {alpha} and {beta}-pinene, and limonene. Water is necessary for the formation of H{sub 2}O{sub 2} and most of the H{sub 2}O{sub 2} is formed via a route that does not involve HO{sub 2} radicals. These results indicate that the reaction of O{sub 3} with natural alkenes may be a significant source of atmospheric H{sub 2}O{sub 2}, particularly in forest and rural areas.

  18. Fluid inclusion volatile analysis by gas chromatography with photoionization micro-thermal conductivity detectors: Applications to magmatic MoS 2 and other H 2O-CO 2 and H 2O-CH 4 fluids

    NASA Astrophysics Data System (ADS)

    Bray, C. J.; Spooner, E. T. C.

    1992-01-01

    Eighteen fluid inclusion volatile peaks have been detected and identified from 1-2 g samples (quartz) by gas chromatography using heated (~105C) on-line crushing, helium carrier gas, a single porous polymer column (HayeSep R; 10' 1/8?: 100/120#; Ni alloy tubing), two temperature programme conditions for separate sample aliquots, micro-thermal conductivity (TCD) and photoionization detectors (PID; 11.7 eV lamp), and off-line digital peak processing. In order of retention time these volatile peaks are: N 2, Ar, CO, CH 4, CO 2, C 2H 4, C 2H 6, C 2H 2, COS, C 3H 6, C 3H 8, C 3H 4 (propyne), H 2O (22.7 min at 80C), SO 2, iso- C4H10 C4H8 (1-butene) CH3SH, C 4H 8 (iso-butylene), (?) C 4H 6 (1,3 butadiene) and n- C4H10 C4H8 (trans-2-butene) (80 and -70C temperature programme conditions combined). H 2O is analysed directly. O 2 can be analysed cryogenically between N 2 and Ar, but has not been detected in natural samples to date in this study. H 2S, SO 2, NH 3, HCl, HCN, and H 2 ca nnot be analysed at present. Blanks determined by crushing heat-treated Brazilian quartz (800-900C/4 h) are zero for 80C temperature programme conditions, except for a large, unidentified peak at ~64 min, but contain H 2O, CO 2, and some low molecular weight hydrocarbons at -70C temperature conditions due to cryogenic accumulation from the carrier gas and subsequent elution. TCD detection limits are ~30 ppm molar in inclusions; PID detection limits are ~ 1 ppm molar in inclusions and lower for unsaturated hydrocarbons (e.g., ~0.2 ppm for C 2H 4; ~ 1 ppb for C 2H 2; ~0.3 ppb for C 3H 6). Precisions (1?) are ~ 1-2% and ~ 13% for H 2O in terms of total moles detected; the latter value is equivalent to 0.6 mol% at the 95 mol% H 2O level. Major fluid inclusion volatile species have been successfully analysed on a ~50 mg fluid inclusion section chip (~7 mm ~10 mm ~100 ?m). Initial inclusion volatile analyses of fluids of interpreted magmatic origin from the Cretaceous Boss Mtn. monzogranite stock-related MoS 2 deposit, central British Columbia of ~97 mol% H 2O, ~3% CO 2, ~ 140-150 ppm N 2, and ~16-39 ppm CH 4 (~300-350C) are reasonable in comparison with high temperature (~400-900C) volcanic gas analyses from four, active calc-alkaline volcanoes; e.g., the H 2O contents of volcanic gases from the White Island (New Zealand), Mount St. Helens (Washington, USA), Merapi (Bali, Indonesia), and Momotombo (Nicaragua) volcanoes are 88-95%, >90% (often >95%), 88-95% and ~93%, respectively; CO 2 contents are ~3-10%, 1-10%, 3-8%, and ~3.5%. CO 2/N 2 ratios for the Boss Mtn. MoS 2 fluids of ~ 190-220 are in the range for known volcanic gas ratios (e.g., ~ 150- 240; White Island). The ?S content of the Boss Mtn. MoS 2 fluid prior to S loss by sulphide precipitation may have been ~2 mol% since CO 2/?S molar ratios of analysed high-temperature volcanic gases are ~ 1.5. This estimate is supported by ?S contents for White Island, Merapi and Momotombo volcanic gases of ~2%, ~0.5-2.5%, and ~2%. COS has been determined in H 2O-CO 2 fluid inclusions of interpreted magmatic origin from the Boss Mtn. MoS 2 deposit and the Tanco zoned granitic pegmatite, S.E. Manitoba at ~50-100 ppm molar levels, which are consistent with levels in volcanic gases. It appears that low, but significant, concentrations of C 2-C 4 alkanes (~ 1-20 ppm), C 2-C 4 alkenes (~ 1-480 ppb) and alkynes (e.g., C 3H 4) have been detected in magmatically derived fluids (Boss Mtn. MoS 2 deposit; Tanco granitic pegmatite). Significantly higher, low molecular weight hydrocarbon concentrations have been determined in a CH 4-rich (~ 2%), externally derived fluid of possible metamorphic or deep crustal origin trapped as inclusions in metasomatic wall-rock tourmaline adjacent to the Tanco pegmatite (e.g., 300/470 ppm C 2H 6; 50/90 ppm C 3H 8; 3-60 ppm C 2H 4/C 3H 6 n-C 4H 10).

  19. Polybutenes

    ERIC Educational Resources Information Center

    Daniels, D. J.; And Others

    1973-01-01

    Discusses the use of aluminum chloride and other Friedel-Crafts type catalysts to polymerize 2-methylpropene and the application of such products in industry and agriculture. Includes a laboratory experiment on the polybutene preparation suitable for high school purposes. (CC)

  20. Metal-containing plasma-polymerized coatings for laser-fusion targets

    SciTech Connect

    Letts, S.A.; Jordan, C.W.

    1981-09-14

    Addition of metal to plastic layers in some direct drive laser fusion targets is needed to reduce electron induced fuel preheat. A plasma polymerization coating system was constructed to produce a metal seeded polymer by adding an organometallic gas to the usual trans-2-butene and hydrogen feedstocks. Since organometallic gases are highly reactive and toxic, safety is a major concern in the design of a coating system. Our coating apparatus was designed with three levels of containment to assure protection of the operator. The gas handling system has redundant valves and was designed to fail safe. Several sensor controlled interlocks assure safe operating conditions. Waste materials are collected on a specially designed cold trap. Waste disposal is accomplished by heating the traps and purging volatile products through a reactor vessel. The design, operating procedure, and safety interlocks of this novel coating system are described.

  1. Use of propane as a quench gas in argon-filled proportional counters and comparison with other quench gases

    NASA Technical Reports Server (NTRS)

    Agrawal, P. C.; Ramsey, B. D.

    1988-01-01

    An experimental investigation of propane and six other quench gases was carried out in argon-filled proportional counters. The objective of the study was to find the best gas mixture for optimizing the gas gain and the energy resolution as well as to understand the role of the ionization potential of quench gases in determining these parameters. It was found that the best gas gains and energy resolutions are obtained with propane, ethane, and isobutane in that order. The ionization potentials of these three lie below the argon metastable potentials and have the lowest value of resonance defect compared to the other quench gases. The better results obtained with these mixtures can be explained by an increased ionization yield resulting from the Penning effect. Propylene and trans-2-butene give inferior performance compared to the above three gases. Methane and carbon dioxide, the most commonly used quench gases in the argon-filled detectors, provide the worst results.

  2. Photo-oxidation of Polymers Synthesized by Plasma and Initiated CVD

    DOE PAGESBeta

    Baxamusa, Salmaan H.; Suresh, Aravind; Ehrmann, Paul; Laurence, Ted; Hanania, Jiries; Hayes, Jeff; Harley, Stephen; Burkey, Daniel D.

    2015-11-09

    Plasma polymers are often limited by their susceptibility to spontaneous and photo-oxidation. We show that the unusual photoluminescence (PL) behavior of a plasma polymer of trans-2-butene is correlated with its photoluminescence strength. These photo-processes occur under blue light illumination (λ=405 nm), distinguishing them from traditional ultraviolet degradation of polymers. These photo-active defects are likely formed during the plasma deposition process and we show that a polymer synthesized using initiated (i)CVD, non-plasma method, has 1000× lower PL signal and enhanced photo-stability. In conclusion, non-plasma methods such as iCVD may therefore be a route to overcoming material aging issues that limit themore » adoption of plasma polymers.« less

  3. A Combined Experimental and Theoretical Study of the Reaction OH + 2-Butene in the 400-800 K Temperature Range.

    PubMed

    Antonov, Ivan O; Kwok, Justin; Zdor, Judit; Sheps, Leonid

    2015-07-16

    We report a combined experimental and theoretical study of the OH + cis-2-butene and OH + trans-2-butene reactions at combustion-relevant conditions: pressures of 1-20 bar and temperatures of 400-800 K. We probe the OH radical time histories by laser-induced fluorescence and analyze these experimental measurements with aid from time-dependent master-equation calculations. Importantly, our investigation covers a temperature range where experimental data on OH + alkene chemistry in general are lacking, and interpretation of such data is challenging due to the complexity of the competing reaction pathways. Guided by theory, we unravel this complex behavior and determine the temperature- and pressure-dependent rate coefficients for the three most important OH + 2-butene reaction channels at our conditions: H abstraction, OH addition to the double bond, and back-dissociation of the OH-butene adduct. PMID:25860092

  4. On the pressure dependence of the NO 2 product yield in the reaction of NO 3 radicals with selected alkenes

    NASA Astrophysics Data System (ADS)

    Oizmann, M.; Benter, Th.; Liesner, M.; Schindler, R. N.

    An explanation is given for the difference in pressure dependences of the NO 2 product yield in the reactions NO 3- alkene and NO 3- 1.3-alkadiene including styrene. A simple model is used to describe the decomposition over stabilization ratio for the chemically activated intermediate nitrooxy-alkyl radical. It is shown that the resonance stabilization of this radical in the case of conjugated olefins is sufficiently high to account for the difference observed. The model is applied to experimental data from the reactions of NO 3 with trans-2-butene, 2,3-dimethyl-2-butene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and styrene. Kinetic parameters for the decomposition reaction of the intermediate radicals into NO 2 and epoxide are estimated and consequences for their reactions under tropospheric conditions are discussed.

  5. Photo-oxidation of Polymers Synthesized by Plasma and Initiated CVD

    SciTech Connect

    Baxamusa, Salmaan H.; Suresh, Aravind; Ehrmann, Paul; Laurence, Ted; Hanania, Jiries; Hayes, Jeff; Harley, Stephen; Burkey, Daniel D.

    2015-11-09

    Plasma polymers are often limited by their susceptibility to spontaneous and photo-oxidation. We show that the unusual photoluminescence (PL) behavior of a plasma polymer of trans-2-butene is correlated with its photoluminescence strength. These photo-processes occur under blue light illumination (λ=405 nm), distinguishing them from traditional ultraviolet degradation of polymers. These photo-active defects are likely formed during the plasma deposition process and we show that a polymer synthesized using initiated (i)CVD, non-plasma method, has 1000× lower PL signal and enhanced photo-stability. In conclusion, non-plasma methods such as iCVD may therefore be a route to overcoming material aging issues that limit the adoption of plasma polymers.

  6. Topological description of the bond-breaking and bond-forming processes of the alkene protonation reaction in zeolite chemistry: an AIM study.

    PubMed

    Zalazar, María Fernanda; Peruchena, Nélida Maria

    2011-10-01

    Density functional theory and atoms in molecules theory were used to study bond breakage and bond formation in the trans-2-butene protonation reaction in an acidic zeolitic cluster. The progress of this reaction along the intrinsic reaction coordinate, in terms of several topological properties of relevant bond critical points and atomic properties of the key atoms involved in these concerted mechanisms, were analyzed in depth. At B3LYP/6-31++G(d,p)//B3LYP/6-31G(d,p) level, the results explained the electron density redistributions associated with the progressive bond breakage and bond formation of the reaction under study, as well as the profiles of the electronic flow between the different atomic basins involved in these electron reorganization processes. In addition, we found a useful set of topological indicators that are useful to show what is happening in each bond/atom involved in the reaction site as the reaction progresses. PMID:21193939

  7. Pulmonary function in normal and elastase-treated hamsters exposed to a complex mixture of olefin-ozone-sulfur dioxide reaction products

    SciTech Connect

    Raub, J.A.; Miller, F.J.; Graham, J.A.; Gardner, D.E.; O'Neil, J.J.

    1983-01-01

    An elastase-induced emphysema model was utilized to determine if hamsters with preexisting lung disease were more susceptible to lung damage from air-pollutant exposure. Male golden hamsters, divided into two treatment groups, were given a single intratracheal injection of either 6 units of porcine pancreatic elastase (EMP) or buffer (CNT). After a 4-week recovery period, equal numbers of each group were exposed 23 hr/day x 28 day to filtered air (AIR) or to the complex by-products from a dark-phase-reaction mixture of trans-2-butene, ozone, and sulfur dioxide (MIX). Lung-function measurements on the elastase-treated groups showed changes consistent with mild emphysema. There were no significant differences in lung volumes or lung compliance between the AIR- and MIX-exposed animals. However, the nitrogen washout slope decreased and the diffusing capacity for carbon monoxide increased in both the CNT and EMP hamsters exposed to the MIX. The change in diffusing capacity was greater in normal hamsters than in hamsters with emphysema, and it is hypothesized that animals with impaired lung function had a decreased ability to respond to a pulmonary insult from the mix.

  8. The Use of Conditional Probability Functions and Potential Source Contribution Functions to Identify Source Regions and Advection Pathways of Hydrocarbon Emissions in Houston, Texas

    SciTech Connect

    Xie, YuLong; Berkowitz, Carl M.

    2007-09-01

    In this study, we demonstrate the utility of conditional probability functions (CPFs), potential source contribution functions (PSCFs), and hierarchical clustering analysis to identify the source region and transport pathways of hydrocarbons measured at five photochemical assessment monitoring stations (PAMS) near the Houston ship channel from June to October 2003. Over 50 volatile organic compound (VOC) concentrations were measured on the hourly collected samples. Routine surface observations of wind directions measured at each of the receptor sites were used extensively. We show that VOCs with similar CPF patterns likely have common transport pathways. This was established with the multivariate technique, which uses the hierarchical clustering analysis to allow clusters of groups of VOCs to form with similar CPF patterns. This method revealed that alkenes, and in particular those with geometric isomers such as cis-/trans-2-butene and cis-/trans-2-pentene, have similar CPF patterns. The alkane isomers often show CPF patterns among themselves, and similarly, aromatic compounds often show similar patterns among themselves too. We also show how trajectory information can be used in conjunction with the PSCF analysis to produce a graphic analysis suggesting specific source areas for a given VOC. The use of these techniques in the chemically and meteorologically complex environment of Houston, Texas, suggests its further utility in other areas with relatively simpler conditions.

  9. The use of conditional probability functions and potential source contribution functions to identify source regions and advection pathways of hydrocarbon emissions in Houston, Texas

    NASA Astrophysics Data System (ADS)

    Xie, Yulong; Berkowitz, Carl M.

    In this study, we demonstrate the utility of conditional probability functions (CPFs), potential source contribution functions (PSCFs), and hierarchical clustering analysis (HAC) to identify the source region and transport pathways of hydrocarbons measured at five photochemical assessment monitoring stations (PAMS) near the Houston Ship Channel from June to October 2003. In contrast to scatter plots, which only show the pair-wise correlation of species, commonality in CPF figures shows both correlation and information on the source region of the species in question. In this study, we use over 50 hourly volatile organic compound (VOC) concentrations and surface wind observations to show that VOCs with similar CPF patterns likely have common transport pathways. This was established with the multivariate technique, which uses the hierarchical clustering analysis to define clusters of VOCs having similar CPF patterns. This method revealed that alkenes, and in particular those with geometric isomers such as cis-/ trans-2-butene and cis-/ trans-2-pentene, have similar CPF patterns and hence, a common area of origin. The alkane isomers often show CPF patterns among themselves, and similarly, aromatic compounds often show similar patterns. We also show how calculated trajectory information can be used in the PSCF analysis to produce a graphic picture that identifies specific geographic areas associated with a given VOC (or other pollutant). The use of these techniques in the chemically and meteorologically complex environment of Houston, Texas, suggests its further utility in other areas with relatively simpler conditions.

  10. Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes. Final report

    SciTech Connect

    Norton, J.R.

    1994-04-25

    Assignment of the vibrational modes Of Os{sub 2}(CO){sub 8}(CHCH{sub 3}) and Os(CO){sub 4}(C{sub 2}H{sub 4)} has given fingerprint vibrational spectra for the following species when chemisorbed on metal catalyst surfaces: ethylidene and ethylene bound in a metallacyclopropane mode. The formation and fragmentation of diosmacyclobutanes have been shown to involve slippage of the outgoing olefin onto a single osmium, and associative exchange of the olefin from that site. The incorporation of vinylcyclopropane without rearrangement has confirmed the absence of a diradical intermediate. The anomalous stability of the diosmacyclobutane derived from trans-2-butene has proven due to greater destabilization (by the substituent methyls) of the slipped intermediate than of the ground state. Reaction of an osmacyclobutane with 1,3- or 1,2-dienes (allenes) gives 1,2 rather than 1,4 addition to the diosmium unit. Treatment of Os(CO){sub 4}(C{sub 2}H{sub 4}) with triflic acid results in the formation of Os(CO){sub 4}(C{sub 2}H{sub 5})OTf. The authors have found that the reaction of an aryl iodine(III) reagent with propargyl stannanes or silanes results in o-iodo propargyl arenes.

  11. Moessbauer spectra of ferrite catalysts used in oxidative dehydrogenation

    NASA Technical Reports Server (NTRS)

    Cares, W. R.; Hightower, J. W.

    1971-01-01

    Room temperature Mossbauer spectroscopy was used to examine bulk changes which occur in low surface area CoFe2O4 and CuFe2O4 catalysts as a result of contact with various mixtures of trans-2-butene and O2 during oxidative dehydrogenation reactions at about 420 C. So long as there was at least some O2 in the gas phase, the CoFe2O4 spectrum was essentially unchanged. However, the spectrum changed from a random spinel in the oxidized state to an inverse spinel as it was reduced by oxide ion removal. The steady state catalyst lies very near the fully oxidized state. More dramatic solid state changes occurred as the CuFe2O4 underwent reduction. Under severe reduction, the ferrite was transformed into Cu and Fe3O4, but it could be reversibly recovered by oxidation. An intense doublet located near zero velocity persisted in all spectra of CuFe2O4 regardless of the state of reduction.

  12. Evaluation of Fluidized Beds for Mass Production of IFE Targets

    SciTech Connect

    Huang, H.; Vermillion, B.A.; Brown, L.C.; Besenbruch, G.E.; Goodin, D.T.; Stemke, R.W.; Stephens, R.B.

    2005-01-15

    Of the building blocks of an inertial fusion energy (IFE) plant, target fabrication remains a significant credibility issue. For this reason, an extensive parametric study has been conducted on mass production of glow discharge polymer (GDP) shells in a vertical fluidized bed. Trans-2-butene was used as a reactant gas with hydrogen as a diluting and etching agent. Coating rates in the range of 1 to 2 {mu}m/h were demonstrated on batches of 30 shells where National Ignition Facility-quality surfaces were obtained for 3- to 5-{mu}m-thick coatings. Thick coatings up to 325 {mu}m were also demonstrated that are visually transparent, without void and stress fracture. A phenomenological understanding of the GDP growth mechanisms to guide future experiments was further established. Specifically, gas-phase precipitation and high-impact collisions were identified as the main surface-roughening mechanisms. The former produces dense cauliflower-like surface patterns that can be eliminated by adjusting the gas flow rates and the flow ratio. The latter produces isolated domelike surface defects that can be reduced by introducing concerted motion between the shells. By converting from a vertical to a horizontal configuration, fully transparent coatings were obtained on 350 shells. Collisions in a fluidized bed have been identified as the limiting factor in meeting IFE specifications, and a related-rotary kiln technique is recommended for scale-up.

  13. Enthalpy and entropy barriers explain the effects of topology on the kinetics of zeolite-catalyzed reactions.

    PubMed

    Van der Mynsbrugge, Jeroen; De Ridder, Jeroen; Hemelsoet, Karen; Waroquier, Michel; Van Speybroeck, Veronique

    2013-08-26

    The methylation of ethene, propene, and trans-2-butene on zeolites H-ZSM-58 (DDR), H-ZSM-22 (TON), and H-ZSM-5 (MFI) is studied to elucidate the particular influence of topology on the kinetics of zeolite-catalyzed reactions. H-ZSM-58 and H-ZSM-22 are found to display overall lower methylation rates compared to H-ZSM-5 and also different trends in methylation rates with increasing alkene size. These variations may be rationalized based on a decomposition of the free-energy barriers into enthalpic and entropic contributions, which reveals that the lower methylation rates on H-ZSM-58 and H-ZSM-22 have virtually opposite reasons. On H-ZSM-58, the lower methylation rates are caused by higher enthalpy barriers, owing to inefficient stabilization of the reaction intermediates in the large cage-like pores. On the other hand, on H-ZSM-22, the methylation rates mostly suffer from higher entropy barriers, because excessive entropy losses are incurred inside the narrow-channel structure. These results show that the kinetics of crucial elementary steps hinge on the balance between proper stabilization of the reaction intermediates inside the zeolite pores and the resulting entropy losses. These fundamental insights into their inner workings are indispensable for ultimately selecting or designing better zeolite catalysts. PMID:23897717

  14. An extended baseline examination of indoor VOCs in a city of low ambient pollution: Perth, Western Australia

    NASA Astrophysics Data System (ADS)

    Maisey, S. J.; Saunders, S. M.; West, N.; Franklin, P. J.

    2013-12-01

    This study of indoor air quality reports VOC concentrations in 386 suburban homes located in Perth Western Australia, a city of low ambient pollution and temperate climate. Details of indoor VOC concentrations, temperature, relative humidity, and information on house characteristics and occupant activities were collected during the sampling periods. The concentration of VOCs observed in typical homes was low and individual compounds rarely exceeded 5 ?g m-3. Median individual VOC concentrations ranged from 0.06 ?g m-3 for 1,1,1 trichloroethane and butyl ether to 26.6 ?g m-3 for cis/trans 2-butene. Recently renovated homes had higher concentrations of VOCs than non renovated homes, including ?VOCs (p = 0.026), ?BTEX (p = 0.03), ?xylene (p = 0.013), toluene (p = 0.05), cyclohexane (p = 0.039), and propyl benzene (p = 0.039). Statistical analyses showed house age and attached garages were not significant factors for any of the VOCs tested. The concentrations of indoor VOCs in Perth were lower than overseas observations and those reported in recent Australian studies, with inferences made to differences in the climate and the occupant behaviour. The results are a baseline profile of indoor VOCs over the period 2006-2011, in an Australian city of low population density and of generally low ambient pollution.

  15. The use of design-of-experiments methodology to optimize polymer capsule fabrication. 1998 summer research program for high school juniors at the University of Rochester`s Laboratory for Laser Energetics: Student research reports

    SciTech Connect

    Lai, L.

    1999-03-01

    Future inertial-fusion experiments on Omega will utilize {approximately} 1 mm-diameter cryogenic targets that have a {approximately} 100-{micro}m-thick, uniformly-frozen fuel layer on their interior. It is desired that they have a stress-free wall thickness < 1 {micro}m and an rms surface roughness < 20 nm. A design-of-experiments (DOE) approach was used to characterize a glow-discharge-polymerization coater built at LLE to fabricate smooth, stress-free capsules with submicron wall thicknesses. The DOE approach was selected because several parameters can be changed simultaneously in a manner which allows the minimum number of runs to be performed to obtain statistically-relevant data. Planar, silicon substrates were coated with {approximately} 3--5 {micro}m of polymer and profilometry was used to determine the coating rate, the film stress, and the surface roughness. The coating rate was found to depend on the trans-2-butene/hydrogen ratio, the total gas-flow rate, the total chamber pressure, and the RF power. In addition, a two-parameter interaction between the total pressure and the RF power also affects the coating rate. The film stress depends on the total chamber pressure and the total mass-flow rate. The surface roughness is independent of the parameters studied. Preliminary results indicate that capsules can be produced rapidly without affecting the smoothness of their outside surface and without residual stress in their walls.

  16. A sputtering derived atomic oxygen source for studying fast atom reactions

    NASA Technical Reports Server (NTRS)

    Ferrieri, Richard A.; Yung, Y. Chu; Wolf, Alfred P.

    1987-01-01

    A technique for the generation of fast atomic oxygen was developed. These atoms are created by ion beam sputtering from metal oxide surfaces. Mass resolved ion beams at energies up to 60 KeV are produced for this purpose using a 150 cm isotope separator. Studies have shown that particles sputtered with 40 KeV Ar(+) on Ta2O5 were dominantly neutral and exclusively atomic. The atomic oxygen also resided exclusively in its 3P ground state. The translational energy distribution for these atoms peaked at ca 7 eV (the metal-oxygen bond energy). Additional measurements on V2O5 yielded a bimodal distribution with the lower energy peak at ca 5 eV coinciding reasonably well with the metal-oxygen bond energy. The 7 eV source was used to investigate fast oxygen atom reactions with the 2-butene stereoisomers. Relative excitation functions for H-abstraction and pi-bond reaction were measured with trans-2-butene. The abstraction channel, although of minor relative importance at thermal energy, becomes comparable to the addition channel at 0.9 eV and dominates the high-energy regime. Structural effects on the specific channels were also found to be important at high energy.

  17. Influence of process variables on the continuous alkylation of isobutane with 2-butene on superacid sulfated zirconia catalysts

    SciTech Connect

    Corma, A.; Martinez, A.; Martinez, C.

    1994-09-01

    Two sulfated zirconia catalysts have been prepared by impregnation of zirconium hydroxide with H{sub 2}SO{sub 4} 0.3 N and 1 N. Both samples showed superacid sites as shown by a desorption temperature peak in the NH{sub 3} TPD at ca. 813 K. The activity and selectivity of these catalysts have been studied for the alkylation of isobutane with trans-2 butene in a computer-controlled continuous fixed bed reactor coupled with a sampling system which allows to make differential analysis of the products from very short reaction times. In this way, the influence of the main process variables, i.e, time on stream, reaction temperature, olefin WHSV, and isoparaffin/olefin ratio, on the 2-butene conversation and product distribution has been investigated. Cracking of larger carbocations and alkylation of isobutane with 2-butene to give trimethylpentanes were the predominant reactions occurring on the superacid catalyst in the initial stages of the reaction. The alkylation/cracking ratio increased when decreasing reaction temperature. A fast catalyst decay with time on stream was also observed, and this was accompanied by an increase in the oligomerization of butene. 23 refs., 5 figs., 4 tabs.

  18. Isobutane/2-butene alkylation on ultrastable Y zeolites: Influence of zeolite unit cell size

    SciTech Connect

    Corma, A.; Martinez, A.; Martinez, C. )

    1994-03-01

    The alkylation reaction of isobutane with trans-2-butene has been carried out on a series of steam-dealuminated Y zeolites with unit cell sizes ranging from 2.450 to 2.426 nm. A fixed-bed reactor connected to an automatized multiloop sampling system allowed differential product analysis from very short (1 min or less) to longer times on stream. A maximum in the initial 2-butene conversion was found on samples with unit cell sizes between 2.435 and 2.450 nm. However, the TMP/DMH ratio, i.e., the alkylation-to-oligomerization ratio, continuously increased with zeolite unit cell size. The concentration of reactants in the pores, the strength distribution of Bronsted acid sites, and the extent of hydrogen transfer reactions, which in turn depend on the framework Si/Al ratio of a given zeolite, were seen to affect activity and product distribution of the catalysts. Finally, the influence of these factors on the aging characteristics of the samples was also discussed. 17 refs., 7 figs., 4 tabs.

  19. Synthesis and biological activity of new conformationally restricted analogues of pepstatin.

    PubMed

    Szewczuk, Z; Rebholz, K L; Rich, D H

    1992-01-01

    A new statine derivative, 3-hydroxy-4-amino-5-mercaptopentanoic acid; cysteinylstatine (CySta), was synthesized and used to prepare a series of conformationally restricted analogues of pepstatin (Iva-Val-Val-Sta-Ala-Sta) in which the conformational constraint was introduced via a bis-sulfide connecting the appropriately substituted residues in the P1 and the P3 inhibitor side chains. The precursor peptide, Iva-Cys-Val-CySta-Ala-Iaa, was synthesized and alkylated with a series of dibromoalkanes and alkenes to produce the cyclic structures. This strategy permitted the carbon atom spacing between the P1 and the P3 inhibitor side chains to be systematically varied so as to produce inhibitors with 15-, 16-, and 17-membered ring systems. Additional non-cyclic analogues were synthesized as controls by alkylating the bisthiol intermediates with methyl iodide. The inhibitory potency of the analogues were determined against porcine pepsin and penicillopepsin by using standard enzyme kinetic assays. The cyclic inhibitor were found to be potent inhibitors of both aspartic proteases; inhibitor that contained a trans-2-butene link between the two sulfur atoms was found to be the most potent inhibitor with a Ki less than 1 nM against pepsin and 3.94 nM against penicillopepsin. This series of compounds illustrates a new type of conformational restriction that can be used to probe for the bioactive conformation of peptides. PMID:1478780

  20. Effects of rf power on chemical composition and surface roughness of glow discharge polymer films

    NASA Astrophysics Data System (ADS)

    Zhang, Ling; He, Xiaoshan; Chen, Guo; Wang, Tao; Tang, Yongjian; He, Zhibing

    2016-03-01

    The glow discharge polymer (GDP) films for laser fusion targets were successfully fabricated by plasma enhanced chemical vapor deposition (PECVD) at different radio frequency (rf) powers. The films were deposited using trans-2-butene (T2B) mixed with hydrogen as gas sources. The composition and state of plasma were diagnosed by quadrupole mass spectrometer (QMS) and Langmuir probe during the deposition process. The composition, surface morphology and roughness were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and white-light interferometer (WLI), respectively. Based on these observation and analyses, the growth mechanism of defects in GDP films were studied. The results show that, at low rf power, there is a larger probability for secondary polymerization and formation of multi-carbon C-H species in the plasma. In this case, the surface of GDP film turns to be cauliflower-like. With the increase of rf power, the degree of ionization is high, the relative concentration of smaller-mass hydrocarbon species increases, while the relative concentration of larger-mass hydrocarbon species decreases. At higher rf power, the energy of smaller-mass species are high and the etching effects are strong correspondingly. The GDP film's surface roughness shows a trend of decrease firstly and then increase with the increasing rf power. At rf power of 30 W, the surface root-mean-square roughness (Rq) drops to the lowest value of 12.8 nm, and no "void" defect was observed.

  1. Reactions of hydroxyl radicals with alkenes in low-temperature matrices

    NASA Astrophysics Data System (ADS)

    Feltham, Emma J.; Almond, Matthew J.; Marston, George; Wiltshire, Karen S.; Goldberg, Nicola

    2000-11-01

    The reactions of hydroxyl radicals with a number of stable alkenes have been studied in low-temperature matrices. The reactions were initiated by broad band UV-visible irradiation of matrices containing H 2O 2 and the alkene under investigation. The hydroxyalkyl radical products were identified principally by comparison of their spectra with the spectra of corresponding stable alcohols. Accordingly, IR spectra were recorded for the following series of alcohols isolated in argon matrices methanol, ethanol, ethanol- d6, propan-1-ol, propan-2-ol, butan-2-ol, 2-methylpropan-1-ol ( iso-butyl alcohol), 2-methylpropan-2-ol ( tert-butyl alcohol), 2-methylbutan-2-ol ( tert-amyl alcohol), 3-methylbutan-2-ol and 2,3-dimethylbutan-2-ol. The hydroxyalkyl radicals, which appear to be formed from the alkenes studied were as follows from ethene, 2-hydroxyethyl radical; from cis- or trans-but-2-ene, 1-methyl-2-hydroxypropyl radical; from propene, 1-methyl-2-hydroxyethyl and 2-hydroxypropyl radicals; from but-1-ene, 1-hydroxymethylpropyl and 2-hydroxybutyl radicals; from 2-methylpropene ( iso-butene), 1,1-dimethyl-2-hydroxyethyl and 2-methyl-2-hydroxypropyl radicals; the radical products from buta-1,3-diene and isoprene could not be identified. In the cases, where two radical products were possible, i.e. when propene, but-1-ene or 2-methylpropene were the substrates, it was found that the concentration of the secondary or tertiary radical always exceeded that of the primary radical. However, the relative concentration of these radicals appears to be determined by subsequent photolysis to give carbonyl compounds. There seems, therefore, to be little preference for the secondary and tertiary radicals over the primary radicals in the primary addition process. Comments on the mechanism of the transformation from radical to carbonyl compound based upon identification of intermediates within the matrix and isotopic substitution experiments are made. The characterisation of the 2-hydroxyethyl radical has been backed up by experiments utilising isotopic substitution with 13C and D ( 2H). The other radicals have been identified with varying degrees of certainty. Those radicals, which are observed at the highest concentration and which are, therefore, characterised more certainly are 2-hydroxyethyl ( 1), from ethene; 1-methyl-2-hydroxypropyl ( 2), from cis- and trans-but-2-ene; 1-methyl-2-hydroxyethyl ( 3), from propene; 1-hydroxymethylpropyl ( 5), from but-1-ene; and 1,1- dimethyl-2-hydroxyethyl ( 8), from 2-methylpropene.

  2. Hydrogenolysis and homologation of linear and branched pentenes on Ru/SiO/sub 2/ catalysts: implication in the mechanism of C-C bond formation and cleavage on metal surfaces

    SciTech Connect

    Rodriguez, E.; Leconte, M.; Basset, J.M.; Tanaka, K.; Tanaka, K.I.

    1988-01-06

    Hydrogenolysis and homologation of 1-pentene to butenes and hexenes take place simultaneously and at the same rate over a Ru/SiO/sub 2/ catalysts at 110/sup 0/C, suggesting that these two reactions are mechanistically related. /sup 13/C labeling experiments indicate that C-C cleavage occurs at the double bond of 1-pentene-1-/sup 13/C leading to unlabeled 1-butene and labeled hexenes. The product distribution in the hydrogenolysis of 1-pentene, 2-pentenes, 3-methyl-1-butene, 2-methyl-2-butene, and 2-methyl-1-butene is accounted for by a carbene-olefin mechanism, which can therefore be considered as a reasonable common path for the formation and cleavage of carbon-carbon bonds on metal surfaces.

  3. Synthesis of the E and Z isomers of the antiestrogen tamoxifen and its metabolite, hydroxytamoxifen, in tritium-labeled form

    SciTech Connect

    Robertson, D.W.; Katzenellenbogen, J.A.

    1982-06-04

    Both isomers of the potent antiestrogen tamoxifen (1,2-diphenyl-1-(4-(2-(dimethylamino)ethoxy)phenyl)-1-butene: E isomer = ICI-47699; Z isomer = ICI-46474, Nolvadex) and its metabolite, hydroxytamoxifen (1-(4-(2-(dimethylamino)ethoxy)phenyl)-1-(4-hydroxyphenyl)-2-phenyl-1-butene), have been synthesized in a high specific activity, tritium-labeled form by catalytic tritium-halogen exchange performed on brominated precursors. The synthesis of another precursor to labeled tamoxifen which would enable the incorporation of three tritium atoms into the molecule by tritium-halogen exchange is reported.

  4. Hydrogenation of lower alkenes and conjugated diene catalyzed by Ga2O3

    NASA Astrophysics Data System (ADS)

    Shishido, Tetsuya; Kuno, Hirotaka; Teramura, Kentaro; Tanaka, Tsunehiro

    2012-06-01

    Hydrogenation of lower alkenes such as ethylene, propylene, and 1-butene proceeded over gallium oxide (Ga2O3). The rate of the hydrogenation was faster in the order of ethylene ? propylene > 1-butene over Ga2O3. Ga2O3 also showed the activity for hydrogenation of 1,3-butadiene where 1,4-addition of hydrogen to 1,3-butadiene mainly took place to give 2-butenes as main products. The formation rate of hydrogenated products depended on the amounts of H2 and alkenes adsorbed on Ga2O3. This implies that the hydrogenation proceeds on the basis of the Langmuir-Hinshelwood mechanism.

  5. Roughness Optimization at High Modes for GDP CHx Microshells

    SciTech Connect

    Theobald, M.; Dumay, B.; Chicanne, C.; Barnouin, J.; Legaie, O.; Baclet, P.

    2004-03-15

    For the ''Megajoule'' Laser (LMJ) facility of the CEA, amorphous hydrogenated carbon (a-C:H) is the nominal ablator to be used for inertial confinement fusion (ICF) experiments. These capsules contain the fusible deuterium-tritium mixture to achieve ignition. Coatings are prepared by glow discharge polymerization (GDP) with trans-2-butene and hydrogen. The films properties have been investigated. Laser fusion targets must have optimized characteristics: a diameter of about 2.4 mm for LMJ targets, a thickness up to 175 {mu}m, a sphericity and a thickness concentricity better than 99% and an outer and an inner roughness lower than 20 nm at high modes. The surface finish of these laser fusion targets must be extremely smooth to minimize hydrodynamic instabilities.Movchan and Demchishin, and later Thornton introduced a structure zone model (SZM) based on both evaporated and sputtered metals. They investigated the influence of base temperature and the sputtering gas pressure on structure and properties of thick polycrystalline coatings of nickel, titanium, tungsten, aluminum oxide. An original cross-sectional analysis by atomic force microscopy (AFM) allows amorphous materials characterization and permits to make an analogy between the amorphous GDP material and the existing model (SZM). The purpose of this work is to understand the relationship between the deposition parameters, the growing structures and the surface roughness.The coating structure as a function of deposition parameters was first studied on plane silicon substrates and then optimized on PAMS shells. By adjusting the coating parameters, the structures are modified, and in some case, the high modes roughness decreases dramatically.

  6. Sources of Volatile Organic Compounds (VOCs) in the UAE

    NASA Astrophysics Data System (ADS)

    Abbasi, Naveed; Majeed, Tariq; Iqbal, Mazhar; Riemer, Daniel; Apel, Eric; Lootah, Nadia

    The gas chromatography-flame ionization detection/mass spectrometry system has been used to identify major volatile organic compounds (VOCs) sources in the UAE (latitude 24.45N; longitude 54.22E). VOCs are emitted from an extensive number of sources in urban environments including fuel production, distribution, and consumption. Transport sources contribute a substantial portion of the VOC burden to the urban atmosphere in developed regions. UAE is located at the edge of the Persian Gulf and is highly affected by emissions from petrochemical industries in neighbouring Saudi Arabia, Qatar, and Iran. VOCs emerging from these industries can be transported to the UAE with jet streams. The analysis of the collected air samples at three locations in Sharjah, UAE during the autumn and winter seasons indicates the presence of more than 100 VOC species. The concentrations of these species vary in magnitudes but the most prominent are: acetylene, ethane, propane, butane, pentane, benzene, and toluene. The possible tracers for various emission sources have also been identified such as 2-methylpentane, 1, 3-butadiene and 2, 2-dimethlybutane for vehicle exhaust, the light hydrocarbons, namely n-butane, trans-2-butene, and n-pentane for gasoline vapor, and n-nonane, n-decane, and n-undecane for diesel vapor and asphalt application processes. As various emission sources are characterized by overlapping VOC species, the ratio of possible VOC tracers are used to quantify the contribution of different sources. Our aim in this paper is to explore and discuss possible impacts of transported emissions on the local VOC emission inventory from various sources for the UAE. This work is partially supported by Office of Development and Alumni Affairs at the American University of Sharjah, U.A.E.

  7. Transfer hydrogenation of alkenes using Ni/Ru/Pt/Au heteroquatermetallic nanoparticle catalysts: sequential cooperation of multiple nano-metal species.

    PubMed

    Ito, Yoshikazu; Ohta, Hidetoshi; Yamada, Yoichi M A; Enoki, Toshiaki; Uozumi, Yasuhiro

    2014-10-18

    Quatermetallic alloy nanoparticles of Ni/Ru/Pt/Au were prepared and found to promote the catalytic transfer hydrogenation of non-activated alkenes bearing conjugating units (e.g., 4-phenyl-1-butene) with 2-propanol, where the composition metals, Ni, Ru, Pt, and Au, act cooperatively to provide significant catalytic ability. PMID:25177750

  8. 77 FR 3750 - Notice of Intent To Grant a Partially Exclusive License; Cobalt Technologies, Inc.

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-01-25

    ....//patent application 12/511796: Diesel and Jet Fuels Based on the Oligomerization of 1-Butene, filed on July 29, 2009.// patent application 12/769757: Turbine and Diesel Fuels and Methods of Making the Same... Olefin Feedstocks for the Production of Turbine and Diesel Fuels, filed on April 27,...

  9. Determination of Tamoxifen and its Major Metabolites in Exposed Fish

    EPA Science Inventory

    Tamoxifen (TAM), (Z)-1-(p-dimethylaminoethoxyphenyl)-1, 2-diphenyl-1-butene, is a nonsteroidal agent that has been used in breast cancer treatment for decades. Its major metabolites are 4-hydroxytamoxifen (4-OHT), N-desmethyltamoxifen (DMT), and endoxifen. While TAM and metabolit...

  10. Systematic preparation of selective heterogeneous catalysts

    SciTech Connect

    Augustine, R.L.

    1991-11-07

    The Single Turnover (STO) procedure, involving pulses of hydrogen and 1-butene, was developed for studying the types of active sites present on supported metal catalysts. The STO procedure was used to study direct saturated sites and other topics. Frontier molecular orbital studies were also made.

  11. Systematic preparation of selective heterogeneous catalysts. Final report, September 1, 1984--August 31, 1991

    SciTech Connect

    Augustine, R.L.

    1991-11-07

    The Single Turnover (STO) procedure, involving pulses of hydrogen and 1-butene, was developed for studying the types of active sites present on supported metal catalysts. The STO procedure was used to study direct saturated sites and other topics. Frontier molecular orbital studies were also made.

  12. Non-methane hydrocarbons (NMHCs) and their contribution to ozone formation potential in a petrochemical industrialized city, Northwest China

    NASA Astrophysics Data System (ADS)

    Jia, Chenhui; Mao, Xiaoxuan; Huang, Tao; Liang, Xiaoxue; Wang, Yanan; Shen, Yanjie; Jiang, Wanyanhan; Wang, Huiqin; Bai, Zhilin; Ma, Minquan; Yu, Zhousuo; Ma, Jianmin; Gao, Hong

    2016-03-01

    Hourly air concentrations of fifty-three non-methane hydrocarbons (NMHCs) were measured at downtown and suburb of Lanzhou, a petrochemical industrialized city, Northwest China in 2013. The measured data were used to investigate the seasonal characteristics of NMHCs air pollution and their contributions to the ozone formation in Lanzhou. Annually averaged NMHCs concentration was 38.29 ppbv in downtown Lanzhou. Among 53 NMHCs, alkanes, alkenes, and aromatics accounted for 57%, 23% and 20% of the total NMHCs air concentration, respectively. The atmospheric levels of toluene and propane with mean values of 4.62 and 4.56 ppbv were higher than other NMHCs, respectively. The ambient levels of NMHCs in downtown Lanzhou were compared with measured NMHCs data collected at a suburban site of Lanzhou, located near a large-scale petrochemical industry. Results show that the levels of alkanes, alkenes, and aromatics in downtown Lanzhou were lower by factors of 3-11 than that in west suburb of the city. O3-isopleth plots show that ozone was formed in VOCs control area in downtown Lanzhou and NOx control area at the west suburban site during the summertime. Propylene-equivalent (Prop-Equiv) concentration and the maximum incremental reactivity (MIR) in downtown Lanzhou indicate that cis-2-butene, propylene, and m/p-xylene were the first three compounds contributing to ozone formation potentials whereas in the petrochemical industrialized west suburb, ethane, propene, and trans-2-Butene played more important role in the summertime ozone formation. Principal component analysis (PCA) and multiple linear regression (MLR) were further applied to identify the dominant emission sources and examine their fractions in total NMHCs. Results suggest that vehicle emission, solvent usage, and industrial activities were major sources of NMHCs in the city, accounting for 58.34%, 22.19%, and 19.47% of the total monitored NMHCs in downtown Lanzhou, respectively. In the west suburb of the city, however, vehicle emission was less important as compared with sources from petrochemical industries, as characterized by relatively higher ethane (C2H4)/ ethyne (acetylene) and propene (C3H6)/ethyne ratios which ruled out tailpipes emission as major contributors to the VOCs sources.

  13. Study on Sources of Volatile Organic Compounds (CMB) in Pearl River Delta region, China

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Shao, M.; Lu, S.; Chang, C.; Wang, C. J.; Wang, B.

    2007-05-01

    The profiles of major Volatile organic compounds (VOCs) sources including vehicle exhaust, gasoline vapor, painting, asphalt, liquefied petroleum gas (LPG), biomass burning and petrochemical industry in Pearl River Delta were experimentally determined. Source samples were taken by using dilution chamber for mobile and stationary sources, laboratory simulation for biomass burning. The concentrations of 108 VOC species of sources were quantified by using canister with pre-concentration-GC/MS system, from which 52 PAMS hydrocarbons and one kind of chlorinated hydrocarbon were deployed to build the source profiles for source apportionment of VOCs. Based the measurement of source profiles, the possible tracers for various emission sources were identified, e.g 2-methylbutane and 1,3-butadiene were the tracers for motor vehicle exhaust, the characteristic compounds of architectural and furnishing coatings are aromatics such as toluene and m/p-xylene; the light hydrocarbons, namely n-butane, trans-2-butene and n-pentane, dominated the composition of gasoline vapor; and the nonane, decane and undecane are found to represent the asphalt emissions etc.. The CMB receptor model was applied to source apportionment of 58 hydrocarbons measured at seven sites during the PRD campaign, 2004. The 12 kinds of VOC sources include gasoline/diesel-powered vehicle exhaust, gasoline/diesel headspace vapor, vehicle evaporative emissions, liquid petroleum gas (LPG) leakage, painting vapors, asphalt emission from paved road, biomass burning, coal burning, chemical industry and petroleum refinery. Vehicle exhaust was the largest sources contributing over half of the ambient VOCs at the three urban sites (GuangZhou, FoShan and ZhongShan). LPG leakage played an important role with the percentage of 8- 16% in most sites in PRD. Contributions from solvents usage were highest at DongGuan, an industrial site. At XinKen, the solvents and coatings had the largest percentage of 31% probably due to the influence of its upwind area of DongGuan. The local biomass burning was also found to be a noticeable source at XK.

  14. The effect of cavitating ultrasound on the aqueous phase hydrogenation of cis-2-buten-1-ol and cis-2-penten-1-ol on Pd-black

    SciTech Connect

    Disselkamp, Robert S.; Denslow, Kayte M.; Hart, Todd R.; White, James F.; Peden, Charles HF.

    2005-07-15

    We have studied the effect of cavitating ultrasound on the heterogeneous aqueous hydrogenation of cis-2-buten-1-ol (C4 olefin) and cis-2-penten-1-ol (C5 olefin) on Pd-black to form the trans-olefins (trans-2-buten-1-ol and trans-2-penten-1-ol) and saturated alcohols (1-butanol and 1-pentanol, respectively). Silent (and magnetically stirred) experiments served as control experiments. As described in an earlier publication by our group, we have added an inert dopant, 1-propanol, in the reaction mixture to ensure the rapid onset of cavitation in the ultrasound-assisted reactions that can lead to altered selectivity compared to silent reaction systems [R.S. Disselkamp, Ya-Huei Chin, C.H.F. Peden, J. Catal. 227 (2004) 552]. The motivation for this study is to examine whether cavitating ultrasound can reduce the [trans-olefin/saturated alcohol] molar ratio during the course of the reaction. This could have practical application in that it may offer an alternative processing methodology of synthesizing healthier edible seed oils by reducing trans-fat content.We have observed that cavitating ultrasound results in a [(trans-olefin/saturated alcohol)ultrasound/(trans-olefin/saturated alcohol)silent] ratio quantity less than 0.5 at the reaction mid-point for both the C4 and C5 olefin systems. This indicates that ultrasound reduces trans-olefin production compared to the silent control experiment. Furthermore, there is an added 30% reduction for the C5 versus C4 olefin compounds again at reaction mid-point. We attribute differences in the ratio quantity as a moment of inertia effect. In principle, the C4 versus C5 olefins has a {approx}52% increase in moment of inertia about C2 C3 double bond slowing isomerization. Since seed oils are C18 multiple cis-olefins and have a moment of inertia even greater than our C5 olefin here, our study suggests that even a greater reduction in trans-olefin content may occur for partial hydrogenation of C18 seed oils.

  15. The Effect of Cavitating Ultrasound on the Aqueous Phase Hydrogenation of Cis-2-buten-1-ol and Cis-2-penten-1-ol on Pd-black

    SciTech Connect

    Disselkamp, Robert S.; Denslow, Kayte M.; Hart, Todd R.; White, James F.; Peden, Charles HF.

    2005-07-15

    We have studied the effect of cavitating ultrasound on the heterogeneous aqueous hydrogenation of cis-2-buten-1-ol (C4 olefin) and cis-2-penten-1-ol (C5 olefin) on Pd-black to form the trans-olefins (trans-2-buten-1-ol and trans-2-penten-1-ol) and saturated alcohols (1-butanol and 1-pentanol, respectively). Silent (and magnetically stirred) experiments served as control experiments. As described in an earlier publication by our group, we have added an inert dopant, 1-propanol, in the reaction mixture to ensure the rapid onset of cavitation in the ultrasound-assisted reactions that can lead to altered selectivity compared to silent reaction systems [Disselkamp et al., J. Catal., 227 (2004) 552]. The motivation for this study is to examine whether cavitating ultrasound can reduce the [trans-olefin/saturated alcohol] molar ratio during the course of the reaction. This could have practical application in that it may offer an alternative processing methodology of synthesizing healthier edible seed oils by reducing trans-fat content. We have observed that cavitating ultrasound results in a [(trans-olefin/saturated alcohol)ultrasound/(trans-olefin/saturated alcohol)silent] ratio quantity less than 0.5 at the reaction mid-point for both the C4 and C5 olefin systems. This indicates that ultrasound reduces trans-olefin production compared to the silent control experiment. Furthermore, there is an added 30% reduction for the C5 versus C4 olefin compounds again at reaction mid-point. We attribute differences in the ratio quantity as a moment of inertia effect. In principle, the C4 versus C5 olefins has a {approx}52% increase in moment of inertia about C2=C3 double bond slowing isomerization. Since seed oils are C18 multiple cis olefins and have an moment of inertia even greater than our C5 olefin here, our study suggests that even a greater reduction in trans-olefin content may occur for partial hydrogenation of C18 seed oils.

  16. Theoretical kinetics studies of two model reactions in biodiesel and diesel combustion

    NASA Astrophysics Data System (ADS)

    Sha, Yuan

    We use 1-methylallyl radical (CH3CH=CH-CH2 ? CH3CH-CH=CH2) as a model of allylic radicals generated during combustion of unsaturated diesel fuel molecules. The chemically activated isomerization of 1-methylallyl generated in the highly exothermic (35 kcal/mol) OH + trans-2-butene reaction was considered by using RRKM/Master Equation calculations from 0.01 to 100 atm and from 300 to 700 K. Density functional theory (DFT) with the M05-2X, M06-2X and B3LYP functionals are used for structures, energies, vibrational frequencies, anharmonic constants, and the torsional potentials of methyl rotations. The cis:trans ratio formed upon quenching the radicals were, as might be expected, dependent on the functional, but, were even more sensitive when an vibrations were treated as anharmonic. The fraction of cis- 1-methylallyl is significant, if not dominant at 300 -700 K and 0.01 -10 atm. Sensitivity studies were carried out to determine the dependence of the cis:trans ratio on the extent of chemical activation, treatment of the K-rotor as active or inactive, and the rate of collisional energy transfer. All these parameters significantly influence the cis:trans ratio. The 1,5 H-migration reaction of 3-hydroperoxy-1-propylperoxy radical (HOOCH2CH2CH2OO) is a important as a model of a critical propagation step in diesel autoignition from alkanes or molecules with long alkyl tails. Its product may be the meta-stable alpha,gamma-dihydroperoxypropyl radical or, if unstable, OH + 3-hydroperoxypropanal. To study the possibly different tunneling effects of the two possible products, the quantum mechanical rate constants, including tunneling, are directly determined using semi-classical transition state theory (SCTST) at 200 K to 1700 K. Small-curvature tunneling (SCT) is to compute tunneling corrections to classical rate constants. The two reactions do not have obvious tunneling differences at above 700 K. Below 700 K, SCTST tunneling corrections are significantly higher than SCT corrections, for reasons which are poorly understood. The anharmonic, tunneling, and variational corrections to the TST rate constant are combined together as a total correction for transition state theory rate constants, resulting in rate constants 10 times larger at 500-1700 K than that by standard transition state theory with harmonic treatment of vibrations. The pressure-dependent rate constant are calculated using RRKM/Master Equation methods.

  17. HIRAC - A Highly Instrumented Reactor for Atmospheric Chemistry

    NASA Astrophysics Data System (ADS)

    Hemavibool, K.; Malkin, T. L.; Glowacki, D. R.; Goddard, A.; Heard, D. E.; Seakins, P. W.; Pilling, M. J.

    2008-12-01

    Environmental chambers are an important part of an integrated and multifaceted approach to understanding chemical processes in the atmosphere, by bridging the gap between laboratory measurements of individual elementary reactions and the complexity of the real atmosphere. The University of Leeds HIRAC chamber is a 2 m3 stainless steel vessel capable of operating at a variety of temperatures and pressures, enabling wide ranging kinetics experiments. Photolysis reactions are initiated by 8 rows of internal lights positioned to maximise the volume of the cell (> 85 % ) receiving a uniform ( 10 % ) light intensity. HIRAC's includes a suite of analytical devices comprising of: a long path FTIR system (operating from the UV to the far IR), GC-HID and GC-FID for HCHO and hydrocarbons detection respectively, commercial NOx/O3/H2O vapour and CO analysers, and laser-induced fluorescence at low pressure (FAGE) detection system for OH and HO2 measurement (detection limit of ~106 molecule cm- 3). HIRAC aims to validate mechanisms of hydrocarbon oxidation relevant for models such as the Master Chemical Mechanism (MCM), to measure the kinetics of reactions which cannot be studied by isolated techniques such as laser flash photolysis or discharge flow, and to provide a test bed for the development and calibration of field instrumentation. This poster intends to give an insight in to the characterisation of HIRAC and initial results. Relative rate measurements have been used to measure the kinetics of OH radical and Cl atom reactions with a variety of VOCs, using GC and FTIR detection. Relative rate measurements avoid the effects of secondary reactions and the need for direct measurement of highly reactive radicals. Measurements have been made with very high precision, generating high quality fall-off curves for the pressure dependent ethene and Cl atom reactions. The reaction between O3 and trans-2-butene has been studied by the detection of reagents and product acetaldehyde, as well as OH and HO2 concentrations, with excellent precision. A model based on the MCM was able to calculate the temporal profiles extremely well.

  18. Borenium Ion Catalyzed Hydroboration of Alkenes with N-Heterocyclic Carbene Boranes

    PubMed Central

    Prokofjevs, Aleksandrs; Boussonnire, Anne; Li, Linfeng; Bonin, Hlne; Lacte, Emmanuel; Curran, Dennis P.; Vedejs, Edwin

    2012-01-01

    Treatment of alkenes such as 3-hexene, 3-octene, and 1-cyclohexyl-1-butene with the N-heterocyclic carbene-derived borane 2 and catalytic HNTf2 effects hydroboration at room temperature. With 3-hexene, surprisingly facile migration of the boron atom from C3 of the hexyl group to C2 was observed over a time scale of minutes to hours. Oxidative workup gave a mixture of alcohols containing 2-hexanol as the major product. A similar preference for the C(2) alcohol was observed after oxidative workup of the 3-octene, and 1-cyclohexyl-1-butene hydroborations. NHC-borenium cations (or functional equivalents) are postulated as the species that accomplish the hydroborations, and the C(2) selective migrations are attributed to the 4-center inter-conversion of borenium cations with cationic NHC-borane olefin ?-complexes. PMID:22713106

  19. Borenium ion catalyzed hydroboration of alkenes with N-heterocyclic carbene-boranes.

    PubMed

    Prokofjevs, Aleksandrs; Boussonnire, Anne; Li, Linfeng; Bonin, Hlne; Lacte, Emmanuel; Curran, Dennis P; Vedejs, Edwin

    2012-07-25

    Treatment of alkenes such as 3-hexene, 3-octene, and 1-cyclohexyl-1-butene with the N-heterocyclic carbene (NHC)-derived borane 2 and catalytic HNTf(2) (Tf = trifluoromethanesulfonyl (CF(3)SO(2))) effects hydroboration at room temperature. With 3-hexene, surprisingly facile migration of the boron atom from C(3) of the hexyl group to C(2) was observed over a time scale of minutes to hours. Oxidative workup gave a mixture of alcohols containing 2-hexanol as the major product. A similar preference for the C(2) alcohol was observed after oxidative workup of the 3-octene and 1-cyclohexyl-1-butene hydroborations. NHC-borenium cations (or functional equivalents) are postulated as the species that accomplish the hydroborations, and the C(2) selective migrations are attributed to the four-center interconversion of borenium cations with cationic NHC-borane-olefin ?-complexes. PMID:22713106

  20. Synthesis of amphiphilic diblock copolymer for surface modification of Ethylene-Norbornene Copolymers

    NASA Astrophysics Data System (ADS)

    Levinsen, Simon; Svendsen, Winnie Edith; Horsewell, Andy; Almdal, Kristoffer

    2014-03-01

    The aim of this work is to produce polymer modifiers in order to develop hydrophilic polymeric surfaces for use in microfluidics. The use of hydrophilic polymers in microfluidics will have many advantages e.g. preventing protein absorbance. Here we present an amphiphilic diblock copolymer consisting of a bulk material compatible block and a hydrophilic block. To utilize the possibility of incorporating diblock copolymers into ethylene-norbornene copolymers, we have in this work developed a model poly(ethylene-1-butene) polymer compatible with the commercial available ethylene-norbornene copolymer TOPAS. Through matching of the radius of gyration for the model polymer and TOPAS the miscibility was achieved. The poly(ethylene-1-butene) polymer was synthesized from a hydrogenated anionic polymerized polybutadiene polymer. As hydrophilic block poly(ethylene oxide) was subsequently added also with anionic polymerization. Recent miscibility results between the model polymer and TOPAS will be presented, as well ongoing efforts to study the hydrophilic surface.

  1. The Thermodynamic Conjugation Stabilization of 1,3-Butadiyne Is Zero

    ERIC Educational Resources Information Center

    Rogers, Donald W.; Zavitsas, Andreas A.; Matsunaga, Nikita

    2010-01-01

    Many textbooks point out that the thermodynamic stabilization enthalpy of 1 mol of 1,3-butadiene relative to 2 mol of 1-butene or to 1 mol of 1,4-pentadiene is slightly less than 4 kcal mol[superscript -1], owing to conjugation between the double bonds in the 1,3 configuration. It is reasonable to suppose that the analogous thermochemical

  2. Kinetic measurements on elementary fossil fuel combustion reactions over wide temperature ranges

    SciTech Connect

    Fontijn, A.

    1991-01-01

    The goals of this work are to provide accurate data on the temperature dependence of the kinetics of elementary combustion reactions (i) for use by combustion modelers, and (ii) to gain a better fundamental understanding of, and hence predictive ability for, the chemistry involved. In this reporting period our work on the O + Hcl reaction was published, experimental work on the O + benzene and O + 1-butene reactions was completed, and measurements on the O + isobutene reaction were initiated.

  3. The Thermodynamic Conjugation Stabilization of 1,3-Butadiyne Is Zero

    ERIC Educational Resources Information Center

    Rogers, Donald W.; Zavitsas, Andreas A.; Matsunaga, Nikita

    2010-01-01

    Many textbooks point out that the thermodynamic stabilization enthalpy of 1 mol of 1,3-butadiene relative to 2 mol of 1-butene or to 1 mol of 1,4-pentadiene is slightly less than 4 kcal mol[superscript -1], owing to conjugation between the double bonds in the 1,3 configuration. It is reasonable to suppose that the analogous thermochemical…

  4. Replacing precious metals with carbide catalysts for hydrogenation reactions

    SciTech Connect

    Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; Wang, Tiefeng

    2015-03-03

    Molybdenum carbide (Mo?C and Ni/Mo?C) catalysts were compared with Pd/SiO? for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO?, Mo?C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo?C could be completely regenerated by H? treatment at 723 K for the three molecules. The Ni modified Mo?C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Ni modified Mo?C catalysts, 8.6%Ni/Mo?C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO?. Compared to Pd/SiO?, both Mo?C and Ni/Mo?C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.

  5. A Glutathione S-Transferase with Activity towards cis-1,2-Dichloroepoxyethane Is Involved in Isoprene Utilization by Rhodococcus sp. Strain AD45

    PubMed Central

    van Hylckama Vlieg, Johan E. T.; Kingma, Jaap; van den Wijngaard, Arjan J.; Janssen, Dick B.

    1998-01-01

    Rhodococcus sp. strain AD45 was isolated from an enrichment culture on isoprene (2-methyl-1,3-butadiene). Isoprene-grown cells of strain AD45 oxidized isoprene to 3,4-epoxy-3-methyl-1-butene, cis-1,2-dichloroethene to cis-1,2-dichloroepoxyethane, and trans-1,2-dichloroethene to trans-1,2-dichloroepoxyethane. Isoprene-grown cells also degraded cis-1,2-dichloroepoxyethane and trans-1,2-dichloroepoxyethane. All organic chlorine was liberated as chloride during degradation of cis-1,2-dichloroepoxyethane. A glutathione (GSH)-dependent activity towards 3,4-epoxy-3-methyl-1-butene, epoxypropane, cis-1,2-dichloroepoxyethane, and trans-1,2-dichloroepoxyethane was detected in cell extracts of cultures grown on isoprene and 3,4-epoxy-3-methyl-1-butene. The epoxide-degrading activity of strain AD45 was irreversibly lost upon incubation of cells with 1,2-epoxyhexane. A conjugate of GSH and 1,2-epoxyhexane was detected in cell extracts of cells exposed to 1,2-epoxyhexane, indicating that GSH is the physiological cofactor of the epoxide-transforming activity. The results indicate that a GSH S-transferase is involved in the metabolism of isoprene and that the enzyme can detoxify reactive epoxides produced by monooxygenation of chlorinated ethenes. PMID:9687433

  6. Replacing precious metals with carbide catalysts for hydrogenation reactions

    DOE PAGESBeta

    Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; Wang, Tiefeng

    2015-03-03

    Molybdenum carbide (Mo₂C and Ni/Mo₂C) catalysts were compared with Pd/SiO₂ for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO₂, Mo₂C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo₂C could be completely regenerated by H₂ treatment at 723 K for the three molecules. The Ni modified Mo₂C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Nimore » modified Mo₂C catalysts, 8.6%Ni/Mo₂C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO₂. Compared to Pd/SiO₂, both Mo₂C and Ni/Mo₂C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.« less

  7. Replacing precious metals with carbide catalysts for hydrogenation reactions

    SciTech Connect

    Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; Wang, Tiefeng

    2015-03-03

    Molybdenum carbide (Mo₂C and Ni/Mo₂C) catalysts were compared with Pd/SiO₂ for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO₂, Mo₂C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo₂C could be completely regenerated by H₂ treatment at 723 K for the three molecules. The Ni modified Mo₂C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Ni modified Mo₂C catalysts, 8.6%Ni/Mo₂C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO₂. Compared to Pd/SiO₂, both Mo₂C and Ni/Mo₂C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.

  8. Measurements of nonmethane hydrocarbons in Phoenix, Arizona

    SciTech Connect

    Doskey, P. V.; Kotamarthi, V. R.; Rudolph, J.

    1999-10-12

    Nonmethane hydrocarbons (NMHCs) are precursors to oxidant formation. They are oxidized by hydroxyl radical (OH), forming a complex mixture of peroxy radicals that oxidize NO to NO{sub 2} without consuming ozone (O{sub 3}) and thus allow O{sub 3} to increase in the atmospheric boundary layer. The reactivities of the NMHCs that compose biogenic and anthropogenic emissions vary greatly. For example, isoprene, which is emitted by deciduous vegetation, has an atmospheric lifetime with respect to oxidation by OH of about 20 min in polluted air ([OH] = 10{sup 7} radicals cm{sup {minus}3}). The atmospheric lifetimes of 2-methylpropene, 2-methylbutane, and the xylenes, which are found in vehicle emissions, are approximately 30 min, 7 hr, and 1.5 hr, respectively. The authors made measurements of the NMHCs at a surface site and aloft aboard the Battelle Gulfstream (G-1) aircraft, as part of an air quality study in the Phoenix area during May 1998. Diurnal variations in the NMHC distributions and their propene-equivalent concentrations are used to examine origins and reactivities of the air masses that were sampled at the surface site.

  9. Direct and indirect hydrogen abstraction in Cl + alkene reactions.

    PubMed

    Preston, Thomas J; Dunning, Greg T; Orr-Ewing, Andrew J; Vzquez, Saulo A

    2014-07-31

    Reactions between Cl atoms and propene can lead to HCl formation either by direct H abstraction or through a chloropropyl addition complex. Barring stabilizing collisions, the chloropropyl radical will either decompose to reactants or form HCl and allyl products. Using velocity-map imaging to measure the quantum state and velocity of the HCl products provides a view into the reaction dynamics, which show signs of both direct and indirect reaction mechanisms. Simulated trajectories of the reaction highlight the role of the direct H-abstraction pathways, and the resultant simulated scattering images show reasonable agreement with measurement. The simulations also show the importance of large excursions of the Cl atom far from equilibrium geometries within the chloropropyl complex, and these large-amplitude motions are the ultimate drivers toward HCl + allyl fragmentation. Gas-phase measurements of larger alkenes, 2-methylpropene and 2,3-dimethylbut-2-ene, show slightly different product distributions but still feature similar reaction dynamics. The current suite of experiments offers ready extensions to liquid-phase bimolecular reactions. PMID:24917363

  10. Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts.

    PubMed

    Yue, Lin; He, Chi; Hao, Zhengping; Wang, Shunbing; Wang, Hailin

    2014-03-01

    Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption-desorption, X-ray fluorescence (XRF), H2 temperature programmed reduction (H2-TPR), and NH3 temperature programmed desorption (NH3-TPD). Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2-methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from isomerization and protolysis reactions. PMID:25079284

  11. Ice core records of monoterpene- and isoprene-SOA tracers from Aurora Peak in Alaska since 1660s: Implication for climate change variability in the North Pacific Rim

    NASA Astrophysics Data System (ADS)

    Pokhrel, Ambarish; Kawamura, Kimitaka; Ono, Kaori; Seki, Osamu; Fu, Pingqing; Matoba, Sumio; Shiraiwa, Takayuki

    2016-04-01

    Monoterpene and isoprene secondary organic aerosol (SOA) tracers are reported for the first time in an Alaskan ice core to better understand the biological source strength before and after the industrial revolution in the Northern Hemisphere. We found significantly high concentrations of monoterpene- and isoprene-SOA tracers (e.g., pinic, pinonic, and 2-methylglyceric acids, 2-methylthreitol and 2-methylerythritol) in the ice core, which show historical trends with good correlation to each other since 1660s. They show positive correlations with sugar compounds (e.g., mannitol, fructose, glucose, inositol and sucrose), and anti-correlations with α-dicarbonyls (glyoxal and methylglyoxal) and fatty acids (e.g., C18:1) in the same ice core. These results suggest similar sources and transport pathways for monoterpene- and isoprene-SOA tracers. In addition, we found that concentrations of C5-alkene triols (e.g., 3-methyl-2,3,4-trihydroxy-1-butene, cis-2-methyl 1,3,4-trihydroxy-1-butene and trans-2-methyl-1,3,4-trihydroxy-1-butene) in the ice core have increased after the Great Pacific Climate Shift (late 1970s). They show positive correlations with α-dicarbonyls and fatty acids (e.g., C18:1) in the ice core, suggesting that enhanced oceanic emissions of biogenic organic compounds through the marine boundary layer are recorded in the ice core from Alaska. Photochemical oxidation process for these monoterpene- and isoprene-/sesquiterpene-SOA tracers are suggested to be linked with the periodicity of multi-decadal climate oscillations and retreat of sea ice in the Northern Hemisphere.

  12. A study of the unreduced molybdena-alumina system

    SciTech Connect

    Pantoja, A.; Sarrin, J.; Gonzalez, L.; Noguera, O.; Perez Zurita, M.J.; Galavis, J.L.; Goldwasser, J. )

    1993-07-01

    The isomerization and metathesis of 1-butene was carried out over a series of molybdena-alumina catalysts (1.0-8.2 wt% Mo) prepared by the adsorption equilibrium method. Catalytic conversion measurements (including the effect of preadsorbed water), tracer experiments (1-butene-d[sub o]+1-butene-d[sub 8]), pyridine adsorption followed by IR spectroscopy, and ESR studies were used as tools for the characterization of the solids. The pyridine adsorption experiments showed an increase in the number of acid sites as well as in the acid strength with increasing metal loading. The catalytic measurements showed a related increase in the rate of isomerization as the %Mo is increased. The cis/trans ratios decreased with increasing molybdenum loading, suggesting an increase in the acid strength of the remaining alumina hydroxyl groups. The results suggest a Broensted acid mechanism for the isomerization reaction over catalysts with molybdenum loading [ge] 3.9% Mo. The 1.0% molybdena-alumina catalyst behaved totally different. The results suggest a [pi]-allylic mechanism operative on the unperturbed alumina surface. The rate of formation of ethylene and propylene (products of metathesis) increased dramatically with increasing molybdenum loading. The catalysts evacuated at 500[degrees]C were considerably more active for the metathesis transformations than after evacuation at 500[degrees]C and/or after contacting the catalyst with the olefin. No Mo(V) signal was observed for the 1.0% Mo catalyst. The results suggest that the more easily reducible the catalyst is, the easier it would be to effect olefin metathesis. 35 refs., 4 figs., 6 tabs.

  13. Development of a pulsed uniform supersonic gas expansion system based on an aerodynamic chopper for gas phase reaction kinetic studies at ultra-low temperatures.

    PubMed

    Jimnez, E; Ballesteros, B; Canosa, A; Townsend, T M; Maigler, F J; Napal, V; Rowe, B R; Albaladejo, J

    2015-04-01

    A detailed description of a new pulsed supersonic uniform gas expansion system is presented together with the experimental validation of the setup by applying the CRESU (French acronym for Cintique de Raction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique to the gas-phase reaction of OH radicals with 1-butene at ca. 23 K and 0.63 millibars of helium (carrier gas). The carrier gas flow, containing negligible mixing ratios of OH-precursor and 1-butene, is expanded from a high pressure reservoir (337 millibars) to a low pressure region (0.63 millibars) through a convergent-divergent nozzle (Laval type). The novelty of this experimental setup is that the uniform supersonic flow is pulsed by means of a Teflon-coated aerodynamic chopper provided with two symmetrical apertures. Under these operational conditions, the designed Laval nozzle achieves a temperature of (22.4 1.4) K in the gas jet. The spatial characterization of the temperature and the total gas density within the pulsed uniform supersonic flow has also been performed by both aerodynamical and spectroscopic methods. The gas consumption with this technique is considerably reduced with respect to a continuous CRESU system. The kinetics of the OH+1-butene reaction was investigated by the pulsed laser photolysis/laser induced fluorescence technique. The rotation speed of the disk is temporally synchronized with the exit of the photolysis and the probe lasers. The rate coefficient (k(OH)) for the reaction under investigation was then obtained and compared with the only available data at this temperature. PMID:25933898

  14. Development of a pulsed uniform supersonic gas expansion system based on an aerodynamic chopper for gas phase reaction kinetic studies at ultra-low temperatures

    NASA Astrophysics Data System (ADS)

    Jimnez, E.; Ballesteros, B.; Canosa, A.; Townsend, T. M.; Maigler, F. J.; Napal, V.; Rowe, B. R.; Albaladejo, J.

    2015-04-01

    A detailed description of a new pulsed supersonic uniform gas expansion system is presented together with the experimental validation of the setup by applying the CRESU (French acronym for Cintique de Raction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique to the gas-phase reaction of OH radicals with 1-butene at ca. 23 K and 0.63 millibars of helium (carrier gas). The carrier gas flow, containing negligible mixing ratios of OH-precursor and 1-butene, is expanded from a high pressure reservoir (337 millibars) to a low pressure region (0.63 millibars) through a convergent-divergent nozzle (Laval type). The novelty of this experimental setup is that the uniform supersonic flow is pulsed by means of a Teflon-coated aerodynamic chopper provided with two symmetrical apertures. Under these operational conditions, the designed Laval nozzle achieves a temperature of (22.4 1.4) K in the gas jet. The spatial characterization of the temperature and the total gas density within the pulsed uniform supersonic flow has also been performed by both aerodynamical and spectroscopic methods. The gas consumption with this technique is considerably reduced with respect to a continuous CRESU system. The kinetics of the OH+1-butene reaction was investigated by the pulsed laser photolysis/laser induced fluorescence technique. The rotation speed of the disk is temporally synchronized with the exit of the photolysis and the probe lasers. The rate coefficient (kOH) for the reaction under investigation was then obtained and compared with the only available data at this temperature.

  15. Tungsten imido catalysts for selective ethylene dimerisation.

    PubMed

    Wright, Christopher M R; Turner, Zo R; Buffet, Jean-Charles; O'Hare, Dermot

    2016-02-01

    A tungsten imido complex W(NDipp)Me3Cl (Dipp = 2,6-(i)Pr-C6H3) is active for the selective dimerisation of ethylene to yield 1-butene under mild conditions. Immobilisation and activation of W(NDipp)Cl4(THF) on layered double hydroxides, silica or polymethylaluminoxane yields active solid state catalysts for the selective dimerisation of ethylene. The polymethylaluminoxane-based catalyst displays a turnover frequency (4.0 molC2H4 molW(-1) h(-1)) almost 7 times that of the homogeneous catalyst. PMID:26779579

  16. Abscission: The Role of Ethylene, Ethylene Analogues, Carbon Dioxide, and Oxygen

    PubMed Central

    Abeles, F. B.; Gahagan, H. E.

    1968-01-01

    Ethylene was the most effective abscission accelerant examined, with decreasing activity shown by propene, carbon monoxide, acetylene, vinyl fluoride, 1-butene, and 1,3-butadiene. Carbon dioxide inhibited abscission, but its effect was overcome by ethylene. Oxygen was required for abscission as an electron acceptor for respiration and not as a potentiator or activator of the ethylene attachment site. The molecular requirements for abscission were similar to those shown by other workers for other biological processes under the influence of ethylene. PMID:16656908

  17. XAFS Study of the Photo-Active Site of Mo/MCM-41

    NASA Astrophysics Data System (ADS)

    Miyamoto, Daisuke; Ichikuni, Nobuyuki; Shimazu, Shogo

    2007-02-01

    An Mo/MCM-41 catalyst was prepared and used for study of propene and 1-butene photo-metathesis reactions. XAFS analysis revealed that hydrogen reduction leads to a decreased role for the Mo=O site. The Mo-O site plays an important role for the olefin photo-metathesis reaction on the H2 reduced Mo/MCM-41. From EXAFS analysis, the active site of photo-metathesis reaction is the Mo=O part for oxidized Mo/MCM-41, whereas it is the Mo-O site for reduced Mo/MCM-41.

  18. Density Fluctuations in Crystallizing Polymers: Fact or Fiction?

    NASA Astrophysics Data System (ADS)

    Baert, Jimmy; Van Puyvelde, Peter

    2008-07-01

    The fact that, in polymer crystallization, nucleation might be accompanied by large scale density fluctuations has been investigated for the flow-induced crystallization of isotactic poly-1-butene (PB-1). Small Angle Light Scattering (SALS) was applied to measure density and orientation fluctuations, whereas complementary results were obtained from optical microscopy. The observations seem to indicate that the detected density fluctuations result from the presence of weakly anisotropic structures, rather than being an indication of densification before the onset of crystallization. In addition, the present work provides a critical review of polymer crystallization studies using SALS.

  19. Action spectroscopy for single-molecule reactions - Experiments and theory

    NASA Astrophysics Data System (ADS)

    Kim, Y.; Motobayashi, K.; Frederiksen, T.; Ueba, H.; Kawai, M.

    2015-05-01

    We review several representative experimental results of action spectroscopy (AS) of single molecules on metal surfaces using a scanning tunneling microscope (STM) by M. Kawai's group over last decade. The experimental procedures to observe STM-AS are described. A brief description of a low-temperature STM and experimental setup are followed by key experimental techniques of how to determine an onset bias voltage of a reaction and how to measure a current change associated with reactions and finally how to observe AS for single molecule reactions. The experimental results are presented for vibrationally mediated chemical transformation of trans-2-butene to 1.3-butadiene molecule and rotational motion of a single cis-2-butene molecule among four equivalent orientations on Pd(1 1 0). The AS obtained from the motion clearly detects more vibrational modes than inelastic electron tunneling spectroscopy with an STM. AS is demonstrated as a useful and novel single molecule vibrational spectroscopy. The AS for a lateral hopping of water dimer on Pt(1 1 1) is presented as an example of novelty. Several distinct vibrational modes are detected as the thresholds in the AS. The assignment of the vibrational modes determined from the analysis of the AS is made from a view of the adsorption geometry of hydrogen-bond donor or acceptor molecules in water dimer. A generic theory of STM-AS, i.e., a reaction rate or yield as a function of bias voltage, is presented using a single adsorbate resonance model for single molecule reactions induced by the inelastic tunneling current. Formulas for the reaction rate R (V) and Y (V) , i.e., reaction yield per electron Y (V) = eR (V) / I are derived. It provides a versatile framework to analyze any vibrationally mediated reactions of single adsorbates on metal surfaces. Numerical examples are presented to demonstrate generic features of the vibrational generation rate and Y (V) at different levels of approximations and to show how the effective broadening of the vibrational density of states (as described by Gaussian or Lorentzian functions) manifest themselves in Y (V) near the threshold bias voltage corresponding to a vibrational excitation responsible for reactions. A prefactor of Y (V) is explicitly derived for various types of elementary processes. Our generic formula of Y (V) also underlines the need to observe Y (V) at both bias voltage polarities, which can provide additional insight into the adsorbate projected density of states near the Fermi level within a span of the vibrational energy. The theory is applied to analysis of some highlights of the experimental results: Xe transfer, hopping of a single CO molecule on Pd(1 1 0), a dissociation of a single dimethyl disulfide (CH3S)2 and a hopping of a dissociated product, i.e., single methyl thiolate CH3S on Cu(1 1 1). It underlines that an observation of Y (V) at both bias polarities permits us to certain insight into the molecular alignment with respect to the Fermi level.

  20. Electron collisions with methyl-substituted ethylenes: Cross section measurements and calculations for 2-methyl-2-butene and 2,3-dimethyl-2-butene.

    PubMed

    Szmytkowski, Czes?aw; Stefanowska, Sylwia; Zawadzki, Mateusz; Ptasi?ska-Denga, El?bieta; Mo?ejko, Pawe?

    2015-08-14

    We report electron-scattering cross sections determined for 2-methyl-2-butene [(H3C)HC = C(CH3)2] and 2,3-dimethyl-2-butene [(H3C)2C = C(CH3)2] molecules. Absolute grand-total cross sections (TCSs) were measured for incident electron energies in the 0.5-300 eV range, using a linear electron-transmission technique. The experimental TCS energy dependences for the both targets appear to be very similar with respect to the shape. In each TCS curve, three features are discernible: the resonant-like structure located around 2.6-2.7 eV, the broad distinct enhancement peaking near 8.5 eV, and a weak hump in the vicinity of 24 eV. Theoretical integral elastic (ECS) and ionization (ICS) cross sections were computed up to 3 keV by means of the additivity rule (AR) approximation and the binary-encounter-Bethe method, respectively. Their sums, (ECS+ICS), are in a reasonable agreement with the respective measured TCSs. To examine the effect of methylation of hydrogen sides in the ethylene [H2C = CH2] molecule on the TCS, we compared the TCS energy curves for the sequence of methylated ethylenes: propene [H2C = CH(CH3)], 2-methylpropene [H2C = C(CH3)2], 2-methyl-2-butene [(H3C)HC = C(CH3)2], and 2,3-dimethyl-2-butene [(H3C)2C = C(CH3)2], measured in the same laboratory. Moreover, the isomeric effect is also discussed for the C5H10 and C6H12 compounds. PMID:26277137

  1. Electron collisions with methyl-substituted ethylenes: Cross section measurements and calculations for 2-methyl-2-butene and 2,3-dimethyl-2-butene

    NASA Astrophysics Data System (ADS)

    Szmytkowski, Czes?aw; Stefanowska, Sylwia; Zawadzki, Mateusz; Ptasi?ska-Denga, El?bieta; Mo?ejko, Pawe?

    2015-08-01

    We report electron-scattering cross sections determined for 2-methyl-2-butene [(H3C)HC = C(CH3)2] and 2,3-dimethyl-2-butene [(H3C)2C = C(CH3)2] molecules. Absolute grand-total cross sections (TCSs) were measured for incident electron energies in the 0.5-300 eV range, using a linear electron-transmission technique. The experimental TCS energy dependences for the both targets appear to be very similar with respect to the shape. In each TCS curve, three features are discernible: the resonant-like structure located around 2.6-2.7 eV, the broad distinct enhancement peaking near 8.5 eV, and a weak hump in the vicinity of 24 eV. Theoretical integral elastic (ECS) and ionization (ICS) cross sections were computed up to 3 keV by means of the additivity rule (AR) approximation and the binary-encounter-Bethe method, respectively. Their sums, (ECS+ICS), are in a reasonable agreement with the respective measured TCSs. To examine the effect of methylation of hydrogen sides in the ethylene [H2C = CH2] molecule on the TCS, we compared the TCS energy curves for the sequence of methylated ethylenes: propene [H2C = CH(CH3)], 2-methylpropene [H2C = C(CH3)2], 2-methyl-2-butene [(H3C)HC = C(CH3)2], and 2,3-dimethyl-2-butene [(H3C)2C = C(CH3)2], measured in the same laboratory. Moreover, the isomeric effect is also discussed for the C5H10 and C6H12 compounds.

  2. Microstructure of High Pressure Polyolefin/n-Alkane & Dimethyl Ether Solutions

    NASA Astrophysics Data System (ADS)

    van Zanten, John; McHugh, Mark; Li, Dan; Guney-Altay, Ozge; Dinoia, Todd; Kermis, Thomas; Park, Il-Hyun

    2003-03-01

    A series of dilute and semi-dilute poly(ethylene-co-1-butene)/n-alkane and dimethyl ether (DME) solutions have been investigated with high pressure small angle neutron scattering and dynamic light scattering. The n-alkane solvents considered in these investigations were ethane, propane, butane and pentane. The solutions have been examined at 110-150 °C and at pressures up to 2500 bar. In the semi-dilute concentration range, the classic high concentration isotopic labeling technique is used in conjunction with small angle neutron scattering to determine both the solution correlation length and coil dimensions for poly(ethylene-co-1-butene) dissolved in either ethane, pentane or DME. Chain collapse is observed upon approach to the phase boundary in n-alkane solutions but is absent in DME solutions. For the dilute solution regime, solutions of varying concentration in all of the n-alkanes and DME are considered in order to determine both the polymer diffusion coefficient at infinite dilution as well as the dynamic second viral coefficient which is primarily dominated by the second osmotic virial coefficient. The polymer coil hydrodynamic radii behavior in dilute solutions is essentially the same as that observed for the semi-dilute solutions. Coil behavior in the dilute and semi-dilute concentration regimes is compared and contrasted.

  3. Volatile organic compound constituents from an integrated iron and steel facility.

    PubMed

    Tsai, Jiun-Horng; Lin, Kuo-Hsiung; Chen, Chih-Yu; Lai, Nina; Ma, Sen-Yi; Chiang, Hung-Lung

    2008-09-15

    This study measured the volatile organic compound (VOC) constituents of four processes in an integrated iron and steel industry; cokemaking, sintering, hot forming, and cold forming. Toluene, 1,2,4-trimethylbenzene, isopentane, m,p-xylene, 1-butene, ethylbenzene, and benzene were the predominant VOC species in these processes. However, some of the chlorinated compounds were high (hundreds ppbv), i.e., trichloroethylene in all four processes, carbon tetrachloride in the hot forming process, chlorobenzene in the cold forming process, and bromomethane in the sintering process. In the sintering process, the emission factors of toluene, benzene, xylene, isopentane, 1,2,4-trimethylbenzene, and ethylbenzene were over 9 g/tonne-product. In the vicinity of the manufacturing plant, toluene, isopentane, 1,2,4-trimethylbenzene, xylene and ethylbenzene were high. Toluene, 1,2,4-trimethylbenzene, xylene, 1-butene and isopentane were the major ozone formation species. Aromatic compounds were the predominant VOC groups, constituting 45-70% of the VOC concentration and contributing >70% to the high ozone formation potential in the stack exhaust and workplace air. The sequence of VOC concentration and ozone formation potential was as follows: cold forming>sintering>hot forming>cokemaking. For the workplace air, cokemaking was the highest producer, which was attributed to the fugitive emissions of the coke oven and working process release. PMID:18289777

  4. A simplified chemistry module for atmospheric transport and dispersion models: Proof-of-concept using SCIPUFF

    NASA Astrophysics Data System (ADS)

    Burns, Douglas S.; Rottmann, Shawn D.; Plitz, Angela B. L.; Wiseman, Floyd L.; Moore, William; Chynwat, Veeradej

    2012-09-01

    An atmospheric chemistry module was developed to predict the fate of environmentally hazardous compounds discharged into the atmosphere. The computationally efficient model captures the diurnal variation within the environment and in the degradation rates of the released compounds, follows the formation of toxic degradation products, runs rapidly, and in principle can be integrated with any atmospheric transport and dispersion model. To accomplish this, a detailed atmospheric chemistry mechanism for a target toxic industrial compound (TIC) was reduced to a simple empirical effective degradation rate term (keff). Empirically derived decay functions for keff were developed as a function of important meteorological parameters such as solar flux, temperature, humidity, and cloud cover for various land uses and locations by statistically analyzing data generated from a detailed chemistry mechanism run over a wide range of (typical) atmospheric conditions. 1-Butene and two degradation products (propanal and nitrooxybutanone) were used as representative chemicals in the algorithm development for this proof-of-concept demonstration of the capability of the model. The quality of the developed model was evaluated via comparison with experimental chamber data and the results (decay rates) compared favorably for ethene, propene, and 1-butene (within a factor of two 75% or more of the time).

  5. Near-threshold absolute photoionization cross-sections of some reaction intermediates in combustion

    NASA Astrophysics Data System (ADS)

    Wang, Juan; Yang, Bin; Cool, Terrill A.; Hansen, Nils; Kasper, Tina

    2008-02-01

    The use of photoionization mass spectrometry for the development of quantitative kinetic models for the complex combustion chemistry of both conventional hydrocarbon fuels and oxygenated biofuels requires near-threshold measurements of absolute photoionization cross-sections for numerous reaction intermediates. Near-threshold absolute cross-sections for molecular and dissociative photoionization for 20 stable reaction intermediates (methane, ethane, propane, n-butane, cyclopropane, methylcyclopentane, 1-butene, cis-2-butene, isobutene, 1-pentene, cyclohexene, 3,3-dimethyl-1-butene, 1,3-hexadiene, 1,3-cyclohexadiene, methyl acetate, ethyl acetate, tetrahydrofuran, propanal, 1-butyne, 2-butyne) are presented. Previously measured total photoionization cross-sections for 9 of these molecules are in good agreement with the present results. The measurements are performed with photoionization mass spectrometry (PIMS) using a monochromated VUV synchrotron light source with an energy resolution of 40 meV (fwhm) comparable to that used for flame-sampling molecular beam PIMS studies of flame chemistry and reaction kinetics.

  6. Vanadium-phosphorus-oxygen industrial catalysts for C/sub 4/ hydrocarbon selective oxidation to maleic anhydride

    SciTech Connect

    Wenig, R.W.

    1987-06-01

    The selective oxidation of n-butane to maleic anhydride by vanadium-phosphorus-oxygen (V-P-O) industrial catalysts varying in P-to-V ratio has been studied in a fixed bed integral reactor system. Catalyst characterization studies including x-ray diffraction, laser Raman spectroscopy, infrared spectroscopy, x-ray photoelectron spectroscopy, scanning electron microscopy, x-ray energy dispersive spectroscopy, and BET surface area measurements were used. A strong effect of P-to-V synthesis ratio on catalyst structure, catalyst morphology, vanadium oxidation state, and reactivity in n-butane selective oxidation was observed. A slight ''excess'' of catalyst phosphorus (P/V = 1.1 catalyst) was found to stabilize an active and selective (VO)/sub 2/P/sub 2/O/sub 7/ phase. The mechanism of n-butane selective oxidation to maleic anhydride was studied by in situ infrared spectroscopy using n-butane, 1-butene, 1,3-butadiene, crotyl alcohol, maleic acid, crotonic acid, and maleic anhydride feeds. During paraffin selective oxidation, highly reactive olefin species and maleic acid were observed on the surfaces of V-P-O catalysts. Further evidence in support of conjugated or possibly strained olefin and maleic acid reaction intermediates in n-butane and 1-butene partial oxidation to maleic anhydride was gathered.

  7. Structure and entanglements in short chain branched polyolefin melts

    NASA Astrophysics Data System (ADS)

    Moorthi, K.; Kamio, K.; Ramos, J.; Theodorou, D. N.

    2013-02-01

    Atomistic models of short chain branched (SCB) polyethylene melts containing up to 20-40 mol% of comonomer (1-butene, 1-hexene, 1-octene or 1-decene) have been equilibrated at 450 K using a connectivity altering Monte Carlo method, and analyzed for topological constraints using Z1 and CReTA codes. The calculated tube diameters, , of SCB melts are found to scale with the backbone weight fraction, ?, as ?-0.46, close to the scaling predicted by the binary contact model, ?-0.5 and in disagreement with the packing model prediction ?-1.27. Similar scaling relationships are observed experimentally for polymer solutions, and reproduced by the present methods.

  8. Precision Polyolefin Structure: Modeling Polyethylene Containing Methyl and Ethyl Branches

    NASA Astrophysics Data System (ADS)

    Rojas, Giovanni; Wagener, Kenneth B.

    Sequenced copolymers of ethylene and diverse species have been created using acyclic diene metathesis (ADMET) polymerization, a step growth, condensation- type polymerization driven to high conversion by the removal of ethylene. ADMET permits control over branch content and branch length, which can be predetermined during the monomer synthesis, allowing sequence control in the resultant unsaturated polymer. Monomers are symmetrical ?,?dienes with a pendant functionality. Diverse functional groups are compatible with ADMET polymerization when Schrocks or first-generation Grubbs catalysts are used. Saturation with hydrogen after ADMET polymerization affords a polyethylene (PE) backbone bearing specific functionalities in precise places. Varying both the pendant functional group and the spacing between functionalities alters the physical and chemical properties of the polymer. Incorporation of alkyl chains into the PE backbone via ADMET leads to the study of perfect structures modeling the copolymerization of ethylene with ?-olefins such as 1-propene, 1-butene, 1-hexene, and 1-octene.

  9. Synthesis of an un-supported, high-flow ZSM-22 zeolite membrane

    DOEpatents

    Thoma, Steven G. (Albuquerque, NM); Nenoff, Tina M. (Albuquerque, NM)

    2006-10-10

    Novel methods for synthesizing wholly un-supported, high-flow catalytic membranes consisting of 100% crystalline ZSM-22 crystals with no binder phase, having sufficient porosity to allow high Weight Hourly Space Velocities of feedstock to pass through without generating back pressure. The ZSM-22 membranes perform favorably to existing bulk ZSM-22 catalysts (e.g., via 1-butene conversion and selectivity). The method of membrane synthesis, based on Vapor Phase Transport, allows free-standing, binder-less membranes to be fabricated in varied geometries and sizes so that membranes can be tailor-made for particular geometries applications. The ZSM-22 precursor gel may be consolidated into a semi-cohesive body prior to vapor phase crystallization, for example, by uniaxial pressing. These crystalline membranes may be modified by ion exchange, pore ion exchange, framework exchange, synthesis modification techniques to incorporate other elements into the framework, such as K, H, Mg, Zn, V, Ga, and Pt.

  10. Three-Dimensional Conformation of Folded Polymers in Single Crystals

    NASA Astrophysics Data System (ADS)

    Hong, You-lee; Yuan, Shichen; Li, Zhen; Ke, Yutian; Nozaki, Koji; Miyoshi, Toshikazu

    2015-10-01

    The chain-folding mechanism and structure of semicrystalline polymers have long been controversial. Solid-state NMR was applied to determine the chain trajectory of 13C CH3 -labeled isotactic poly(1-butene) (i PB 1 ) in form III chiral single crystals blended with nonlabeled i PB 1 crystallized in dilute solutions under low supercooling. An advanced 13C - 13C double-quantum NMR technique probing the spatial proximity pattern of labeled 13C nuclei revealed that the chains adopt a three-dimensional (3D) conformation in single crystals. The determined results indicate a two-step crystallization process of (i) cluster formation via self-folding in the precrystallization stage and (ii) deposition of the nanoclusters as a building block at the growth front in single crystals.

  11. A remarkable shape-catalytic effect of confinement on the rotational isomerization of small hydrocarbons

    SciTech Connect

    Santiso, Erik E; Gubbins, Keith E; Buongiorno Nardelli, Marco

    2008-01-01

    As part of an effort to understand the effect of confinement by porous carbons on chemical reactions, we have carried out density functional theory calculations on the rotational isomerization of three four-membered hydrocarbons: n-butane, 1-butene, and 1,3-butadiene. Our results show that the interactions with the carbon walls cause a dramatic change on the potential energy surface for pore sizes comparable to the molecular dimensions. The porous material enhances or hinders reactions depending on how similar is the shape of the transition state to the shape of the confining material. The structure of the stable states and their equilibrium distributions are also drastically modified by confinement. Our results are consistent with a doubly exponential behavior of the reaction rates as a function of pore size, illustrating how the shape of a catalytic support can dramatically change the efficiency of a catalyst. (51 refs.)

  12. Fuel structure and pressure effects on the formation of soot particles in diffusion flames. Annual technical report, 15 January 1988-15 January 1989

    SciTech Connect

    Santoro, R.J.

    1989-02-15

    Studies emphasizing the effects of fuel molecular structure on soot formation processes in laminar-diffusion flames were investigated. Particular attention was given to the particle inception and surface growth processes for a series of fuels. Studies of butane, 1-butene, and 1,3 butadiene have revealed that fuel structure strongly affects the soot-particle-inception process. However, subsequent surface-growth processes are largely determined by the available surface area. Thus, the surface growth process is independent of the fuel molecular structure following the initial particle-inception stage. Studies of the particle-inception region indicate that increased soot formation is strongly correlated with visible-fluorescence measurements attributed to large polynuclear aromatic hydrocarbon species in the flame.

  13. Transition metal promoted reactions of boron hydrides. 13. Platinum catalyzed synthesis of 6,9-dialkyldecaboranes

    SciTech Connect

    Mazighi, K.; Carroll, P.J.; Sneddon, L.G. )

    1993-05-12

    Both chloroplatinic acid and platinum bromide have been found to catalyze the reactions of decaborane(14) with terminal olefins, including ethylene, propylene, 1-butene, and 1-pentene, to give the corresponding 6,9-R[sub 2]B[sub 10]H[sub 12] derivatives in high yields. Chemical studies of 6,9-(n-C[sub 5]H[sub 11])[sub 2]B[sub 10]H[sub 12] (1) show that, in contrast to decaborane(14), 1 does not react to form dibase adducts with the Lewis bases Et[sub 3]N, Ph[sub 3]P, Et[sub 2]S, or MeCN. However, 1 undergoes many other reactions, including deprotonation to 6,9-(n-C[sub 5]H[sub 11])[sub 2]B[sub 10]H[sub 11][sup [minus

  14. Aluminum coordination and active sites on aluminas, Y zeolites and pillared layered silicates. Progress report, June 1, 1990--January 31, 1992

    SciTech Connect

    Fripiat, J.J.

    1991-12-31

    Our work has been deployed in four directions, namely, (1) Study of the distribution of aluminum within three possible kinds of coordination shells: four-fold (IV), five-fold (V), and six-fold (VI), in aluminas and dealuminated zeolites by high-resolution solid state NMR or magic angle NMR. Besides the classical one pulse spectra, nutation spectra have been studied. (2) Study of the electron deficient sites by electron paramagnetic resonance (EPR) of probe molecules on aluminas and decationated zeolites. Electron deficient sites are considered as Lewis sites. (3) Study of the model isomerization reaction 1 butene {yields} 2 cis or trans butene on the aluminas characterized in 1 and 2. (4) Synthesis of a silicate lattice in which silicon has been partially replaced by aluminum. The chosen silicate is that of the zeolite (fibrous) sepiolite. It has been characterized as indicated in 1 and 2.

  15. Oligomerize for better gasoline

    SciTech Connect

    Nierlich, F. )

    1992-02-01

    This paper reports on normal butene containing isobutene-depleted C{sub 4} hydrocarbons like raffinate II which are oligomerized using the Octol process in the liquid phase on a heterogeneous catalyst system to yield mainly C{sub 8} and C{sub 12} olefins. Raffinate II, the spent C{sub 4} fraction of an MTBE unit, is an ideal feedstock for further n-butene processing because of its high olefin concentration ranging between 70% and 80%. By modifications of MTBE technology, implementation of selective hydrogenation for removal of residual butadiene and superfractionating raffinate II, polymer grade 1-butene can be produced. Until the mid-70s raffinate I, the team cracker C{sub 4} cut after butadiene extraction, was mainly burned or blended into gasoline. Now nearly all raffinate I is or will be consumed for the purpose of converting isobutylene to MTBE.

  16. Tetrahydrothiophene desulfurization on Co-Mo/. gamma. -Al sub 2 O sub 3 : A temporal analysis of products (TAP) investigation

    SciTech Connect

    Moser, W.R.; Rossetti, G.A. Jr. ); Gleaves, J.T.; Ebner, J.R. )

    1991-01-01

    The catalytic reactions of tetrahydrothiophene, thiophene, 1-butene, 1,3-butadiene, and n-butane with hydrogen were studied at low pressure over a commercial cobalt molybdate catalyst. The formation sequence of tetrahydrothiophene desulfurization products was monitored with submilli-second time resolution using the temporal analysis of products (TAP) transient microreactor technique. The TAP experiments showed that butene and were the only hydrocarbon desulfurization products formed, although rapid dehydrogenation to thiophene was also observed. The exceptional time resolution of the TAP spectrometer provided evidence that the butene formed could not be accounted for by a mechanism involving butadiene hydrogenation. The results suggested a desulfurization mechanism for tetrahydrothiophene wherein C{sub 4} hydrocarbon formation proceeds via a surface butene thiolate intermediate produced by a single {beta}-hydride elimination of the intermediate, while rapid C-S bond hydrogenolysis involving surface hydrogen is responsible for butene formation.

  17. Catalytic oxidation of furan on a Mo-Ti-O catalyst. Infrared and thermodesorption study

    SciTech Connect

    Rivasseau, J.; Canesson, P.; Blanchard, M.

    1980-10-16

    The adsorption and oxidation of furan, an intermediate in the conversion of 1-butene to maleic anhydride, were studied on a catalyst containing 15.6% molybdenum as trioxide on titanium dioxide that yielded 53% maleic anhydride at 63% conversion. The results showed at furan adsorbed in two distinct modes, of which one was observed only on oxidized surface and the other was always present but depended on the degree of reduction. The adsorbed furan was oxidized in the presence of oxygen at temperatures above 235/sup 0/C, but it desorbed only above 320/sup 0/C. The Mo=O species did not seem to be important in the oxidation of furan to maleic anhydride.

  18. In situ fourier transform infrared study of crotyl alcohol, maleic acid, crotonic acid, and maleic anhydride oxidation on a V-P-O industrial catalyst

    SciTech Connect

    Wenig, R.W.; Schrader, G.L.

    1987-10-22

    Crotyl alcohol, maleic acid, crotonic (2-butenoic) acid, and maleic anhydride were fed to an in situ infrared cell at 300/sup 0/C containing a P/V = 1.1 vanadium-phosphorous-oxide (V-P-O) catalyst used for the selective oxidation of n-butane. Crotyl alcohol was used as a mechanistic probe for the formation of reactive olefin species observed during previous n-butane and 1-butene studies. Crotonic acid, maleic acid, and maleic anhydride were fed as probes for the existence of other possible adsorbed intermediates. Olefin species and maleic acid are proposed as possible reaction intermediates in n-butane selective oxidation to maleic anhydride. The involvement of peroxide species in the oxidation of butadiene to maleic acid is also discussed.

  19. Solid acid catalysts from clays: preparation of mesoporous catalysts by chemical activation of metakaolin under acid conditions.

    PubMed

    Lenarda, M; Storaro, L; Talon, A; Moretti, E; Riello, P

    2007-07-15

    Natural kaolin was treated at 850 or 950 degrees C in air flow to give respectively the metakaolin samples MK8 and MK9. The obtained materials were successively treated at 90 degrees C with a 1 M solution of H(2)SO(4), for various time lengths. The acid treatment of MK8 was found to give a high surface area microporous material with good catalytic properties related to the high density of acid sites, while MK9 gave an ordered mesoporous material with a low density of acid sites. The materials were characterized by several techniques, X-ray powder diffraction, thermogravimetric analysis, N(2) physisorption, scanning electron microscopy, and temperature-programmed desorption of ammonia. The 1-butene isomerization was used as test reaction to evaluate the acidity of the samples. PMID:17451736

  20. Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

    DOEpatents

    Dumesic, James A [Verona, WI; Ruiz, Juan Carlos Serrano [Madison, WI; West, Ryan M [Madison, WI

    2014-01-07

    Described is a method to make liquid chemicals. The method includes deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be conveted to a mixture of n-butenes. The pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes.

  1. Shock tube study of the fuel structure effects on the chemical kinetic mechanisms responsible for soot formation, part 2

    NASA Technical Reports Server (NTRS)

    Frenklach, M.; Clary, D. W.; Ramachandra, M. K.

    1985-01-01

    Soot formation in oxidation of allene, 1,3-butadiene, vinylacetylene and chlorobenzene and in pyrolysis of ethylene, vinylacetylene, 1-butene, chlorobenzene, acetylen-hydrogen, benzene-acetylene, benzene-butadiene and chlorobenzene-acetylene argon-diluted mixtures was studied behind reflected shock waves. The results are rationalized within the framework of the conceptual models. It is shown that vinylacetylene is much less sooty than allene, which indicates that conjugation by itself is not a sufficient factor for determining the sooting tendency of a molecule. Structural reactivity in the context of the chemical kinetics is the dominant factor in soot formation. Detailed chemical kinetic modeling of soot formation in pyrolysis of acetylene is reported. The main mass growth was found to proceed through a single dominant route composed of conventional radical reactions. The practically irreversible formation reactions of the fused polycyclic aromatics and the overshoot by hydrogen atom over its equilibrium concentration are the g-driving kinetic forces for soot formation.

  2. Reaction mechanism studies of unsaturated molecules using photofragment translational spectroscopy

    SciTech Connect

    Longfellow, C.A. |

    1996-05-01

    A number of molecules have been studied using the technique of photofragment translational spectroscopy. In Chapter One a brief introduction to the experimental technique is given. In Chapter Two the infrared multiphoton dissociation (IRMPD) of acetic acid is discussed. Carbon dioxide and methane were observed for the first time as products from dissociation under collisionless conditions. Chapter Three relates an IRMPD experiment of hexafluoropropene. The predominant channel produces CFCF{sub 3} or C{sub 2}F{sub 4} and CF{sub 2}, with the heavier species undergoing further dissociation to two CF{sub 2} fragments. In Chapter Four the ultraviolet (UV) dissociation of hexafluoropropene is investigated. Chapter Five explores the IRMPD of octafluoro-1-butene and octafluoro-2-butene.

  3. Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

    DOEpatents

    Dumesic, James A.; Ruiz, Juan Carlos Serrano; West, Ryan M.

    2015-06-30

    Described is a method to make liquid chemicals. The method includes deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be converted to a mixture of n-butenes. The pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes.

  4. Radiation-induced effects in polymers and related compounds. Final report

    SciTech Connect

    Silverman, J.

    1980-04-01

    The report is divided into two sections. The first section covers progress during the final contract period April 1, 1978-October 31, 1979; it covers work performed in conjunction with the objectives of the contract, some of which was recently completed. The second section is a general summary of the contract activities and accomplishments over the 19 year period covered by AEC-ERDA-DOE support. Studies completed or still in progress since April 1, 1979 are: ESR measurements on alkyl single crystals; work on polymer composites; studies on styrene-polyethylene grafts; experiments on the use of torque rheometry as a means of measuring the effects of ionizing radiation on polymers; investigations on the melting and crystallization behavior of irradiated polymers; and pulse radiolysis of poly(1-butene) and polyethylene.

  5. Aluminum coordination and active sites on aluminas, Y zeolites and pillared layered silicates

    SciTech Connect

    Fripiat, J.J.

    1991-01-01

    Our work has been deployed in four directions, namely, (1) Study of the distribution of aluminum within three possible kinds of coordination shells: four-fold (IV), five-fold (V), and six-fold (VI), in aluminas and dealuminated zeolites by high-resolution solid state NMR or magic angle NMR. Besides the classical one pulse spectra, nutation spectra have been studied. (2) Study of the electron deficient sites by electron paramagnetic resonance (EPR) of probe molecules on aluminas and decationated zeolites. Electron deficient sites are considered as Lewis sites. (3) Study of the model isomerization reaction 1 butene {yields} 2 cis or trans butene on the aluminas characterized in 1 and 2. (4) Synthesis of a silicate lattice in which silicon has been partially replaced by aluminum. The chosen silicate is that of the zeolite (fibrous) sepiolite. It has been characterized as indicated in 1 and 2.

  6. Flame temperature, fuel structure, and fuel concentration effects on soot formation in inverse diffusion flames

    SciTech Connect

    Sidebotham, G.W.; Glassman, I. )

    1992-09-01

    Insights into soot formation processes are gained from chemical sampling and thermocouple probing of co-flowing inverse diffusion flames (IDFs), with the oxidizer in the center. In this paper the transition from near-to slightly sooting flames and the effects of flame temperature, fuel concentration, and fuel structure (using methane, ethene, propene and 1-butene) are investigated. The aromatic content of IDFS scales with the fuel's sooting tendency, and suggests that the formation of the aromatic ring is a controlling step in soot formation. In addition to the relatively well-established reactions involving C4 and C2 species, benzene may form directly from two C3 species for fuels that readily produce C3 species during pyrolysis and/or oxidative pyrolysis. The total concentration of growth species increases almost linearly with fuel concentration, but depends more weakly on flame temperature than would be expected if pure pyrolysis governed the intermediate hydrocarbon behavior.

  7. The vertical distributions of VOCs in the atmosphere of Beijing in autumn.

    PubMed

    Ting, Mao; Yue-Si, Wang; Jie, Jiang; Fang-kun, Wu; Mingxing, Wang

    2008-02-01

    Volatile organic compounds (VOCs) in the air of Beijing City were measured at the heights of 8, 32, 140 and 280 m on the Beijing 325 m meteorological tower in autumn 2005. Concentrations of fifty-five compounds were determined by quantitative analytical methods. Our study utilized GC/MS analysis of 0.5 l air sample that were cryo-concentrated prior to analysis. The vertical distributions of VOCs were also investigated using 1-butene, isopentane, dichloromethane and toluene as representative compounds of several different categories. It is shown that 1-butene followed by 2-butene, isopentane followed by n-pentane, dichloromethane followed by chloroform and toluene followed by benzene are the most abundant compounds in the categories of alkene, alkane, halocarbon and aromatic hydrocarbon, respectively. The concentrations of TVOCs range from 51.2+/-39.7 ppb to 83.6+/-44.4 ppb on clear days, but from 62.9+/-19.0 ppb to 105.0+/-59.2 ppb on haze days. While alkenes and halocarbons contribute little to TVOCs, alkanes provide the largest percentage, ranging from about 46% to 63% at four different heights, which are followed by aromatic hydrocarbons ranging from about 15% to 27%. The vertical distributions of VOCs are complex. On clear days most distribution profiles show a decreasing trend with increasing height. On haze days, however, they exhibit first a decrease with increasing altitude from 8 m to 140 m and then a significant increase at 280 m. These results are understood by analyzing how the vertical distributions of VOCs are affected jointly by several factors such as meteorological parameters and transport property. In addition, principal components analysis (PCA) and cluster analysis show that VOCs have different origins at different heights. PMID:17976686

  8. Species and soot concentration measurements in a methane/air nonpremixed flame doped with C4 hydrocarbons

    SciTech Connect

    Mcenally, C.S.; Pfefferle, L.D.

    1998-10-01

    The fuel in a co-flowing methane/air nonpremixed flame was doped with 7400 ppm of 1,3-butadiene, 1-butene, isobutene, and n-butane. Temperature, mole fractions of 24 stable C1 to C12 hydrocarbons, and soot volume fraction were measured along the centerline of the five resulting flames. The additives significantly increased the concentrations of aromatic species and of soot. The specific changes could be reasonably explained by conversion of the additives to aromatic ring precursors, but not by effects of the additives on temperature and H atom concentrations. Isobutene and 1-butene generated the highest concentrations of C4 products. However, several pathways readily interconvert C3 and C4 species, such that increases in both C3 and C4 species were observed for almost every additive. Recombination of propargyl radicals (C{sub 3}H{sub 3}) appears to be responsible for most aromatic ring formation on the centerline of these flames. Reactions of acetylene with n-C{sub 4}H{sub 5} and/or n-C{sub 4}H{sub 3} may also contribute in the 1.3-butadiene-doped flame. Benzene appears to be in partial equilibrium with acetylene in the upper half of the flames. The kinetic processes that establish this equilibrium are most likely ring fragmentation reactions in one direction and acetylene addition to n-C{sub 4}H{sub 3} in the other. The probable source of the n-C{sub 4}H{sub 3} is acetylene addition to C{sub 2}H, with the strong temperature-dependence of C{sub 2}H concentrations responsible for limiting this process to the upper half of the flames. Production of one-ring aromatic species is an important rate-limiting step to soot formation in these flames.

  9. First examples of homogeneous hydrogenolysis of thiophene to 1-butanethiolate and ethylthioketene ligands: Synthesis and reactivity of ([eta][sup 4]-C[sub 4]H[sub 5]S)ReH[sub 2](PPh[sub 3])[sub 2

    SciTech Connect

    Rosini, G.P.; Jones, W.D. )

    1992-12-30

    The reaction of ReH[sub 7](PPh[sub 3])[sub 2] with excess thiophene in the presence of the hydrogen acceptor 3,3-dimethyl-1-butene results in the formation of a new organometallic complex which has been identified as the thioallyl complex ([eta][sup 4]-C[sub 4]H[sub 5]S)ReH[sub 2](PPh[sub 3])[sub 2] (1). The thermolysis of a solution of 1 at 60[degrees]C with excess trimethylphosphine results in the formation of free tetrahydrothiophene and the new cyclometalated organometallic complex [ovr Re(PMe[sub 3])[sub 4](PPh[sub 2]C][sub 6]H[sub 4]) (2). Photolysis of a solution of 1 with excess trimethylphospine proceeds differently, yielding a mixture of four new organometallic complexes, all of which contain a C-S-cleaved 1-butene-1-thiolate ligand. Two of the complexes contain an S-bound ethenethiolate ligand and exist as cis and trans isomers of Re(SCH[double bond]CHEt)(PMe[sub 3])[sub 5] (3a,b), while the other two complexes contain an [eta][sup 3]-allyl-bound ethenethiolate ligand and exist as cis and trans isomers of Re([eta][sup 3]-SCH[double bond]CHEt)(PMe[sub 3])[sub 4] (4a,b). In both complexes the cis is the more thermodynamically stable isomer. The cis complex 3a is seen to isomerize to the trans 3b photochemically (cis:trans = 1.6:1), while thermally the trans isomerizes almost totally to the cis (cis:trans = 10:1 after several days). In the presence of a large excess of PMe[sub 3], only complexes 3a,b are seen, whereas removal of the free phosphine from solution gives only complexes 4a,b. 23 refs., 6 figs., 3 tabs.

  10. Inhibitory potency of 4-carbon alkanes and alkenes toward CYP2E1 activity.

    PubMed

    Hartman, Jessica H; Miller, Grover P; Boysen, Gunnar

    2014-04-01

    CYP2E1 has been implicated in the bioactivation of many small molecules into reactive metabolites which form adducts with proteins and DNA, and thus a better understanding of the molecular determinants of its selectivity are critical for accurate toxicological predictions. In this study, we determined the potency of inhibition of human CYP2E1 for various 4-carbon alkanes, alkenes and alcohols. In addition, known CYP2E1 substrates and inhibitors including 4-methylpyrazole, aniline, and dimethylnitrosamine were included to determine their relative potencies. Of the 1,3-butadiene-derived metabolites studied, 3,4-epoxy-1-butene was the strongest inhibitor with an IC50 of 110 ?M compared to 1700 ?M and 6600 ?M for 1,2-butenediol and 1,2:3,4-diepoxybutane, respectively. Compared to known inhibitors, inhibitory potency of 3,4-epoxy-1-butene is between 4-methylpyrazole (IC50 = 1.8 ?M) and dimethylnitrosamine (IC50 = 230 ?M). All three butadiene metabolites inhibit CYP2E1 activity through a simple competitive mechanism. Among the 4-carbon compounds studied, the presence and location of polar groups seems to influence inhibitory potency. To further examine this notion, the investigation was extended to include structurally and chemically similar analogues, including propylene oxide and various butane alcohols. Those results demonstrated preferential recognition of CYP2E1 toward the type and location of polar and hydrophobic structural elements. Taken together, CYP2E1 metabolism may be modified in vivo by exposure to 4-carbon compounds, such as drugs, and nutritional constituents, a finding that highlights the complexity of exposure to mixtures. PMID:24561005

  11. Observation of 2-methyltetrols and related photo-oxidation products of isoprene in boreal forest aerosols from Hyytil, Finland

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Ruuskanen, T.; Maenhaut, W.; Kulmala, M.; Claeys, M.

    2005-05-01

    Oxidation products of isoprene including 2-methyltetrols (2-methylthreitol and 2-methylerythritol), 2-methylglyceric acid and triol derivatives of isoprene (2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene) have been detected in boreal forest PM1 aerosols collected at Hyytil, southern Finland, during a 2004 summer period, at significant atmospheric concentrations (in total 51 ng m-3 in summer versus 0.46 ng m-3 in fall). On the basis of these results, it can be concluded that photo-oxidation of isoprene is an important atmospheric chemistry process that contributes to secondary organic aerosol formation during summer in this conifer forest ecosystem. In addition to isoprene oxidation products, malic acid, which can be regarded as an end-oxidation product of unsaturated fatty acids, was also detected at high concentrations during the summer period (46 ng m-3 in summer versus 5.2 ng m-3 in fall), while levoglucosan, originating from biomass burning, became relatively more important during the fall period (29 ng m-3 in fall versus 10 ng m-3 in summer). Pinic acid, a major photo-oxidation product of ?-pinene in laboratory experiments, could only be detected at trace levels in the summer PM1 aerosol samples from Hyytil, suggesting that further oxidation of pinic acid occurs and/or that different oxidation pathways are followed. We hypothesize that photo-oxidation of isoprene may participate in the early stages of new particle formation, a phenomenon which has been well documented in the boreal forest environment.

  12. Observation of 2-methyltetrols and related photo-oxidation products of isoprene in boreal forest aerosols from Hyytil, Finland

    NASA Astrophysics Data System (ADS)

    Kourtchev, I.; Ruuskanen, T.; Maenhaut, W.; Kulmala, M.; Claeys, M.

    2005-10-01

    Oxidation products of isoprene including 2-methyltetrols (2-methylthreitol and 2-methylerythritol), 2-methylglyceric acid and triol derivatives of isoprene (2-methyl-1,3,4-trihydroxy-1-butene (cis and trans) and 3-methyl-2,3,4-trihydroxy-1-butene) have been detected in boreal forest PM1 aerosols collected at Hyytil, southern Finland, during a 2004 summer period, at significant atmospheric concentrations (in total 51 ng m-3 in summer versus 0.46 ng m-3 in fall). On the basis of these results, it can be concluded that photo-oxidation of isoprene is an important atmospheric chemistry process that contributes to secondary organic aerosol formation during summer in this conifer forest ecosystem. In addition to isoprene oxidation products, malic acid, which can be regarded as an intermediate in the oxidation of unsaturated fatty acids, was also detected at high concentrations during the summer period (46 ng m-3 in summer versus 5.2 ng m-3 in fall), while levoglucosan, originating from biomass burning, became relatively more important during the fall period (29 ng m-3 in fall versus 10 ng m-3 in summer). Pinic acid, a major photo-oxidation product of ?-pinene in laboratory experiments, could only be detected at trace levels in the summer samples, suggesting that further oxidation of pinic acid occurs and/or that different oxidation pathways are followed. We hypothesize that photo-oxidation of isoprene may participate in the early stages of new particle formation, a phenomenon which has been well documented in the boreal forest environment.

  13. Selective oxidation of C*4* hydrocarbons over (VO)*2*P*2*O*7 catalyst: Nature of the redox mechanism

    SciTech Connect

    Kamat, S.N.

    1992-09-09

    For selective oxidation of n-butane to maleic anhydride, (VO)[sub 2]P[sub 2]O[sub 7] has been identified as the most active and selective V-P-0 phase. A three stage solid state procedure was used to synthesize a (VO)[sub 2]P[sub 2]O[sub 7] catalyst labeled with [sup 18]O. Spectroscopy, etc. pointed to a highly site-specific [sup 18]O labeling. Anaerobic pulse micro-reactor studies using C[sub 4] hydrocarbons (n-butane, 1-butene) as reactants were conducted with this labeled catalyst. [sup 18]O incorporation into oxygenated products was determined by mass spectrometry. A comparison between the [sup 18]O content of products to those in various catalyst lattice sites allowed to associate specific surface layer reactive sites with the different mechanistic steps in the selective and nonselective pathways. These studies further revealed that n-butane is irreversibly chemisorbed and activated at the vanadyl dimer sites in a highly specific manner. Oxygen insertion at nearby V-O/[sup P]-V sites leads to form a furan-like surface species, which undergoes additional oxygen addition at P-O-V sites forming maleic anhydride. More than one nonselective pathways were evident: either by the direct combustion of n-butane, involving its cracking at V=O sites; or by the consecutive oxidation of the reaction intermediates and maleic anhydride. Reactivity of a site was found to be dependent on the nature of the hydrocarbon feed. Thus, the initial interaction of n-butane was found to be fundamentally different from 1-butene. Quantitative measurements showed that participation of the bulk oxygen is limited, and the redox mechanism is thus limited to a few near surface monolayers.

  14. Selective oxidation of C*4* hydrocarbons over (VO)*2*P*2*O*7 catalyst: Nature of the redox mechanism

    SciTech Connect

    Kamat, S.N.

    1992-09-09

    For selective oxidation of n-butane to maleic anhydride, (VO){sub 2}P{sub 2}O{sub 7} has been identified as the most active and selective V-P-0 phase. A three stage solid state procedure was used to synthesize a (VO){sub 2}P{sub 2}O{sub 7} catalyst labeled with {sup 18}O. Spectroscopy, etc. pointed to a highly site-specific {sup 18}O labeling. Anaerobic pulse micro-reactor studies using C{sub 4} hydrocarbons (n-butane, 1-butene) as reactants were conducted with this labeled catalyst. {sup 18}O incorporation into oxygenated products was determined by mass spectrometry. A comparison between the {sup 18}O content of products to those in various catalyst lattice sites allowed to associate specific surface layer reactive sites with the different mechanistic steps in the selective and nonselective pathways. These studies further revealed that n-butane is irreversibly chemisorbed and activated at the vanadyl dimer sites in a highly specific manner. Oxygen insertion at nearby V-O/{sup P}-V sites leads to form a furan-like surface species, which undergoes additional oxygen addition at P-O-V sites forming maleic anhydride. More than one nonselective pathways were evident: either by the direct combustion of n-butane, involving its cracking at V=O sites; or by the consecutive oxidation of the reaction intermediates and maleic anhydride. Reactivity of a site was found to be dependent on the nature of the hydrocarbon feed. Thus, the initial interaction of n-butane was found to be fundamentally different from 1-butene. Quantitative measurements showed that participation of the bulk oxygen is limited, and the redox mechanism is thus limited to a few near surface monolayers.

  15. Characterization of Dispersed Heteropoly Acid on Mesoporous Zeolite Using Solid-State P-31 NMR Spin-Lattice Relaxation

    SciTech Connect

    Zhu, Kake; Hu, Jian Z.; She, Xiaoyan; Liu, Jun; Nie, Zimin; Wang, Yong; Peden, Charles HF; Kwak, Ja Hun

    2009-09-01

    Dispersion and quantitative characterization of supported catalysts is a grand challenge in catalytic science. In this paper, heteropoly acid H3PW12O40 (HPA) is dispersed on mesoporous zeolite silicalite-1 derived from hydrothermal synthesis using carbon black nanoparticle templates, and the catalytic activity is studied for 1-butene isomerization. The HPAs supported on conventional zeolite and on mesoporous zeolite exhibit very different activities and thus provide good model systems to investigate the structure dependence of the catalytic properties. The HPA on mesoporous silicalite-1 shows enhanced catalytic activity for 1-butene isomerization, while HPA on conventional silicalite-1 exhibits low activity. To elucidate the structural difference, supported HPA catalysts are characterized using a variety of techniques, including 31P magic angle spinning nuclear magnetic resonance, and are shown to contain a range of species on both mesoporous and conventional zeolites. However, contrary to studies reported in the literature, conventional NMR techniques and chemical shifts alone do not provide sufficient information to distinguish the dispersed and aggregated surface species. The dispersed phase and the nondispersed phase can only be unambiguously and quantitatively characterized using spin-lattice relaxation NMR techniques. The HPA supported on mesoporous zeolite contains a fast relaxation component related to the dispersed catalyst, giving a much higher activity, while the HPA supported on conventional zeolite has essentially only the slow relaxation component with very low activity. The results obtained from this work demonstrate that the combination of spinning sideband fitting and spin-lattice relaxation techniques can provide detailed structural information on not only the Keggin structure for HPA but also the degree of dispersion on the support.

  16. Characterization of dispersed heteropoly Acid on mesoporous zeolite using solid-state 31P NMR spin-lattice relaxation.

    PubMed

    Zhu, Kake; Hu, Jianzhi; She, Xiaoyan; Liu, Jun; Nie, Zimin; Wang, Yong; Peden, Charles H F; Kwak, Ja Hun

    2009-07-22

    Dispersion and quantitative characterization of supported catalysts is a grand challenge in catalytic science. In this paper, heteropoly acid H(3)PW(12)O(40) (HPA) is dispersed on mesoporous zeolite silicalite-1 derived from hydrothermal synthesis using carbon black nanoparticle templates, and the catalytic activity is studied for 1-butene isomerization. The HPAs supported on conventional zeolite and on mesoporous zeolite exhibit very different activities and thus provide good model systems to investigate the structure dependence of the catalytic properties. The HPA on mesoporous silicalite-1 shows enhanced catalytic activity for 1-butene isomerization, while HPA on conventional silicalite-1 exhibits low activity. To elucidate the structural difference, supported HPA catalysts are characterized using a variety of techniques, including (31)P magic angle spinning nuclear magnetic resonance, and are shown to contain a range of species on both mesoporous and conventional zeolites. However, contrary to studies reported in the literature, conventional NMR techniques and chemical shifts alone do not provide sufficient information to distinguish the dispersed and aggregated surface species. The dispersed phase and the nondispersed phase can only be unambiguously and quantitatively characterized using spin-lattice relaxation NMR techniques. The HPA supported on mesoporous zeolite contains a fast relaxation component related to the dispersed catalyst, giving a much higher activity, while the HPA supported on conventional zeolite has essentially only the slow relaxation component with very low activity. The results obtained from this work demonstrate that the combination of spinning sideband fitting and spin-lattice relaxation techniques can provide detailed structural information on not only the Keggin structure for HPA but also the degree of dispersion on the support. PMID:19601683

  17. Structure-property evolution during polymer crystallization

    NASA Astrophysics Data System (ADS)

    Arora, Deepak

    The main theme of this research is to understand the structure-property evolution during crystallization of a semicrystalline thermoplastic polymer. A combination of techniques including rheology, small angle light scattering, differential scanning calorimetry and optical microscopy are applied to follow the mechanical and optical properties along with crystallinity and the morphology. Isothermal crystallization experiments on isotactic poly-1-butene at early stages of spherulite growth provide quantitative information about nucleation density, volume fraction of spherulites and their crystallinity, and the mechanism of connecting into a sample spanning structure. Optical microscopy near the fluid-to-solid transition suggests that the transition, as determined by time-resolved mechanical spectroscopy, is not caused by packing/jamming of spherulites but by the formation of a percolating network structure. The effect of strain, Weissenberg number (We ) and specific mechanical work (w) on rate of crystallization (nucleation followed by growth) and on growth of anisotropy was studied for shear-induced crystallization of isotactic poly-1-butene. The samples were sheared for a finite strain at the beginning of the experiment and then crystallized without further flow (Janeschitz-Kriegl protocol). Strain requirements to attain steady state/leveling off of the rate of crystallization were found to be much larger than the strain needed to achieve steady state of flow. The large strain and We>1 criteria were also observed for morphological transition from spherulitic growth to oriented growth. An apparatus for small angle light scattering (SALS) and light transmission measurements under shear was built and tested at the University of Massachusetts Amherst. As a new development, the polarization direction can be rotated by a liquid crystal polarization rotator (LCPR) with a short response time of 20 ms. The experiments were controlled and analyzed with a LabVIEW(TM) based code (LabVIEW(TM) 7.1) in real time. The SALS apparatus was custom built for ExxonMobil Research in Clinton NJ.

  18. Inhibitory Potency of 4-Carbon Alkanes and Alkenes toward CYP2E1 Activity

    PubMed Central

    Hartman, Jessica H.; Miller, Grover P.; Boysen, Gunnar

    2016-01-01

    CYP2E1 has been implicated in the bioactivation of many small molecules into reactive metabolites which form adducts with proteins and DNA, and thus a better understanding of the molecular determinants of its selectivity are critical for accurate toxicological predictions. In this study, we determined the potency of inhibition of human CYP2E1 for various 4-carbon alkanes, alkenes and alcohols. In addition, known CYP2E1 substrates and inhibitors including 4-methylpyrazole, aniline, and dimethylnitrosamine were included to determine their relative potencies. Of the 1,3-butadiene-derived metabolites studied, 3,4-epoxy-1-butene was the strongest inhibitor with an IC50 of 110 μM compared to 1700 μM and 6600 μM for 1,2-butenediol and 1,2:3,4-diepoxybutane, respectively. Compared to known inhibitors, inhibitory potency of 3,4-epoxy-1-butene is between 4-methylpyrazole (IC50 = 1.8 μM) and dimethylnitrosamine (IC50 = 230 μM). All three butadiene metabolites inhibit CYP2E1 activity through a simple competitive mechanism. Among the 4-carbon compounds studied, the presence and location of polar groups seems to influence inhibitory potency. To further examine this notion, the investigation was extended to include structurally and chemically similar analogs, including propylene oxide and various butane alcohols. Those results demonstrated preferential recognition of CYP2E1 toward the type and location of polar and hydrophobic structural elements. Taken together, CYP2E1 metabolism may be modified in vivo by exposure to 4-carbon compounds, such as drugs, and nutritional constituents, a finding that highlights the complexity of exposure to mixtures. PMID:24561005

  19. Decarboxylative-coupling of allyl acetate catalyzed by group 10 organometallics, [(phen)M(CH3)]+.

    PubMed

    Woolley, Matthew; Ariafard, Alireza; Khairallah, George N; Kwan, Kim Hong-Yin; Donnelly, Paul S; White, Jonathan M; Canty, Allan J; Yates, Brian F; O'Hair, Richard A J

    2014-12-19

    Gas-phase carbon-carbon bond forming reactions, catalyzed by group 10 metal acetate cations [(phen)M(O2CCH3)](+) (where M = Ni, Pd or Pt) formed via electrospray ionization of metal acetate complexes [(phen)M(O2CCH3)2], were examined using an ion trap mass spectrometer and density functional theory (DFT) calculations. In step 1 of the catalytic cycle, collision induced dissociation (CID) of [(phen)M(O2CCH3)](+) yields the organometallic complex, [(phen)M(CH3)](+), via decarboxylation. [(phen)M(CH3)](+) reacts with allyl acetate via three competing reactions, with reactivity orders (% reaction efficiencies) established via kinetic modeling. In step 2a, allylic alkylation occurs to give 1-butene and reform metal acetate, [(phen)M(O2CCH3)](+), with Ni (36%) > Pd (28%) > Pt (2%). Adduct formation, [(phen)M(C6H11O2)](+), occurs with Pt (24%) > Pd (21%) > Ni(11%). The major losses upon CID on the adduct, [(phen)M(C6H11O2)](+), are 1-butene for M = Ni and Pd and methane for Pt. Loss of methane only occurs for Pt (10%) to give [(phen)Pt(C5H7O2)](+). The sequences of steps 1 and 2a close a catalytic cycle for decarboxylative carbon-carbon bond coupling. DFT calculations suggest that carbon-carbon bond formation occurs via alkene insertion as the initial step for all three metals, without involving higher oxidation states for the metal centers. PMID:25329236

  20. VOCs Speciation From Steam Boiler Stacks of Industries Located in Naucalpan

    NASA Astrophysics Data System (ADS)

    Mejia, G. M.; Tejeda, D. D.; Bremauntz, M. P.; Valdez, A.; Montufar, P. C.; Martinez, M. A.; Sierra, M. J.; Gonzalez, C. A.

    2007-05-01

    Results of VOCs speciation from industrial steam boiler stacks located in Naucalpan are presented and discussed. This municipality is located north of the Metropolitan Zone of the Valley of Mexico (MZVM). Speciation of VOCs is important to generate information about sources of pollution, to update emission inventories, to study the dynamics of pollutants in the atmosphere, and to estimate possible risks of population exposure. This information is valuable for decision making on air pollution control strategies. Samples from 35 steam boilers form industries burning Diesel, LPG, or CNG were taken using the US-EPA Method 18. Selected samples from the use of different fuels were analyzed using gas chromatography and flame ionization detection (GC-FID) according to US-EPA protocol TO-14. The VOCs analyzed included alkanes of 9 carbons or less, alkenes of 7 carbons or less and aromatics (families of benzene). The results show consistency on the VOCs detected on Diesel samples. The main compounds found were 1- Butene+iButylene, m/p-Xylene, Ethane, Propene, Propane, Acetylene, 2Me-1Butene, and Toluene. The average concentrations of these compounds were in the range of 130 to 385 ppbC. The results of LPG samples did not show a definite pattern of VOCs, although light components predominate and, in some samples, Toluene and Xylene. These last components were not expected for industries reporting the use of LPG, perhaps due to the use of a combination of fuels and mistakes in the reports of fuel used at the time of sampling. The analysis of CNG samples show predominance of light VOCs, in the range of 90 to 300 ppbC. As in the case of LPG, some aromatics showed high concentrations in some samples analyzed perhaps due to the use of different fuels in the boiler. The results of this study are the first results of VOCs speciation obtained form exhaust gases from stacks of Mexican industries. The data reported are valuable to analyze emission inventories of VOCs and to better understand the dynamics of pollutants in the MZVM.

  1. Model vanadium-phosphorus-oxygen catalysts for the selective oxidation of C/sub 4/ hydrocarbons to maleic anhydride

    SciTech Connect

    Moser, T.P.

    1987-06-01

    Two model vanadium-phosphorus-oxygen catalysts, ..beta..-VOPO/sub 4/ and (VO)/sub 2/P/sub 2/O/sub 7/, were investigated for the selective oxidation of C/sub 4/ hydrocarbons to maleic anhydride. In situ laser Raman spectroscopy was used. Complementary techniques including x-ray powder diffraction and x-ray photoelectron spectroscopy were used for characterization of the fresh and used catalytic materials. The direct observation of phase stability and the participation of lattice oxygen during catalysis was possible using the in situ Raman technique. In particular, ..beta..-VOPO/sub 4/ and (VO)/sub 2/P/sub 2/O/sub 7/ demonstrated bulk structural integrity during n-butane oxidation. The relatively greater reducing capacity of 1-butene induced the ..beta..-VOPO/sub 4/ to (VO)/sub 2/P/sub 2/O/sub 7/ phase transformation. Direct structural identification of catalytically active centers for paraffin and olefin oxidation were investigated using an /sup 18/O-enriched ..beta..-VOPO/sub 4/ phase catalyst. Active sites responsible for complete combustion (Site I) and selective oxidation (Site II) were identified. The selective route for 1-butene oxidation involved predominantly Site II centers, while Site I centers were associated with complete combustion. In contrast, n-butane oxidation required the highly active Site I centers for initial activation and for the formation of an intermediate containing two oxygen atoms. Raman band assignments indicated these oxygen sites were associated with PO/sub 4/ units in the ..beta..-VOPO/sub 4/ lattice. Maleic anhydride conversion was particularly sensitive to the catalytic phase present. Significant combustion activity was observed when maleic anhydride was fed directly to an integral flow reactor charged with model catalysts. The combustion activity was least for (VO)/sub 2/P/sub 2/O/sub 7/, nominally a V(IV) phase. The ..beta..-VOPO/sub 4/ catalyst, nominally a V(V) phase, resulted in increased conversions of maleic anhydride.

  2. Synthesis, characterization and catalytic applications of vanadia and silica-based materials

    NASA Astrophysics Data System (ADS)

    Yeragi, Dinesh Chandrakant

    Vanadia gels synthesized from a peroxovanadate precursor were used as catalysts for the selective oxidation of 1,3-butadiene. These vanadia gels were previously characterized using 51V and 17O MAS NMR spectroscopy [Fontenot et al., J. Phys. Chem. B 105, p10496 (2000) and J. Am. Chem. Soc. 124, p8435 (2002)]. These studies had shown the presence of an incommensurate shifted layer (+- 1.7 A along a-axis and +- 0.5 A along the b-axis) between two commensurate layers of the vanadia gel. This created a special site for water adsorption in which the oxygen of the water molecule was adsorbed trans to the vanadyl oxygen and the two hydrogen atoms co-ordinated with two vanadyl oxygens of the next layer. Selective oxidation studies of 1,3-butadiene were carried out with and without water addition to the feed stream to understand the role of oxygen sites and the water adsorption site in the vanadia gel structure for hydrocarbon oxidation. The reaction mechanism involved intermediates such as 3,4-epoxy-1-butetne, crotonaldehyde, 2,5-dihydrofuran, 2-butene-1,4-dial and furan. The effect of water addition on the pathway for 1,3-butadiene selective oxidation was also investigated over peroxovanadate-derived vanadia and VMoO catalysts by using 3,4-epoxy-1-butene, crotonaldehyde, 2,5-dihydrofuran and furan as feed. Addition of 0-12% water to a reactant feed of 1.4% butadiene in an air-He mixture significantly increased catalytic activity and selectivity for crotonaldehyde and furan. Competitive adsorption was believed to occur between the hydrocarbon products and water; formation of acid sites through dissociative adsorption of water was also believed to be important. Temperature programmed desorption (TPD) experiments revealed five distinct adsorption sites that could be associated with terminal V=O, corner sharing V-O-V, and edge sharing V-O oxygen. The adsorption of water trans to the vanadyl oxygen (V=O) formed an equilibrium structure resulting in the increased reactivity of the vanadyl oxygen species for 1,2-electrophilic addition across the C=C double bond in 1,3-butadiene to form 3,4-epoxy-1-butene. A proposed dissociative mechanism of adsorbed water on the catalyst surface resulted in acidic H+ species that participated in ring opening mechanisms and nucleophilic O-2 species that could easily exchange with the lattice oxygen sites, thus replenishing the catalytic activity.

  3. Determining the melt miscibility of commercial polyolefin blends by Small-Angle Light Scattering

    NASA Astrophysics Data System (ADS)

    Peng, Ping

    2005-03-01

    The melt miscibility of high-density polyethylene (HDPE) (Mw = 52 kg/mol, PDI = 2.9) and linear low-density polyethylenes (LLDPEs) based on homogeneous ethylene-1-butene copolymers (EB0187: 18.7 mol% butene branches, Mw = 58.1 kg/mol and EB0059: 5.9 mol% butene branches, Mw = 70 kg/mol) is determined by Small-Angle Light Scattering (SALS) under parallel-polarized optical alignment. Blends with branching density differences (?y) ranging from 5.9 to 18.7 mol% were studied. For the HDPE/EB0187 blend, (?y = 18.7%), cooling and isothermal measurements (2 h) in the melt can be used to determine the miscibility and the phase boundary. When this blend is rapidly cooled room temperature, the resulting SALS patterns show that the size of phase separated domain ( 1 ?m) is much smaller than the average spherulite size (68 ?m). These results consist with our microscopic observations and the transmitted light measured simultaneously with the VV scattering in the melt. From the compositions studied, we can conclude that this blend exhibits UCST behavior. For blends with lower ?y, isothermal measurements provide a sensitive means for determining the melt miscibility. Based on the above observations, we can conclude that SALS can be used to determine the melt miscibility of polyolefin blends.

  4. Gas-Phase and Computational Study of Identical Nickel- and Palladium-Mediated Organic Transformations Where Mechanisms Proceeding via M(II) or M(IV) Oxidation States Are Determined by Ancillary Ligands.

    PubMed

    Vikse, Krista L; Khairallah, George N; Ariafard, Alireza; Canty, Allan J; O'Hair, Richard A J

    2015-10-28

    Gas-phase studies utilizing ion-molecule reactions, supported by computational chemistry, demonstrate that the reaction of the enolate complexes [(CH2CO2-C,O)M(CH3)](-) (M = Ni (5a), Pd (5b)) with allyl acetate proceed via oxidative addition to give M(IV) species [(CH2CO2-C,O)M(CH3)(?(1)-CH2-CH?CH2)(O2CCH3-O,O')](-) (6) that reductively eliminate 1-butene, to form [(CH2CO2-C,O)M(O2CCH3-O,O')](-) (4). The mechanism contrasts with the M(II)-mediated pathway for the analogous reaction of [(phen)M(CH3)](+) (1a,b) (phen = 1,10-phenanthroline). The different pathways demonstrate the marked effect of electron-rich metal centers in enabling higher oxidation state pathways. Due to the presence of two alkyl groups, the metal-occupied d orbitals (particularly dz(2)) in 5 are considerably destabilized, resulting in more facile oxidative addition; the electron transfer from dz(2) to the C?C ?* orbital is the key interaction leading to oxidative addition of allyl acetate to M(II). Upon collision-induced dissociation, 4 undergoes decarboxylation to form 5. These results provide support for the current exploration of roles for Ni(IV) and Pd(IV) in organic synthesis. PMID:26469559

  5. [Aluminum coordination and active sites on aluminas, Y-zeolites and pillared layered silicates]. Progress report

    SciTech Connect

    Fripiat, J.J.

    1994-02-01

    This report is organized in four sections. In the first the authors will outline structural features which are common to all fine grained alumina, as well as to non-framework alumina in zeolites. This section will be followed by a study of the surface vs. bulk coordination of aluminum. The third section will deal with measurement of the number of acid sites and the scaling of their strength. The fourth and last section will describe three model reactions: the isomerization of 1-butene and of 2 cis-butene; the isomerization and disproportionation of oxtho-xylene; and the transformation of trichloroethane into vinyl chloride followed by the polymerization of the vinyl chloride. The relationship between chemical activity and selectivity and what is known of the local structure of the active catalytic sites will be underlined. Other kinds of zeolites besides Y zeolite have been studied. Instead of the aluminum pillared silicates they found it more interesting to study the substitution of silicon by aluminum in a layered structure containing a permanent porosity (aluminated sepiolite).

  6. Explosive photodissociation of methane induced by ultrafast intense laser

    SciTech Connect

    Kong Fanao; Luo Qi; Xu Huailiang; Sharifi, Mehdi; Song Di; Chin, See Leang

    2006-10-07

    A new type of molecular fragmentation induced by femtosecond intense laser at the intensity of 2x10{sup 14} W/cm{sup 2} is reported. For the parent molecule of methane, ethylene, n-butane, and 1-butene, fluorescence from H (n=3{yields}2), CH (A {sup 2}{delta}, B {sup 2}{sigma}{sup -}, and C {sup 2}{sigma}{sup +}{yields}X {sup 2}{pi}), or C{sub 2} (d {sup 3}{pi}{sub g}{yields}a {sup 3}{pi}{sub u}) is observed in the spectrum. It shows that the fragmentation is a universal property of neutral molecule in the intense laser field. Unlike breaking only one or two chemical bonds in conventional UV photodissociation, the fragmentation caused by the intense laser undergoes vigorous changes, breaking most of the bonds in the molecule, like an explosion. The fragments are neutral species and cannot be produced through Coulomb explosion of multiply charged ion. The laser power dependence of CH (A{yields}X) emission of methane on a log-log scale has a slope of 10{+-}1. The fragmentation is thus explained as multiple channel dissociation of the superexcited state of parent molecule, which is created by multiphoton excitation.

  7. Temperature and Loading-Dependent Diffusion of Light Hydrocarbons in ZIF-8 as Predicted Through Fully Flexible Molecular Simulations.

    PubMed

    Verploegh, Ross J; Nair, Sankar; Sholl, David S

    2015-12-23

    Accurate and efficient predictions of hydrocarbon diffusivities in zeolitic imidazolate frameworks (ZIFs) are challenging, due to the small pore size of materials such as ZIF-8 and the wide range of diffusion time scales of hydrocarbon molecules in ZIFs. Here we have computationally measured the hopping rates of 15 different molecules (kinetic diameters of 2.66-5.10 ) in ZIF-8 via dynamically corrected transition state theory (dcTST). Umbrella sampling combined with the one-dimensional weighted histogram analysis method (WHAM) was used to calculate the diffusion free energy barriers. Both the umbrella sampling and dynamical correction calculations included ZIF-8 flexibility, which is found to be critical in accurately describing molecular diffusion in this material. Comparison of the computed diffusivities to extant experimental results shows remarkable agreement within an order of magnitude for all the molecules. The dcTST method was also applied to study the effect of hydrocarbon loadings. Self and transport diffusion coefficients of methane, ethane, ethylene, propane, propylene, n-butane, and 1-butene in ZIF-8 are reported over a temperature range of 0-150 C and loadings from infinite dilution to liquid-like loadings. PMID:26606267

  8. On the performance of FAU and MFI zeolites for the adsorptive removal of a series of volatile organic compounds from air using molecular simulation.

    PubMed

    Calero, S; Gmez-lvarez, P

    2015-10-21

    Volatile organic compound (VOC) emissions can cause serious risk to human health and the environment. In this work, we used Monte Carlo simulations to assess the performance of industrially important zeolites for the adsorption-based removal of a number of common air pollutants, particularly small saturated and unsaturated hydrocarbons: propane, butane, propene, and 1-butene. We focused on the cage-like FAU and channel-like MFI zeolites. The adsorption isotherms of the multicomponent N2/O2/Ar/VOC mixtures at real concentrations and room temperature reveal a considerable influence of the host topology and pore dimensions. While the adsorption of the VOCs from the mixture in FAU is almost negligible, it is remarkable in MFI. The adsorption selectivity of each VOC over the air compounds exhibits a maximum at about 10(6)-10(7) Pa, and then decreases to virtually zero due to entropic effects. This behaviour for selectivity is maintained regardless of the chain length and the presence of double bonds in the VOC, but the values are indeed affected. Also, we examined the selectivity at 10(7) Pa for a number of other widely used zeolites, with pore features ensuring the diffusion of the adsorbates. Apart from MFI, we also found the channel-like MEL and MTW zeolite candidates for the targeted air decontamination. PMID:26392021

  9. Selective photooxidation of small alkenes by O[sub 2] with red light in zeolite Y

    SciTech Connect

    Blatter, F.; Frei, H. )

    1994-03-09

    Upon loading number of UV photons per unit a and O[sub 2] into zeolite NaY, photochemistry was observed at wavelengths as long as 760 nm. Similarly, photoexcitation of trans- or cis-2-butene and O[sub 2] in this zeolite resulted in chemical reaction at a threshold wavelength of 600 nm. Reactions were initiated either with filtered tungsten-source light or the emission of a CW dye laser and typically conducted at -50[degree]C. Products identified by FT-infrared spectroscopy were 2,3-dimethyl-3-hydroperoxy-l-butene (>90%) and acetone in the case of DMB + O[sub 2]. trans- or cis-2-butene + O[sub 2] gave exclusively 3-hydroperoxy-1-butene. This constitutes the first synthesis of this hydroperoxide by direct photolysis of 2-butene-O[sub 2] pairs. Laser reaction excitation spectra in the 500-700-nm region revealed a continuous absorption for both the DMB[center dot]O[sub 2] and the 2-butene-O[sub 2] systems. It is attributed to a charge-transfer transition. Comparison with corresponding absorption spectra in conventional media shows that the excited alkene-O[sub 2] charge-transfer states are stabilized by electrostatic interactions with the zeolite NaY environment by 12 000cm[sup [minus]1]. Substantially less stabilization was observed in high-silica faujasite. 50 refs., 10 figs., 2 tabs.

  10. Structure determination and sensory analysis of bitter-tasting 4-vinylcatechol oligomers and their identification in roasted coffee by means of LC-MS/MS.

    PubMed

    Frank, Oliver; Blumberg, Simone; Kunert, Christof; Zehentbauer, Gerhard; Hofmann, Thomas

    2007-03-01

    Aimed at elucidating intense bitter-tasting molecules in coffee, various bean ingredients were thermally treated in model experiments and evaluated for their potential to produce bitter compounds. As caffeic acid was found to generate intense bitterness reminiscent of the bitter taste of a strongly roasted espresso-type coffee, the reaction products formed were screened for bitter compounds by means of taste dilution analysis, and the most bitter tastants were isolated and purified. LC-MS/MS as well as 1-D/2-D NMR experiments enabled the identification of 10 bitter compounds with rather low recognition threshold concentrations ranging between 23 and 178 micromol/L. These bitter compounds are the previously unreported 1,3-bis(3',4'-dihydroxyphenyl) butane, trans-1,3-bis(3',4'-dihydroxyphenyl)-1-butene, and eight multiply hydroxylated phenylindanes, among which five derivatives are reported for the first time. In addition, the occurrence of each of these bitter compounds in a coffee brew was verified by means of LC-MS/MS (ESI-) operating in the multiple reaction monitoring (MRM) mode. The structures of these bitter compounds show strong evidence that they are generated by oligomerization of 4-vinylcatechol released from caffeic acid moieties upon roasting. PMID:17269788

  11. ( l brace (. eta. sup 5 -C sub 5 Me sub 4 )Me sub 2 Si(. eta. sup 1 -NCMe sub 3 ) r brace (PMe sub 3 )ScH) sub 2 : A unique example of a single-component. alpha. -olefin polymerization catalyst

    SciTech Connect

    Shapiro, P.J.; Bunel, E.; Schaefer, W.P.; Bercaw, J.E. )

    1990-03-01

    The synthesis and structure of the title compound are described. ({l brace}({eta}{sup 5}-C{sub 5}Me{sub 4})Me{sub 2}Si({eta}{sup 1}-NCMe{sub 3}){r brace}Sc(PMe{sub 3})){sub 2}({mu}-H){sub 2} (3) crystallizes with a molecule of toluene per scandium in the monoclinic system, space group C2/c, with a = 21.238 (3) {angstrom}, b = 11.470 (2) {angstrom}, c = 22.253 (3) {angstrom}, {beta} = 113.16 (1){degree}, V = 4984.0 (14) {angstrom}{sup 3}, Z = 8 (four dimers), and d = 1.24 g{center dot}cm{sup {minus}3}. Propene, 1-butene, and 1-pentene are cleanly, albeit slowly, polymerized with >99% head-to-tail coupling to produce linear, atactic polymers with M{sub n} = 3,000-4,000 and PDI's of 1.7-2.1. Chain transfer is relatively slow and appears to occur by {beta}-H elimination. All evidence points to a one-component catalyst system with all scandium centers functioning alike.

  12. Characteristics of volatile organic compounds from motorcycle exhaust emission during real-world driving

    NASA Astrophysics Data System (ADS)

    Tsai, Jiun-Horng; Huang, Pei-Hsiu; Chiang, Hung-Lung

    2014-12-01

    The number of motorcycles has increased significantly in Asia, Africa, Latin American and Europe in recent years due to their reasonable price, high mobility and low fuel consumption. However, motorcycles can emit significant amounts of air pollutants; therefore, the emission characteristics of motorcycles are an important consideration for the implementation of control measures for motorcycles in urban areas. Results of this study indicate that most volatile organic compound (VOC) emission factors were in the range of several decades mg/km during on-road driving. Toluene, isopentane, 1,2,4-trimethylbenzene, m,p-xylene, and o-xylene were the most abundant VOCs in motorcycle exhaust, with emission factors of hundreds mg/km. Motorcycle exhaust was 15.4 mg/km for 15 carbonyl species. Acetaldehyde, acetone, formaldehyde and benzaldehyde were the major carbonyl species, and their emission factors ranged from 1.4 to 3.5 mg/km 1,2,4-trimethylbenzene, m,p-xylene, 1-butene, toluene, o-xylene, 1,2,3-trimethylbenzene, propene, 1,3,5-trimethylbenzene, isoprene, m-diethylbenzene, and m-ethyltoluene were the main ozone formation potential (OFP) species, and their OFP was 200 mg-O3/km or higher.

  13. The effect of rhenium, sulfur and alumina on the conversion of hydrocarbons over platinum single crystals: Surface science and catalytic studies

    SciTech Connect

    Kim, C.

    1992-04-01

    Conversion reactions of hydrocarbons over Pt-Re model catalyst surfaces modified by sulfur and alumina have been studied. A plasma deposition source has been developed to deposit Pt, Re, and Al on metal substrates variable coverage in ultrahigh vacuum without excessive heating. Conversion of n-hexane was performed over the Re-covered Pt and Pt-covered Re surfaces. The presence of the second metal increased hydrogenolysis activity of both Pt-Re surfaces. Addition of sulfur on the model Catalyst surfaces suppressed hydrogenolysis activity and increased the cyclization rate of n-hexane to methylcyclopentane over Pt-Re surfaces. Sulfiding also increased the dehydrogenation rate of cyclohexane to benzene Over Pt-Re surfaces. It has been proposed that the PtRe bimetallic catalysts show unique properties when combined with sulfur, and electronic interactions exist between platinum, rhenium and sulfur. Decomposition of hydrocarbons on the sulfur-covered Pt-Re surfaces supported that argument. For the conversion of 1-butene over the planar Pt/AlO{sub x}, the addition of Pt increased the selectivity of hydrogenation over isomerization.

  14. The effect of rhenium, sulfur and alumina on the conversion of hydrocarbons over platinum single crystals: Surface science and catalytic studies

    SciTech Connect

    Kim, C.

    1992-04-01

    Conversion reactions of hydrocarbons over Pt-Re model catalyst surfaces modified by sulfur and alumina have been studied. A plasma deposition source has been developed to deposit Pt, Re, and Al on metal substrates variable coverage in ultrahigh vacuum without excessive heating. Conversion of n-hexane was performed over the Re-covered Pt and Pt-covered Re surfaces. The presence of the second metal increased hydrogenolysis activity of both Pt-Re surfaces. Addition of sulfur on the model Catalyst surfaces suppressed hydrogenolysis activity and increased the cyclization rate of n-hexane to methylcyclopentane over Pt-Re surfaces. Sulfiding also increased the dehydrogenation rate of cyclohexane to benzene Over Pt-Re surfaces. It has been proposed that the PtRe bimetallic catalysts show unique properties when combined with sulfur, and electronic interactions exist between platinum, rhenium and sulfur. Decomposition of hydrocarbons on the sulfur-covered Pt-Re surfaces supported that argument. For the conversion of 1-butene over the planar Pt/AlO[sub x], the addition of Pt increased the selectivity of hydrogenation over isomerization.

  15. Preventive activity of olive oil phenolic compounds on alkene epoxides induced oxidative DNA damage on human peripheral blood mononuclear cells.

    PubMed

    Fuccelli, Raffaela; Sepporta, Maria Vittoria; Rosignoli, Patrizia; Morozzi, Guido; Servili, Maurizio; Fabiani, Roberto

    2014-01-01

    The aim of this study was to investigate the ability of epoxides of styrene (styrene-7,8-oxide; SO) and 1,3-butadiene (3,4-epoxy-1-butene; 1,2:3,4:-diepoxybutane) to cause oxidative stress and oxidative DNA damage on human peripheral blood mononuclear cells (PBMCs) and whether a complex mixture of olive oil phenols (OOPE) could prevent these effects. The DNA damage was measured by the single-cell gel electrophoresis (SCGE; comet assay). We found that the DNA damage induced by alkene epoxides could be prevented by N-acetyl-cysteine (10 mM) and catalase (100 U/ml). Alkene epoxides caused a significant (P < 0.05) increase of both peroxide concentration in extra- and intracellular environment and formamidopyrimidine DNA glycosylase (FPG)- and Endonuclease III (ENDO III)-sensitive sites in PBMCs, demonstrating the presence of oxidized bases. OOPE (1 ?g of total phenols/ml) was able to prevent the alkene epoxide induced DNA damage both after 2 and 24 h of incubation. In addition, OOPE completely inhibited the SO-induced intracellular peroxide accumulation in PBMCs and prevented the oxidative DNA damage induced by SO, as evidenced by the disappearance of both FPG- and ENDO III-sensitive sites. This is the first study demonstrating the ability of OOPE to prevent the DNA damage induced by alkene epoxides providing additional information about the chemopreventive properties of olive oil. PMID:25299479

  16. Fluid loss agents for oil well cementing composition

    SciTech Connect

    Savoly, A.; Villa, J.L.; Garvey, C.M.; Resnick, A.L.

    1987-06-23

    This patent describes a method of cementing a conduit in a borehole penetrating an earthen formation by introducing a cementing composition into the space. The cementing composition comprises: water; hydraulic cement; a water dispersible fluid loss additive comprised of a terpolymer of (1) from about 10 to about 75 weight percent of an acid selected from the group consisting of 2-acrylamido-2 methylpropane sulfonic acid, sodium vinyl sulfonate and vinyl benzene sulfonate; (2) from about 10 to 76 weight percent of a nonionic monomer selected from the group consisting of acrylamide, N,N-dimethylacrylamide, N-vinyl pyrrolidone, N-vinyl acetamide and dimethylamino ethyl methacrylate; and (3) from about 1 to 60 weight percent of an unsaturated polybasic acid selected from the group consisting of itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, dimethylmuconic acid and 1-butene 2,3,4-tricarboxylic acid, the polymer having an average molecular weight of between about 200,000 and about 1,000,000 being in its free acid or partially or completely neutralized form and being at least water dispersible.

  17. Photochemistry of 1 and 2-(2-methylphenyl)-1,6-heptadiene. [4a-methyl-1,2,3,4,4a,9,10,10a-octahydrophenanthrene

    SciTech Connect

    Barrows, R.D.; Hornback, J.M.

    1982-01-01

    In an attempt to synthesize partially saturated phenanthrene derivatives by an intramolecular Diels-Alder reaction between a photochemically produced o-xylylene (diene) and a tethered dienophile, it was found that 1 and 2 underwent a photochemically allowed (2 + 2) cycloaddition. Irradiation of 1 gave 6-(2-methylphenyl)bicyclo(3.2.0)heptane in 86% yield. Upon irradiation of 2, a benzvalene rearrangement of 2 first took place, producing the meta isomer 2-(3-methylphenyl)-1,6-heptadiene, followed by a (2 + 2) photocycloaddition giving 1-(3-methylphenyl)bicyclo(3.2.0)heptane in 15% yield. Direct irradiation of 2-(3-methylphenyl)-1,6-heptadiene gave the same bicyclo derivative as 2 in 34% yield. Examination of the fluorescence spectra of 1 and 2 in comparison with 1-(2-methylphenyl)propene and 2-(2-methylphenyl)-1-butene, respectively, has shown that 1 may be biased toward (2 + 2) cycloaddition where 2 is not biased toward (2 + 2) photocycloization. Attempts to produce 4a-methyl-1,2,3,4,4a,9,10,10a-octahydrophenanthrene by an intramolecular Diels-Alder reaction of the o-xylylene produced by irradiation of 3 will also be described.

  18. [Emission Characteristics of VOCs from Typical Restaurants in Beijing].

    PubMed

    Cui, Tong; Cheng, Jing-chen; He, Wan-qing; Ren, Pei-fang; Nie, Lei; Xu, Dong-yao; Pan, Tao

    2015-05-01

    Using the EPA method, emission of volatile organic compounds (VOCs) , sampled from barbecue, Chinese and Western fast-food, Sichuan cuisine and Zhejiang cuisine restaurants in Beijing was investigated. VOCs concentrations and components from different cuisines were studied. The results indicated that based on the calibrated baseline ventilation volume, the VOCs emission level from barbecue was the highest, reaching 12.22 mg m(-3), while those from fast-food of either Chinese or Western, Sichuan cuisine and Zhejiang cuisine were about 4 mg m(-3). The components of VOCs from barbecue were different from those in the other cuisines, which were mainly propylene, 1-butene, n-butane, etc. The non-barbecue cuisines consisted of high concentration of alcohols, and Western fast-food contained relatively high proportion of aldehydes and ketones organic compounds. According to emission concentration of baseline ventilation volume, barbecue released more pollutants than the non-barbecue cuisines at the same scale. So, barbecue should be supervised and controlled with the top priority. PMID:26314095

  19. Karplus Equation for (3)JHH Spin-Spin Couplings with Unusual (3)J(180) < (3)J(0) Relationship.

    PubMed

    Contreras, R H; Suardaz, R; Prez, C; Crespo-Otero, R; San Fabin, J; Garca de la Vega, J M

    2008-09-01

    Vicinal (3)JHH coupling constants for monosubstituted ethane molecules present the unusual relationship (3)JHH (180) < (3)JHH (0) when the substituent contains bonding and antibonding orbitals with strong hyperconjugative interactions involving bond and antibond orbitals of the ethane fragment. This anomalous behavior is studied as a function of the substituent rotation for three model systems (propanal, thiopropanal, and 1-butene) at the B3LYP/TZVP level. The consistency of this level of theory to study this problem is previously established using different ab initio methods and larger basis sets. The origin of the unusual (3)JHH(180) - (3)JHH(0) relationship is attributed to simultaneous ?/? hyperconjugative interactions ?C?-H? ? ?*Cc?X, and ?C?-C? ? ?*Cc?X. These interactions depend on the substituent rotation and their effects are different for (3)JHH(180) than for (3)JHH(0). The modelization carried out shows an increase of those effects as the substituent changes from weaker (CH?CH2) to stronger (CH?S) electron acceptor ?*C?X. PMID:26621434

  20. Ruta montana L. leaf essential oil and extracts: characterization of bioactive compounds and suppression of crown gall disease.

    PubMed

    Hammami, Ins; Smaoui, Slim; Hsouna, Anis Ben; Hamdi, Naceur; Triki, Mohamed Ali

    2015-01-01

    The aims of this study were to assess the antimicrobial efficacy of the leaf essential oil and the leaf extracts of R. montana against Botrytis cinerea, Fusarium oxysporum, Verticillium dahliae, Aspergillus oryzae and Fusarium solani. The oil (1.000 g/disk) and the extracts (1.500 g/disk) revealed a remarkable antifungal effect against the tested plant pathogenic fungi with a radial growth inhibition percentage of 40.0-80.0 % and 5.0-58.0 %, respectively along with their respective MIC values ranging from 100 to 1100 g/mL and 250 to 3000 g/mL. The oil had a strong detrimental effect on spore germination of all the tested plant pathogens along with the concentration as well as time-dependent kinetic inhibition of Fusarium oxysporum. Also, the oil exhibited a potent in vivo antifungal effect against Botrytis cinerea on tomato plants. Experiments carried out in plant revealed that the essential oil was slightly effective in suppression of gall formation induced by Agrobacterium tumefaciens on bitter almond. The results of this study indicate that the oil and extracts of R. montana leaves could become natural alternatives to synthetic fungicides to control certain important plant microbial diseases. The GC-MS analysis determined that 28 compounds, which represented 89.03 % of total oil, were present in the oil containing mainly 1-butene, methylcyclopropane, 2-butene and caryophyllene oxide. PMID:26417353

  1. Structure sensitivity in oxide catalysis

    SciTech Connect

    Kung, H.H.

    1983-03-01

    In this paper it is shown that similar to metal catalysis, metal oxide catalysis can be dependent upon crystalline structure. Two types of structure sensitivity are demonstrated. In one, activity and sensitivity depend upon crystalline size. In the other, they depend on the crystal plane. Comparison of the activity and selectivity of ..cap alpha..-Fe/sub 2/O/sub 3/ with that of ..gamma..-Fe/sub 2/O/sub 3/ in the catalysis of the dehydrogenation of 1-butene to butadiene reveals that the latter is three times more active than the ..cap alpha..-form and that crystalline size and possibly surface structure determine catalytic activity. The ZnO catalysis of methanol conversion to methane, CO and CO/sub 2/ was studied using D/sub 3/COD and CH/sub 3/OD. Catalytic activity and selectivity is solely a function of surface structure. Of the four ZnO surfaces studied using a temperature-dependent programmed desorption technique (single crystal), (flat, non polar-10bar10, stepped-50bar51 and 40bar41, and the Zn polar surfaces-0001), the stepped 40bar41 surface (4 ZnO units/terrace) was the most active.

  2. Hydrocarbon Source Signatures in Houston, Texas: Influence of the Petrochemical Industry

    SciTech Connect

    Jobson, B Tom T.; Berkowitz, Carl M.; Kuster, W. C.; Goldan, P. D.; Williams, E. J.; Fesenfeld, F.; Apel, Eric; Karl, Thomas G.; Lonneman, William A.; Riemer, D.

    2004-12-22

    Observations of C1-C10 hydrocarbon mixing ratios measured by in-situ instrumentation at the La Porte super site during the TexAQS 2000 field experiment are reported. The La Porte data were compared to a roadway vehicle exhaust signature obtained from canister samples collected in the Houston Washburn tunnel during the same summer to better understand the impact of petrochemical emissions of hydrocarbons at the site. It is shown that the abundance of ethene, propene, 1-butene, C2-C4 alkanes, hexane, cyclohexane, methylcyclohexane, isopropylbenzene, and styrene at La Porte were systematically impacted by petrochemical industry emissions. Coherent power law relationships between frequency distribution widths of hydrocarbon mixing ratios and their local lifetimes clearly identify two major source groups, roadway vehicle emissions and industrial emissions. Distributions of most aromatics and long chain alkanes were consistent with roadway vehicle emissions as the dominant source. Airmass reactivity was generally dominated by C1-C3 aldehydes. Propene and ethene sometimes dominated air mass reactivity with HO loss frequencies often greater than 10 s-1. Ozone mixing ratios near 200 ppbv were observed on two separate occasions and these air masses appear to have been impacted by industrial emissions of alkenes from the Houston Ship Channel. The La Porte data provide evidence of the importance of industrial emissions of ethene and propene on air masses reactivity and ozone formation in Houston.

  3. Pyrolytic product characteristics of biosludge from the wastewater treatment plant of a petrochemical industry.

    PubMed

    Lin, Kuo-Hsiung; Hsu, Hui-Tsung; Ko, Ya-Wen; Shieh, Zhu-Xin; Chiang, Hung-Lung

    2009-11-15

    Biosludge was produced from the wastewater treatment plant of a petrochemical industry. The element compositions of pyrolytic residues, CO, CO(2), NOx, SOx, total hydrocarbons and detailed volatile organic compounds of pyrolytic gas, and C, H, N, S content and compositions in biofuel were determined in this study. Generally, 75-80% water content in sludge cakes and about 65-70% weight of water vapor and volatile compounds were volatilized during the drying process. Propene, propane, 1-butene, n-butane, isobutene, toluene and benzene were the major volatile organic compounds (VOCs) of the pyrolytic gas, and the concentrations for most of the top 20 VOC species were greater than 5 ppm. C(5)-C(9) compounds contributed 60% by weight of biofuel; 4-hydroxy-4-methyl-2-pentanone was the highest species, accounting for 28-53% of biofuel at various pyrolytic temperatures. Based on the dried residues, there was 8.5-13% weight in pyrolytic residues, 62-82% weight in liquid products (water and crude oil) and 5.8-30% weight in the gas phase after pyrolytic processing at 500-800 degrees C. Finally, 1.5-2.5 wt% liquid fuel was produced after the distillation process. The pyrolytic residues could be reused, the pyrolytic liquid product could be used as a fuel after distillation, and the pyrolytic gas could be recycled in the pyrolytic process to achieve non-toxic discharge and reduce the cost of sludge disposal. PMID:19570608

  4. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    SciTech Connect

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.

    2008-12-08

    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  5. Polymer Optical Constants from Long-Range Corrected DFT Calculations.

    PubMed

    Maekawa, Shintaro; Moorthi, Krzysztof

    2016-03-10

    A methodology to calculate refractive indices of plastics based on the Lorentz-Lorenz equation has been proposed. The polarizability of the nonconjugated polymer repeat units is predicted using the long-range corrected functionals. The end effect corrections in repeat unit models are essential to achieve accuracy similar to that observed for molecular liquids (ca. 1% in mean absolute deviation). The functionals with 100% Hartree-Fock (HF) exchange in the long-range limit perform best for aromatic and other hydrogen-deficient compounds; the Coulomb-attenuated hybrid exchange-correlation functional (CAM-B3LYP) performs very well for hydrogen-rich (usually, fully saturated) compounds. Exceptionally good agreement is observed for the sets of wavelength-dependent refractive index data for polystyrene, poly(methyl methacrylate), and for poly(perfluoro-4-vinyloxy-1-butene) (CYTOP), for which the root-mean-square deviations are 0.004, 0.002, and 0.004, respectively. PMID:26918918

  6. Removal rates of CHF ( 1A? (0, 0, 0)) by alkenes

    NASA Astrophysics Data System (ADS)

    Ortiz de Zrate, A.; Castao, F.; Fernandez, J. A.; Martinez, R.; Snchez Rayo, M. N.; Hancock, G.

    1992-01-01

    Absolute removal rates of CHF ( 1A? (0, 0, 0)) by ethene (C 2H 4), propene (C 3H 6), 1-butene (1-C 4H 8), isobutene( i-C 4H 8), 1,3-butadiene (C 4H 6), difluoromethane (CH 2F 2), nitric oxide (NO) and argon (Ar) have been measured at room temperature. CHF in the 1A? state was produced by infrared multiphoton dissociation of CH 2F 2 forming the CHF (X 1A') state and further pumping to the 1A? state by absorption of a visible dye laser pulse. Removal processes were found to be second order with the following rate constants in units of 10 -10 cm 3 molecule -1 s -1: k(C 2H 4) = 0.9 0.2. k(C 3H 6) = 1.0 0.2; k (1-1C 4H 8) = 1.1 0.2; k( i-C 4H 8) = 1.1 0.2; k(C 4H 6) = 1.0 0.2; k(Ar) = 0.27 0.02; k(NO) = 0.8 0.1; k(CH 2F 2) = 1.3 0.1. The ParmenterSeaver correlation for collisional removal of 1A? CHF is discussed.

  7. Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

    DOEpatents

    Dumesic, James A.; Ruiz, Juan Carlos Serrano; West, Ryan M.

    2012-04-03

    Described is a method to make liquid chemicals, such as functional intermediates, solvents, and liquid fuels from biomass-derived cellulose. The method is cascading; the product stream from an upstream reaction can be used as the feedstock in the next downstream reaction. The method includes the steps of deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be converted to a mixture of n-butenes. The pentanoic acid so formed can be further reacted to yield a host of valuable products. For example, the pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes. Alternatively, the nonene may be isomerized to yield a mixture of branched olefins, which can be hydrogenated to yield a mixture of branched alkanes. The mixture of n-butenes formed from .gamma.-valerolactone can also be subjected to isomerization and oligomerization to yield olefins in the gasoline, jet and Diesel fuel ranges.

  8. Ruta montana L. leaf essential oil and extracts: characterization of bioactive compounds and suppression of crown gall disease

    PubMed Central

    Hammami, Inés; Smaoui, Slim; Hsouna, Anis Ben; Hamdi, Naceur; Triki, Mohamed Ali

    2015-01-01

    The aims of this study were to assess the antimicrobial efficacy of the leaf essential oil and the leaf extracts of R. montana against Botrytis cinerea, Fusarium oxysporum, Verticillium dahliae, Aspergillus oryzae and Fusarium solani. The oil (1.000 µg/disk) and the extracts (1.500 µg/disk) revealed a remarkable antifungal effect against the tested plant pathogenic fungi with a radial growth inhibition percentage of 40.0-80.0 % and 5.0-58.0 %, respectively along with their respective MIC values ranging from 100 to 1100 µg/mL and 250 to 3000 µg/mL. The oil had a strong detrimental effect on spore germination of all the tested plant pathogens along with the concentration as well as time-dependent kinetic inhibition of Fusarium oxysporum. Also, the oil exhibited a potent in vivo antifungal effect against Botrytis cinerea on tomato plants. Experiments carried out in plant revealed that the essential oil was slightly effective in suppression of gall formation induced by Agrobacterium tumefaciens on bitter almond. The results of this study indicate that the oil and extracts of R. montana leaves could become natural alternatives to synthetic fungicides to control certain important plant microbial diseases. The GC-MS analysis determined that 28 compounds, which represented 89.03 % of total oil, were present in the oil containing mainly 1-butene, methylcyclopropane, 2-butene and caryophyllene oxide. PMID:26417353

  9. Reactive lattice oxygen sites for C sub 4 -hydrocarbon selective oxidation over. beta. -VOPO sub 4

    SciTech Connect

    Lashier, M.E.; Schrader, G.L. )

    1991-03-01

    The role of lattice oxygen species in the catalytic oxidation of n-butene to maleic anhydride has been investigated using {beta}-VOPO{sub 4} labeled with {sup 18}O. The catalyst was prepared by stoichiometric reaction of (VO){sub 2}P{sub 2}O{sub 7} with {sup 18}O{sub 2} using solid state preparation techniques. The {beta}-VOPO{sub 7/2} {sup 18}O{sub 1/2} was characterized using laser Raman and Fourier transform infrared spectroscopies: preferential incorporation at P-O-V sites was observed. A pulse reactor was used to react n-butane, 1-butene, 1,3-butadiene, furan, {gamma}-butyrolactone, and maleic anhydride with the catalyst in the absence of gas-phase O{sub 2}. Incorporation of {sup 18}O into the products was monitored by mass spectrometry. Specific lattice oxygen sites could be associated with the reaction pathways for selective or nonselective oxidation. The results of this study also indicate that the initial interaction of n-butane with {beta}-VOPO{sub 4} is fundamentally different from the initial interaction of olefins or oxygenated species. The approach used in this research-referred to as Isotopic Reactive-Site Mapping-is a potentially powerful method for probing the reactive lattice sites of other selective oxidation catalysts.

  10. New analytical method for the determination of styrene oligomers formed from polystyrene decomposition and its application at the coastlines of the North-West Pacific ocean.

    PubMed

    Saido, Katsuhiko; Koizumi, Koshiro; Sato, Hideto; Ogawa, Naoto; Kwon, Bum Gun; Chung, Seon-Yong; Kusui, Takashi; Nishimura, Masahiko; Kodera, Yoichi

    2014-03-01

    The pollution caused by plastic debris is an environmental problem with increasing concern in the oceans. Among the plastic polymers, polystyrene (PS) is one of the most problematic plastics due to the direct public health risk associated with their dispersion, as well as the numerous adverse environmental impacts which arise both directly from the plastics and from their degradation products. Little is known about their potential distribution characteristics throughout the oceans. For the first time, we report here on the regional distribution of styrene monomer (SM), styrene dimers (SD; 2,4-diphenyl-1-butene, SD1; 1,3-diphenyl propane, SD2), and styrene trimer (2,4,6-triphenyl-1-hexene: ST1), as products of PS decomposition determined from samples of sand and seawater from the shorelines of the North-West Pacific ocean. In order to quantitatively determine SM, SD (=SD1+SD2), and ST1, a new analytical method was developed. The detection limit was 3.3 ?g L(-1), based on a signal-to-noise ratio of three, which was well-suited to quantify levels of SM, SD, and ST1 in samples. Surprisingly, the concentrations of SM, SD, and ST1 in sand samples from the shorelines were consistently greater than those in seawater samples from the same location. The results of this study suggest that SM, SD, and ST1 can be widely dispersed throughout the North-West Pacific oceans. PMID:24394362

  11. [Characteristics of VOCs and their photochemical reactivity in autumn in Nanjing northern suburb].

    PubMed

    Li, Yong-Yu; Zhu, Bin; An, Jun-Lin; Gao, Jin-Hui; Xia, Li; Zhang, Xiang-Zhi; Qin, Wei; Tang, Li-Li

    2013-08-01

    A continuous observation campaign was carried out with the GC5000 volatile organics online monitoring system and the EMS system for one month in November 2011 in the northern suburb of Nanjing, and 56 VOC components and reactive gases (NO(x), CO and O3) were measured. The results showed that the VOC hourly averaged volume fraction in Nanjing northern suburb was about 48.17 x 10(-9), and the minimum value of VOCs occurred at 16:00. The diurnal variation showed a bimodal characteristic, indicating the significant impact of motor vehicle emission. The VOC concentration and O3 concentration exhibited negative correlation in the daytime. The average OH consumption rate of VOCs was approximately 3.26 x 10(-12) cm3 x (molecule x s)(-1), and the largest incremental reactivity was about 3.26 mol x mol(-1); Alkenes contributed the largest-parts of the OH consumption rate (L(OH)) and the ozone formation potential (OFP), followed by aromatics. Although alkanes were the most abundant components of VOCs in the atmosphere, it is not the main contributor of L(OH) and OFP. The key active components in VOCs were ethylene, propylene, 1-butene, m,p-xylene and isoprene, etc. The dominant factor of ozone formation was VOCs in this observation. PMID:24191532

  12. Exploring between the extremes: conversion-dependent kinetics of phosphite-modified hydroformylation catalysis.

    PubMed

    Kubis, Christoph; Selent, Detlef; Sawall, Mathias; Ludwig, Ralf; Neymeyr, Klaus; Baumann, Wolfgang; Franke, Robert; Brner, Armin

    2012-07-01

    The kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a rhodium monophosphite catalyst has been studied in detail. Time-dependent concentration profiles covering the entire olefin conversion range were derived from in situ high-pressure FTIR spectroscopic data for both, pure organic components and catalytic intermediates. These profiles fit to Michaelis-Menten-type kinetics with competitive and uncompetitive side reactions involved. The characteristics found for the influence of the hydrogen concentration verify that the pre-equilibrium towards the catalyst substrate complex is not established. It has been proven experimentally that the hydrogenolysis of the intermediate acyl complex remains rate limiting even at high conversions when the rhodium hydride is the predominant resting state and the reaction is nearly of first order with respect to the olefin. Results from in situ FTIR and high-pressure (HP) NMR spectroscopy and from DFT calculations support the coordination of only one phosphite ligand in the dominating intermediates and a preferred axial position of the phosphite in the electronically saturated, trigonal bipyramidal (tbp)-structured acyl rhodium complex. PMID:22689302

  13. Measurement of proton transfer reaction rates in a microwave cavity discharge flowing afterglow

    NASA Astrophysics Data System (ADS)

    Brooke, George M., IV

    The reaction rate coefficients between the hydronium ion and the molecules ethene (C2H4), propene (C 3H6), 1-butene (C4H8) and hydrogen sulfide (H2S) were measured at 296 K. The measured reaction rates were compared to collision rates calculated using average dipole orientation (ADO) theory. Reaction efficiency depends primarily upon the proton affinity of the molecules. All the measurements were obtained using the newly developed microwave cavity discharge flowing afterglow (MCD-FA) apparatus. This device uses an Asmussen-type microwave cavity discharge ion source that is spatially separated from the flow tube, eliminating many of the problems inherent with the original FA devices. In addition to measuring reaction rate coefficients, the MCD-FA was shown to be an effective tool for measuring trace compounds in atmospheric air. This method has many advantages over current detection techniques since compounds can be detected in almost real time, large mass ranges can be scanned quickly, and repeated calibration is not required. Preliminary measurements were made of car exhaust and exhaled alveolar air. Car exhaust showed the presence of numerous hydrocarbons, such as butene, benzene and toluene while the exhaled alveolar air showed the presence of various volatile organic compounds such as methanol and acetone.

  14. Kinetics and characterization of bismuth molybdate catalysts. 1. A gradientless partial oxidation reactor

    SciTech Connect

    Burban, P.M.; Schuit, G.C.A.; Bicschoff, K.B. ); Koch, T.A. Du Pont Experimental Station, Wilmington, DE )

    1990-12-01

    A gradientless laboratory fixed bed reactor was designed for studying the partial oxidation of 1-butene to 1,3-butadiene over bismuth-molybdate catalysts. By dilution of the catalyst bed with inert silicon carbide, axial catalyst bed temperature gradients were routinely reduced to 2 K or less over the temperature range 650-740 K for the exothermic model reaction. A systematic experimental procedure was developed and used to show that potential transport 'disguises' did not significantly influence the intrinsic rate of butadiene formation measured under both integral and differential conditions. For one Bi{sub 2}MoO{sub 6} catalyst system, rate of butadiene formation data over the temperature range 700-740 K were fit to pseudo first-order (in butene) kinetics. Analytical solutions of the governing equations describing fixed bed reactor transport disguises for first-order catalytic reactions were used to confirm that the reactor operated in a near gradientless fashion, in agreement with experiment.

  15. An operando FTIR spectroscopic and kinetic study of carbon monoxide pressure influence on rhodium-catalyzed olefin hydroformylation.

    PubMed

    Kubis, Christoph; Sawall, Mathias; Block, Axel; Neymeyr, Klaus; Ludwig, Ralf; Brner, Armin; Selent, Detlef

    2014-09-01

    The influence of carbon monoxide concentration on the kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a phosphite-modified rhodium catalyst has been studied for the pressure range p(CO)=0.20-3.83?MPa. Highly resolved time-dependent concentration profiles of the organometallic intermediates were derived from IR spectroscopic data collected in situ for the entire olefin-conversion range. The dynamics of the catalyst and organic components are described by enzyme-type kinetics with competitive and uncompetitive inhibition reactions involving carbon monoxide taken into account. Saturation of the alkyl-rhodium intermediates with carbon monoxide as a cosubstrate occurs between 1.5 and 2?MPa of carbon monoxide pressure, which brings about a convergence of aldehyde regioselectivity. Hydrogenolysis of the acyl intermediate is fast at 30?C and low pressure of p(CO)=0.2?MPa, but is of minus first order with respect to the solution concentration of carbon monoxide. Resting 18-electron hydrido and acyl complexes that correspond to early and late rate-determining states, respectively, coexist as long as the conversion of the substrate is not complete. PMID:25081298

  16. Direct oxidation of hydrocarbons in a solid-oxide fuel cell

    PubMed

    Park; Vohs; Gorte

    2000-03-16

    The direct electrochemical oxidation of dry hydrocarbon fuels to generate electrical power has the potential to accelerate substantially the use of fuel cells in transportation and distributed-power applications. Most fuel-cell research has involved the use of hydrogen as the fuel, although the practical generation and storage of hydrogen remains an important technological hurdle. Methane has been successfully oxidized electrochemically, but the susceptibility to carbon formation from other hydrocarbons that may be present or poor power densities have prevented the application of this simple fuel in practical applications. Here we report the direct, electrochemical oxidation of various hydrocarbons (methane, ethane, 1-butene, n-butane and toluene) using a solid-oxide fuel cell at 973 and 1,073 K with a composite anode of copper and ceria (or samaria-doped ceria). We demonstrate that the final products of the oxidation are CO2 and water, and that reasonable power densities can be achieved. The observation that a solid-oxide fuel cell can be operated on dry hydrocarbons, including liquid fuels, without reforming, suggests that this type of fuel cell could provide an alternative to hydrogen-based fuel-cell technologies. PMID:10749204

  17. Sulforaphene promotes Bax/Bcl2, MAPK-dependent human gastric cancer AGS cells apoptosis and inhibits migration via EGFR, p-ERK1/2 down-regulation.

    PubMed

    Mondal, Arindam; Biswas, Raktim; Rhee, Yun-Hee; Kim, Jongkee; Ahn, Jin-Chul

    2016-01-01

    Gastric cancer migration and invasion considered as main causes of this cancer-related death around the world. Sulforaphene (4-isothiocyanato-4R-(methylsulfinyl)-1-butene), a structural analog of sulforaphane, has been found to exhibit anticancer potential against different cancers. Our aim was to investigate whether dietary isothiocyanate sulforaphene (SFE) can promote human gastric cancer (AGS) cells apoptosis and inhibit migration. Cells were treated with various concentrations of SFE and cell viability, morphology, intracellular ROS, migration and different signaling protein expressions were investigated. The results indicate that SFE decreases AGS cell viability and induces apoptosis in a dose-dependent manner. Intracellular ROS generation, dose- and time-dependent Bax/Bcl2 alteration and signaling proteins like cytochrome c, Casp-3, Casp-8 and PARP-1 higher expression demonstrated the SFE-induced apoptotic pathway in AGS cells. Again, SFE induced apoptosis also accompanied by the phosphorylation of mitogen-activated protein kinases (MAPKs) like JNK and P-38. Moreover, dose-dependent EGFR, p-ERK1/2 down-regulation and cell migration inhibition at non-toxic concentration confirms SFE activity in AGS cell migration inhibition. Thus, this study demonstrated effective chemotherapeutic potential of SFE by inducing apoptisis as well as inhibiting migration and their preliminary mechanism for human gastric cancer management. PMID:26612919

  18. Adsorption and desorption of butanethiol on Au?100?-(520)

    NASA Astrophysics Data System (ADS)

    Bondzie, V.; Dixon-Warren, St. J.; Yu, Y.; Zhang, L.

    1999-07-01

    The adsorption and desorption of butanethiol in ultra-high vacuum on Au{100}-(520) has been investigated using temperature programmed desorption/reaction (TPD/R), low energy electron diffraction and Auger electron spectroscopy. The TPD/R results clearly show that butanethiol adsorbs into both a chemisorbed and a physisorbed state. Desorption of physisorbed butanethiol occurs molecularly at 138 K. By contrast, desorption of the chemisorbed butanethiolate species occurs with decomposition at 500 K to yield primarily 1-butene; the thiol sulfur remains adsorbed on the surface and either desorbs or possibly dissolves into the bulk of the gold sample at above 700 K. The substrate temperature dependence of the chemisorption process suggests a precursor mechanism for the chemisorption kinetics. The TPD/R results also show that chemisorption does not occur on a very clean and ordered Au{100}-(520) surface at 100 K, and that low coverages of pre-adsorbed sulfur atoms facilitate the chemisorption process, suggesting a defect-mediated precursor mechanism.

  19. On the Radiolysis of Ethylene Ices by Energetic Electrons and Implications to the Extraterrestrial Hydrocarbon Chemistry

    NASA Astrophysics Data System (ADS)

    Zhou, Li; Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I.

    2014-07-01

    The chemical processing of ethylene ices (C2H4) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH4), the C2 species acetylene (C2H2), ethane (C2H6), the ethyl radical (C2H5), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C4H8) and n-butane (C4H10). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.

  20. Expanding the scope of metathesis: a survey of polyfunctional, single-site supported tungsten systems for hydrocarbon valorization.

    PubMed

    Popoff, Nicolas; Mazoyer, Etienne; Pelletier, Jérémie; Gauvin, Régis M; Taoufik, Mostafa

    2013-12-01

    Olefin metathesis is increasingly incorporated in polyfunctional industrial processes. The classical WO3/SiO2 olefin metathesis catalyst is combined to other catalysts in order to afford higher added-value chemicals. However, the combination of several reactions, not only in a single reactor, but also stemming from a single, multifunctional surface species is a desirable improvement regarding process issues. Well-defined surface organometallic tungsten species can be designed to implement targeted functionalities (carbene, hydride, alkyl, …). By tuning the metal's coordination sphere, it is possible to combine metathesis with several reactions, such as (de)hydrogenation, dimerization or isomerization. Novel, unconventional reactions for the production and upgrading of alkanes and alkenes have thus been uncovered. The reactivity of this library of supported catalysts is discussed based on the type of mediated transformations: monofunctional (alkene and alkyne metathesis), bifunctional (1-butene or 2-butenes to propylene), trifunctional (ethylene to propylene, alkane metathesis, …). Mechanistic considerations will be discussed to put these results in a wider perspective for future developments. PMID:23945666

  1. A New Process for Maleic Anhydride Synthesis from a Renewable Building Block: The Gas-Phase Oxidehydration of Bio-1-butanol.

    PubMed

    Pavarelli, Giulia; Velasquez Ochoa, Juliana; Caldarelli, Aurora; Puzzo, Francesco; Cavani, Fabrizio; Dubois, Jean-Luc

    2015-07-01

    We investigated the synthesis of maleic anhydride by oxidehydration of a bio-alcohol, 1-butanol, as a possible alternative to the classical process of n-butane oxidation. A vanadyl pyrophosphate catalyst was used to explore the one-pot reaction, which involved two sequential steps: 1) 1-butanol dehydration to 1-butene, catalysed by acid sites, and 2) the oxidation of butenes to maleic anhydride, catalysed by redox sites. A non-negligible amount of phthalic anhydride was also formed. The effect of different experimental parameters was investigated with chemically sourced 1-butanol, and the results were then confirmed by using genuinely bio-sourced 1-butanol. In the case of bio-1-butanol, however, the purity of the product remarkably affected the yield of maleic anhydride. It was found that the reaction mechanism includes the oxidation of butenes to crotonaldehyde and the oxidation of the latter to either furan or maleic acid, both of which are transformed to produce maleic anhydride. PMID:26073302

  2. Electron-scattering cross sections for 1-pentene, H2C=CH-(CH2)2CH3, molecules

    NASA Astrophysics Data System (ADS)

    Szmytkowski, Czesław; Możejko, Paweł; Zawadzki, Mateusz; Ptasińska-Denga, Elżbieta

    2013-03-01

    Cross sections, both experimental and theoretical, are reported for electron scattering from 1-pentene (C5H10) molecules. Absolute grand-total cross sections (TCSs) were measured at electron impact energies ranging from 1 to 300 eV, using a linear electron-transmission technique. The dominant behaviour of the experimental TCS energy function is a distinct asymmetric enhancement with the maximum located around 6.5 eV. Discernible are also three weak TCS structures: a small peak in the vicinity of 1.8 eV and two broad shoulders located between 10 and 30 eV. The additivity rule was employed to calculate the elastic cross section (ECS) from 20 to 3000 eV, while the binary-encounter-Bethe approach was used for the computation of the ionization cross section (ICS), from the threshold up to 3000 eV. Within 30 and 300 eV, the sum of computed cross sections (ECS+ICS) quite reasonably reproduces the experimental TCS values. Comparison is also made between the experimental TCS energy curve for 1-pentene (H2C=CH-(CH2)2CH3) and those measured for the ethylene (H2C=CH2) molecule and its substituted derivatives: propene (H2C=CH-CH3) and 1-butene (H2C=CH-CH2CH3).

  3. Chain-Folding Structures of a Semi-crystalline Polymer in Bulk and Single Crystals Elucidated by 13C-13C Double Quantum NMR

    NASA Astrophysics Data System (ADS)

    Hong, You-Lee; Miyoshi, Toshikazu

    2014-03-01

    Semi-crystalline polymers are crystallized as folded chains in thin lamellae of ca. 5-20 nm from random coils in the melt and solution states. However, understanding of detailed chain-folding structure and crystallization mechanism are still challenging issue due to various experimental limitations. We recently developed a new strategy using 13C-13C double-quantum (DQ) NMR with selectively 13C isotope labeled isotactic poly(1-butene) form I to investigate chain-trajectory in solution and melt grown crystals at various Tcs. This new method can determine the re-entrance sites, the successive folding number (n) , and the fractions (F) of chain-folding in a wide Tc range. In melt grown crystals at Tc = 95 C, a comparison of experimental and simulated DQ efficiency determined that the polymer chains alternatively change chain-folding directions and the stems tightly pack via intramolecular interactions, and the fraction (F) of adjacent re-entry structure ranges from 70% at n = 4 to 100% at mixed structures of n = 1 and 2. Furthermore, DQ efficiency is independent of Tc in bulk crystals. This means chain-folding do not change in a wide Tcs. DMR-1105829.

  4. The influence of overlap interactions on chemical reactions in confinement

    NASA Astrophysics Data System (ADS)

    Santiso, Erik E.; Gubbins, Keith E.; George, Aaron M.; Buongiorno Nardelli, Marco

    2007-03-01

    Chemical reactions are often carried out in nano-structured materials due to their large surface area per unit mass. It is, however, difficult to understand fully the role of the nano-structure in many reactions due to the superposition of multiple effects. Such effects include: the reduced dimensionality of the system, the heterogeneity of the pore surfaces, the selective adsorption of reactants/products, catalytic effects, and transport limitations. Experimental studies often show many of these effects at the same time, making the results difficult to interpret. In this work we present results of density functional theory calculations illustrating the influence of overlap interactions (shape-catalytic effects) on chemical reactions. In particular, we show the effect of confinement in small pores on the rates of rotational isomerizations of n-butane, 1-butene and 1,3-butadiene. We find that the rates of these transitions change as the double exponential of the pore size in the molecular sieving limit. These results are a first step towards an integrated model for the design of catalytic materials.

  5. Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

    NASA Technical Reports Server (NTRS)

    Fahr, Askar; Halpern, Joshua B.; Tardy, Dwight C.

    2007-01-01

    Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance of C-C and C-H bond ruptures, cyclization, decyclization, and complex decompositions are discussed in terms of energetics and structural properties. The pressure dependence of the product yields were computed and dominant reaction paths in this chemically activated system were determined. Both modeling and experiment suggest that the observed pressure dependence of [1-C4H8]/[C4H10] is due to decomposition of the chemically activated combination adduct 1-C4H8* in which the weaker allylic C-C bond is broken: H2C=CHCH2CH3 yields C3H5 + CH3. This reaction occurs even at moderate pressures of approx.200 Torr (26 kPa) and becomes more significant at lower pressures. The additional products detected at lower pressures are formed from secondary radical-radical reactions involving allyl, methyl, ethyl, and vinyl radicals. The modeling studies have extended the predictions of product distributions to different temperatures (200-700 K) and a wider range of pressures (10(exp -3) - 10(exp 5) Torr). These calculations indicate that the high-pressure [1-C4H8]/[C4H10] yield ratio is 1.3 +/- 0.1.

  6. Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

    NASA Astrophysics Data System (ADS)

    Murillo, Luis E.

    Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are also discussed. Chemisorption, TPD, FTIR using a batch reactor for the self-hydrogenation of cyclohexene and CO adsorbed on the bimetallic surfaces were carried out to correlate surface science findings with experiments on supported bimetallic catalysts. To expand the studies on the effect of bimetallic structures on hydrogenation reactions, molecules with multiple functional groups such as alpha,beta-unsaturated aldehydes were also investigated. Studies of selective hydrogenation of a,ss-unsaturated aldehydes toward the desired unsaturated alcohols are of interest for the production of fine chemicals and pharmaceuticals. In these compounds, competitive hydrogenation of the C=C and C=O bonds occurs. TPD and HREELS experiments of acrolein (CH2=CH-CH=O) on Pt-based bimetallic surfaces are performed to investigate their effects on the hydrogenation activity of the C-O bond. The production of the desired unsaturated alcohol, allyl alcohol, has been observed for the first time on Pt-Ni-Pt(111) under UHV conditions. However, the propionaldehyde yield is five times higher than the allyl alcohol yield. Thus, a preferential isomerization reaction of allyl alcohol to propionaldehyde is very likely to occur on the Pt-Ni-Pt(111) surface as observed on the desorption studies of allyl alcohol on this surface. The hydrogenation of acrolein is also carried out under UHV conditions on other 3d-transition metal/Pt(111) surfaces such as Co/Pt(111), Fe/Pt(111), and Cu/Pt(111). So far, the highest activity and allyl alcohol yield are found on the Pt-Ni-Pt(111) surface with pre-adsorbed hydrogen.

  7. Characterization and Dynamics of Substituted Ruthenacyclobutanes Relevant to the Olefin Cross-Metathesis Reaction

    PubMed Central

    Blake, Garrett; VanderVelde, David G.; Grubbs, Robert H.

    2011-01-01

    The reaction of the phosphonium alkylidene [(H2IMes)RuCl2=CHP(Cy)3)]+ BF4 with propene, 1-butene, and 1-hexene at 45 C affords various substituted, metathesis-active ruthenacycles. These metallacycles were found to equilibrate over extended reaction times in response to decreases in ethylene concentrations, which favored increased populations of ?-monosubstituted and ?,?-disubstituted (both cis and trans) ruthenacycles. On an NMR timescale, rapid chemical exchange was found to preferentially occur between the ?-hydrogens of the cis and trans stereoisomers prior to olefin exchange. Exchange on an NMR timescale was also observed between the ?- and ?-methylene groups of the monosubstituted ruthenacycle (H2IMes)Cl2Ru(CHRCH2CH2) (R = CH3, CH2CH3, (CH2)3CH3). EXSY NMR experiments at 87 C were used to determine the activation energies for both of these exchange processes. In addition, new methods have been developed for the direct preparation of metathesis-active ruthenacyclobutanes via the protonolysis of dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(benzylidene) bis(pyridine)ruthenium(II) and its 3-bromopyridine analog. Using either trifluoroacetic acid or silica-bound toluenesulfonic acid as the proton source, the ethylene-derived ruthenacyclobutane (H2IMes)Cl2Ru(CH2CH2CH2) was observed in up to 98% yield via NMR at 40 C. On the basis of these studies, mechanisms accounting for the positional and stereochemical exchange within ruthenacyclobutanes are proposed, as well as the implications of these dynamics towards olefin metathesis catalyst and reaction design are described. PMID:21452876

  8. Triarylphosphine Ligands with Hemilabile Alkoxy Groups. Ligands for Nickel(II)-Catalyzed Olefin Dimerization Reactions. Hydrovinylation of Vi-nylarenes, 1,3-Dienes, and Cycloisomerization of 1,6-Dienes

    PubMed Central

    Biswas, Souvagya; Zhang, Aibin; Raya, Balaram

    2014-01-01

    Substitution of one of the phenyl groups of triphenylphosphine with a 2-benzyloxy-, 2-benzyloxymethyl- or 2-benzyloxyethyl-phenyl moiety results in a set of simple ligands, which exhibit strikingly different behaviour in various nickel(II)-catalyzed olefin dimerization reactions. Complexes of ligands with 2-benzyloxyphenyl-, 2-benzyloxymethylphenyl-diphenylphosphine (L5 and L6 respectively) are most active for hydrovinylation (HV) of vinylarenes, with the former leading to extensive isomerization of the primary 3-aryl-1-butenes into the conjugated 2-aryl-2-butenes even at −55 °C. However, 2-benzyloxymethyl-substituted ligand L6 is slightly less active, leading up to quantitative yields of the primary products of HV at ambient temperature with no trace of isomerization, thus providing the best option for a practical synthesis of these compounds. In sharp contrast, hydrovinylation of a variety of 1,3-dienes is best catalyzed by nickel(II)-complexes of 2-benzyloxyphenyldiphenylphosphine, L5. The other two ligands, 2-benzyloxymethyl-(L6) and 2-benzyloxyethyl-diphenylphosphine (L7) are much less effective in the HV of 1,3-dienes. Nickel(II)-catalyzed cycloisomerization of 1,6-dienes into methylenecyclopentanes, a reaction mechanistically related to the other hydrovinylation reactions, is also uniquely effected by nickel(II)-complexes of L5, but not of L6 or L7. In an attempt to prepare authentic samples of the methylencyclohexane products, nickel(II)-complexes of N-heterocyclic carbene-ligands were examined. In sharp contrast to the phosphines, which give the methylenecyclopentanes, methylenecyclohexanes are the major products in the (N-heterocyclic carbene)nickel(II)-mediated reactions. PMID:25395919

  9. Cytotoxic evaluation of volatile oil from Descurainia sophia seeds on MCF-7 and HeLa cell lines

    PubMed Central

    Khodarahmi, E.; Asghari, G.H.; Hassanzadeh, F.; Mirian, M.; Khodarahmi, G.A.

    2015-01-01

    Descurainia sophia is a plant widely distributed and used as folk medicine throughout the world. Different extracts of aerial parts and seeds of this plant have been shown to inhibit the growth of different cancer cell lines in vitro. In this study, cytotoxic activity of D. sophia seed volatile oil was evaluated. D. sophia seed powder was mixed with distilled water and left at 25 C for 17 h (E1), 23 h (E2) and 28 h (E3) to autolyse. Then, the volatile fractions of E1, E2, and E3 were collected after steam distillation for 3 h. Cytotoxic effects of the volatile oils alone or in combination with doxorubicin (mixture of E1 or E2 at 50 ?g/ml or E1 at 100 ?g/ml with doxorubicin at 0.1, 1, 10 ?M) against MCF-7 cell line were determined using MTT assay. Cytotoxic effect of E1 volatile oil was also determined on HeLa cell line. The results indicated that 1-buten-4-isothiocyanate was the major isothiocyanate found in the volatile oils. The results of cytotoxic evaluations showed that volatile constituents were more toxic on MCF-7 cells with IC50< 100 ?g/ml than HeLa cells with IC50> 100 ?g/ml. No significant differences were observed between cytotoxic activities of E1, E2 and E3 on MCF-7 cell line. Concomitant use of E1 and E2 (50 ?g/ml) with doxurubicin (1 ?M) significantly reduced the viability of MCF-7 cells compared to the negative control, doxorubicin alone, or each volatile fraction. The same result was obtained on HeLa cells, when E1 (100 ?g/ml) was concurrently used with doxorubicin (1 ?M). PMID:26487894

  10. Final report on EURAMET.QM-S6/1195: Bilateral comparison of liquefied hydrocarbon mixtures in constant pressure (piston) cylinders

    NASA Astrophysics Data System (ADS)

    Brown, Andrew S.; Downey, Michael L.; Milton, Martin J. T.; van der Veen, Adriaan M. H.; Zalewska, Ewelina T.; Li, Jianrong

    2013-01-01

    Traceable liquid hydrocarbon mixtures are required in order to underpin measurements of the composition and other physical properties of LPG (liquefied petroleum gas) and LNG (liquefied natural gas), thus meeting the needs of an increasingly large European industrial market. The development of traceable liquid hydrocarbon standards by National Measurement Institutes (NMIs) was still at a relatively early stage at the time this comparison was proposed in 2011. NPL and VSL, who were the only NMIs active in this area, had developed methods for the preparation and analysis of such standards in constant pressure (piston) cylinders, but neither laboratory had Calibration and Measurement Capabilities (CMCs) for these mixtures. This report presents the results of EURAMET 1195, the first comparison of liquid hydrocarbon mixtures between NMIs, which assessed the preparation and analytical capabilities of NPL and VSL for these mixtures. The comparison operated between August 2011 and January 2012. Each laboratory prepared a liquid hydrocarbon standard with nominally the same composition and these standards were exchanged for analysis. The results of the comparison show a good agreement between the laboratories' results and the comparison reference values for the six components with amount fractions greater than 1.0 cmol/mol (propane, propene, iso-butene, n-butane, iso-butane and 1-butene). Measurement of the three components with lower amount fractions (1,3-butadiene, iso-pentane and n-pentane) proved more challenging. In all but one case, the differences from the comparison reference values for these three components were greater than the expanded measurement uncertainty. Main text. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by EURAMET, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

  11. ANALYSIS OF VAPORS FROM METHYLENE CHLORIDE EXTRACTS OF NUCLEAR GRADE HEPA FILTER FIBERGLASS SAMPLES

    SciTech Connect

    FRYE JM; ANASTOS HL; GUTIERREZ FC

    2012-06-07

    While several organic compounds were detected in the vapor samples used in the reenactment of the preparation of mounts from the extracts of nuclear grade high-efficiency particulate air filter fiberglass samples, the most significant species present in the samples were methylene chloride, phenol, phenol-d6, and 2-fluorophenol. These species were all known to be present in the extracts, but were expected to have evaporated during the preparation of the mounts, as the mounts appeared to be dry before any vapor was collected. These species were present at the following percentages of their respective occupational exposure limits: methylene chloride, 2%; phenol, 0.4%; and phenol-d6, 0.6%. However, there is no established limit for 2-fluorophenol. Several other compounds were detected at low levels for which, as in the case of 2-fluorophenol, there are no established permissible exposure limits. These compounds include 2-chlorophenol; N-nitroso-1-propanamine; 2-fluoro-1,1{prime}-biphenyl; 1,2-dihydroacenaphthylene; 2,5-cyclohexadiene-1,4-dione,2,6-bis(1,1-dimethylethyl); trimethyl oxirane; n-propylpropanamine; 2-(Propylamino)ethanol; 4-methoxy-1-butene; 6-methyl-5-hepten-2-one; and 3,4-dimethylpyridine. Some of these were among those added as surrogates or spike standards as part ofthe Advanced Technologies and Laboratories International, Inc. preparation ofthe extract of the HEPA filter media and are indicated as such in the data tables in Section 2, Results; other compounds found were not previously known to be present. The main inorganic species detected (sulfate, sodium, and sulfur) are also consistent with species added in the preparation of the methylene chloride extract of the high-efficiency particulate air sample.

  12. Competitive chain transfer by [beta]-hydrogen and [beta]-methyl elimination for the model Ziegler-Natta olefin polymerization system [Me[sub 2]Si([eta][sup 5]-C[sub 5]Me[sub 4])[sub 2

    SciTech Connect

    Hajela, S.; Bercaw, J.E. )

    1994-04-01

    The reaction of OpSc(H)(PMe[sub 3]) (Op = (([eta][sup 5]-C[sub 6]Me[sub 4])[sub 2]SiMe[sub 2])) with isobutene produces OpSc(CH[sub 3])(PMe[sub 3]) along with isobutene, 2-methylpentane, isobutene, 2-methyl-1-pentene, propane, and n-pentane. These products arise from a series of reactions involving olefin insertion, [beta]-CH[sub 3] and (faster) [beta]-H elimination which proceed until only the 2-methyl-1-alkenes (C[sub 4]H[sub 8], C[sub 6]H[sub 12], etc.) and the predominant organoscandium product OpSc(CH[sub 3])(PMe[sub 3]) remain. A transient observed in the reaction sequence has been unambiguously characterized as OpSc(CH[sub 2]CH[sub 2]CH[sub 3])(PMe[sub a]). Slower [sigma] bond metathesis involving the methyl C-H bonds of PMe[sub 3] and the Sc-C bonds of the scandium alkyls accounts for the observation of saturated alkanes 2-methylalkanes (C[sub 4]H[sub 10], C[sub 6]H[sub 14], etc.), normal alkanes (C[sub 3]H[sub 8],C[sub 5]H[sub 12], etc.), and a minor organoscandium product OpScCh[sub 2]Pme[sub 2] in the product mixture. [beta]-Ethylmigration is not observed for the closely related 2-ethylbutyl derivative, OpSc(CH[sub 2]CH(C[sub 2]H[sub 5])CH[sub 2]CH[sub 3])(PMe[sub 3]), obtained from reaction of 2-ethyl-1-butene with OpSc(H)(PMe[sub 3]). 28 refs., 2 figs., 1 tab.

  13. Alcohol dehydrogenase- and rat liver cytosol-dependent bioactivation of 1-chloro-2-hydroxy-3-butene to 1-chloro-3-buten-2-one, a bifunctional alkylating agent.

    PubMed

    Elfarra, Adnan A; Zhang, Xin-Yu

    2012-11-19

    1,3-Butadiene (BD) is an air pollutant whose toxicity and carcinogenicity have been considered primarily mediated by its reactive metabolites, 3,4-epoxy-1-butene and 1,2,3,4-diepoxybutane, formed in liver and extrahepatic tissues by cytochromes P450s. A possible alternative metabolic pathway in bone marrow and immune cells is the conversion of BD to the chlorinated allylic alcohol 1-chloro-2-hydroxy-3-butene (CHB) by myeloperoxidase in the presence of hydrogen peroxide and chloride ion. In the present study, we investigated the in vitro bioactivation of CHB by alcohol dehydrogenases (ADH) under in vitro physiological conditions (pH 7.4, 37 C). The results provide clear evidence for CHB being converted to 1-chloro-3-buten-2-one (CBO) by purified horse liver ADH and rat liver cytosol. CBO readily reacted with glutathione (GSH) under assay conditions to form three products: two CBO-mono-GSH conjugates [1-chloro-4-(S-glutathionyl)butan-2-one (3) and 1-(S-glutathionyl)-3-buten-2-one (4)] and one CBO-di-GSH conjugate [1,4-bis(S-glutathionyl)butan-2-one (5)]. CHB bioactivation and the ratios of the three GSH conjugates formed were dependent upon incubation time, GSH and CHB concentrations, and the presence of ADH or rat liver cytosol. The ADH enzymatic reaction followed Michaelis-Menten kinetics with a K(m) at 3.5 mM and a k(cat) at 0.033 s(-1). After CBO was incubated with freshly isolated mouse erythrocytes, globin dimers were detected using SDS-PAGE and silver staining, providing evidence that CBO can act as a protein cross-linking agent. Collectively, the results provide clear evidence for CHB bioactivation by ADH and rat liver cytosol to yield CBO. The bifunctional alkylating ability of CBO suggests that it may play a role in BD toxicity and/or carcinogenicity. PMID:23110628

  14. Chemical dynamics in time and energy space

    SciTech Connect

    Myers, J.D.

    1993-04-01

    The development of a versatile picosecond ultraviolet/vacuum ultraviolet temporal spectrometer and its potential use for measuring internal energy redistribution in isolated molecules are described in detail. A detailed description of the double-pass Nd:YAG amplifier and the dye amplifiers is given with the pulse energies achieved in the visible, ultraviolet, and vacuum ultraviolet. The amplified visible pulses are shown to be of sub-picosecond duration and near transform limited. The instrument`s temporal response ({le}10 ps) is derived from an instrument limited measurement of the dissociation lifetime of methyl iodide at 266 nm. The methyl iodide experiment is used to discuss the various sources of noise and background signals that are intrinsic to this type of experiment. Non-time-resolved experiments measuring the branching ratio and kinetic energy distributions of products from the 193 nm photodissociation of cyclopentadiene and thiophene are presented. These studies were done using the molecular beam Photofragment Translational Spectroscopy (PTS) technique. The results from the cyclopentadiene experiment confirm that H atom elimination to yield the cyclopentadienyl radical is the dominant dissociation channel. A barrier of {ge}5 kcal/mol can be understood in terms of the delocalization of the radical electron of the cyclopentadienyl fragment. A concerted elimination yielding cyclopropene and acetylene was also observed and is proposed to occur via a bicyclo-[2.1.0]pent-2-ene intermediate. Two other channels, yielding acetylene plus the CH{sub 2}CHCH triplet carbene, and CH{sub 2} plus 1-buten-3-yne, are postulated to occur via ring opening. The implications of the experimental results for bulk thermal oxidation and pyrolysis models are discussed. The thiophene experiment shows six competing dissociation channels. The postulated intermediates for the various thiophene dissociation channels include bicyclo, ring opened, and possibly ring contracted forms.

  15. On the radiolysis of ethylene ices by energetic electrons and implications to the extraterrestrial hydrocarbon chemistry

    SciTech Connect

    Zhou, Li; Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I.

    2014-07-20

    The chemical processing of ethylene ices (C{sub 2}H{sub 4}) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH{sub 4}), the C2 species acetylene (C{sub 2}H{sub 2}), ethane (C{sub 2}H{sub 6}), the ethyl radical (C{sub 2}H{sub 5}), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C{sub 4}H{sub 8}) and n-butane (C{sub 4}H{sub 10}). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.

  16. Experimental and modeling study of the thermal decomposition of methyl decanoate

    PubMed Central

    Herbinet, Olivier; Glaude, Pierre-Alexandre; Warth, Valérie; Battin-Leclerc, Frédérique

    2013-01-01

    The experimental study of the thermal decomposition of methyl decanoate was performed in a jet-stirred reactor at temperatures ranging from 773 to 1123 K, at residence times between 1 and 4 s, at a pressure of 800 Torr (106.6 kPa) and at high dilution in helium (fuel inlet mole fraction of 0.0218). Species leaving the reactor were analyzed by gas chromatography. Main reaction products were hydrogen, carbon oxides, small hydrocarbons from C1 to C3, large 1-olefins from 1-butene to 1-nonene, and unsaturated esters with one double bond at the end of the alkyl chain from methyl-2-propenoate to methyl-8-nonenoate. At the highest temperatures, the formation of polyunsaturated species was observed: 1,3-butadiene, 1,3-cyclopentadiene, benzene, toluene, indene, and naphthalene. These results were compared with previous ones about the pyrolysis of n-dodecane, an n-alkane of similar size. The reactivity of both molecules was found to be very close. The alkane produces more olefins while the ester yields unsaturated oxygenated compounds. A detailed kinetic model for the thermal decomposition of methyl decanoate has been generated using the version of software EXGAS which was updated to take into account the specific chemistry involved in the oxidation of methyl esters. This model contains 324 species and 3231 reactions. It provided a very good prediction of the experimental data obtained in jet-stirred reactor. The formation of the major products was analyzed. The kinetic analysis showed that the retro-ene reactions of intermediate unsaturated methyl esters are of importance in low reactivity systems. PMID:23710078

  17. Rich methane premixed laminar flames doped by light unsaturated hydrocarbons. III. Cyclopentene

    SciTech Connect

    Gueniche, H.A.; Glaude, P.A.; Fournet, R.; Battin-Leclerc, F.

    2008-01-15

    In line with the studies presented in Parts I (methane flame seeded with allene and propyne) and II (methane flame seeded with 1,3-butadiene) of this paper, the structure of a laminar rich premixed methane flame doped with cyclopentene has been investigated. The gases of this flame contain 15.3% (molar) of methane, 26.7% of oxygen, and 2.4% cyclopentene, corresponding to an overall equivalence ratio of 1.79 and a C{sub 5}H{sub 8}/CH{sub 4} ratio of 15.7%. The flame has been stabilized on a burner at a pressure of 6.7 kPa using argon as dilutant, with a gas velocity at the burner of 36 cm/s at 333 K. The measured temperature ranged from 627 K close to the burner up to 2027 K. Species quantified by gas chromatography included the usual methane C{sub 0}-C{sub 2} combustion products, but also propyne, allene, propene, propane, 1-butene, 1,3-butadiene, 1,2-butadiene, vinylacetylene, diacetylene, cyclopentadiene, 1,3-pentadiene, benzene, and toluene. A new mechanism for the oxidation of cyclopentene has been developed and added to the former model for the oxidation of small unsaturated hydrocarbons, benzene, and toluene described in Parts I and II. The whole mechanism involved 175 species in 1134 reactions. The main reaction pathways of consumption of cyclopentene and of formation of benzene and toluene are presented and discussed from flow rate analyses. (author)

  18. Bimolecular rate constant and product branching ratio measurements for the reaction of C2H with ethene and propene at 79 K.

    PubMed

    Bouwman, Jordy; Goulay, Fabien; Leone, Stephen R; Wilson, Kevin R

    2012-04-19

    The reactions of the ethynyl radical (C(2)H) with ethene (C(2)H(4)) and propene (C(3)H(6)) are studied under low temperature conditions (79 K) in a pulsed Laval nozzle apparatus. Ethynyl radicals are formed by 193 nm photolysis of acetylene (C(2)H(2)) and the reactions are studied in nitrogen as a carrier gas. Reaction products are sampled and subsequently photoionized by the tunable vacuum ultraviolet radiation of the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory. The product ions are detected mass selectively and time-resolved by a quadrupole mass spectrometer. Bimolecular rate coefficients are determined under pseudo-first-order conditions, yielding values in good agreement with previous measurements. Photoionization spectra are measured by scanning the ALS photon energy while detecting the ionized reaction products. Analysis of the photoionization spectra yields-for the first time-low temperature isomer resolved product branching ratios. The reaction between C(2)H and ethene is found to proceed by H-loss and yields 100% vinylacetylene. The reaction between C(2)H and propene results in (85 10)% C(4)H(4) (m/z = 52) via CH(3)-loss and (15 10)% C(5)H(6) (m/z = 66) by H-loss. The C(4)H(4) channel is found to consist of 100% vinylacetylene. For the C(5)H(6) channel, analysis of the photoionization spectrum reveals that (62 16)% is in the form of 4-penten-1-yne, (27 8)% is in the form of cis- and trans-3-penten-1-yne and (11 10)% is in the form of 2-methyl-1-buten-3-yne. PMID:22429068

  19. SmoXYB1C1Z of Mycobacterium sp. Strain NBB4: a Soluble Methane Monooxygenase (sMMO)-Like Enzyme, Active on C2 to C4 Alkanes and Alkenes

    PubMed Central

    Martin, Kiri E.; Ozsvar, Jazmin

    2014-01-01

    Monooxygenase (MO) enzymes initiate the aerobic oxidation of alkanes and alkenes in bacteria. A cluster of MO genes (smoXYB1C1Z) of thus-far-unknown function was found previously in the genomes of two Mycobacterium strains (NBB3 and NBB4) which grow on hydrocarbons. The predicted Smo enzymes have only moderate amino acid identity (30 to 60%) to their closest homologs, the soluble methane and butane MOs (sMMO and sBMO), and the smo gene cluster has a different organization from those of sMMO and sBMO. The smoXYB1C1Z genes of NBB4 were cloned into pMycoFos to make pSmo, which was transformed into Mycobacterium smegmatis mc2-155. Cells of mc2-155(pSmo) metabolized C2 to C4 alkanes, alkenes, and chlorinated hydrocarbons. The activities of mc2-155(pSmo) cells were 0.94, 0.57, 0.12, and 0.04 nmol/min/mg of protein with ethene, ethane, propane, and butane as substrates, respectively. The mc2-155(pSmo) cells made epoxides from ethene, propene, and 1-butene, confirming that Smo was an oxygenase. Epoxides were not produced from larger alkenes (1-octene and styrene). Vinyl chloride and 1,2-dichloroethane were biodegraded by cells expressing Smo, with production of inorganic chloride. This study shows that Smo is a functional oxygenase which is active against small hydrocarbons. M. smegmatis mc2-155(pSmo) provides a new model for studying sMMO-like monooxygenases. PMID:25015887

  20. The chemistry of tributyl phosphate at elevated temperatures in the Plutonium Finishing Plant Process Vessels

    SciTech Connect

    Barney, G.S.; Cooper, T.D.

    1994-06-01

    Potentially violent chemical reactions of the tributyl phosphate solvent used by the Plutonium Finishing Plant at the Hanford Site were investigated. There is a small probability that a significant quantity of this solvent could be accidental transferred to heated process vessels and react there with nitric acid or plutonium nitrate also present in the solvent extraction process. The results of laboratory studies of the reactions show that exothermic oxidation of tributyl phosphate by either nitric acid or actinide nitrates is slow at temperatures expected in the heated vessels. Less than four percent of the tributyl phosphate will be oxidized in these vented vessels at temperatures between 125{degrees}C and 250{degrees}C because the oxidant will be lost from the vessels by vaporization or decomposition before the tributyl phosphate can be extensively oxidized. The net amounts of heat generated by oxidation with concentrated nitric acid and with thorium nitrate (a stand-in for plutonium nitrate) were determined to be about -150 and -220 joules per gram of tributyl phosphate initially present, respectively. This is not enough heat to cause violent reactions in the vessels. Pyrolysis of the tributyl phosphate occurred in these mixtures at temperatures of 110{degrees}C to 270{degrees}C and produced mainly 1-butene gas, water, and pyrophosphoric acid. Butene gas generation is slow at expected process vessel temperatures, but the rate is faster at higher temperatures. At 252{degrees}C the rate of butene gas generated was 0.33 g butene/min/g of tributyl phosphate present. The measured heat absorbed by the pyrolysis reaction was 228 J/g of tributyl phosphate initially present (or 14.5 kcal/mole of tributyl phosphate). Release of flammable butene gas into process areas where it could ignite appears to be the most serious safety consideration for the Plutonium Finishing Plant.

  1. The adsorption of 1,3-butadiene on Pd/Ni multilayers: The interplay between spin polarization and chemisorption strength

    SciTech Connect

    Gomez, Guillermina; Belelli, Patricia G.; Cabeza, Gabriela F.; Castellani, Norberto J.

    2010-12-15

    The adsorption of 1,3-butadiene (BD) on the Pd/Ni(1 1 1) multilayers has been studied using the VASP method in the framework of the density functional theory (DFT). The adsorption on two different configurations of the Pd{sub n}/Ni{sub m}(1 1 1) systems were considered. The most stable adsorption sites are dependent on the substrate composition and on the inclusion or not of spin polarization. On Pd{sub 1}Ni{sub 3}(1 1 1) surface, di-{pi}-cis and 1,2,3,4-tetra-{sigma} adsorption structures are the most stable for non-spin polarized (NSP) and spin polarized (SP) levels of calculation, respectively. Conversely, on Pd{sub 3}Ni{sub 1}(1 1 1) surface, the 1,2,3,4-tetra-{sigma} adsorption structure is the most stable for both NSP and SP levels, respectively. The magnetization of the Pd atoms strongly modifies the adsorption energy of BD and its most stable adsorption mode. On the other hand, as a consequence of BD adsorption, the Pd magnetization decreases. The smaller adsorption energies of BD and 1-butene on the Pd{sub 1}Ni{sub 3}(1 1 1) surface than on Pd(1 1 1) can be associated to the strained Pd overlayer deposited on Ni(1 1 1). -- Graphical Abstract: The adsorption of 1,3-butadiene on Pd/Ni(1 1 1) multilayers was theoretically studied. The most stable adsorption site depends on the substrate composition and on the inclusion of spin polarization. Display Omitted

  2. Rich methane premixed laminar flames doped with light unsaturated hydrocarbons

    SciTech Connect

    Gueniche, H.A.; Glaude, P.A.; Dayma, G.; Fournet, R.; Battin-Leclerc, F.

    2006-09-15

    The structure of three laminar premixed rich flames has been investigated: a pure methane flame and two methane flames doped by allene and propyne, respectively. The gases of the three flames contain 20.9% (molar) of methane and 33.4% of oxygen, corresponding to an equivalence ratio of 1.25 for the pure methane flame. In both doped flames, 2.49% of C{sub 3}H{sub 4} was added, corresponding to a ratio C{sub 3}H{sub 4}/CH{sub 4} of 12% and an equivalence ratio of 1.55. The three flames have been stabilized on a burner at a pressure of 6.7 kPa using argon as dilutant, with a gas velocity at the burner of 36 cm/s at 333 K. The concentration profiles of stable species were measured by gas chromatography after sampling with a quartz microprobe. Quantified species included carbon monoxide and dioxide, methane, oxygen, hydrogen, ethane, ethylene, acetylene, propyne, allene, propene, propane, 1,2-butadiene, 1,3-butadiene, 1-butene, isobutene, 1-butyne, vinylacetylene, and benzene. The temperature was measured using a PtRh (6%)-PtRh (30%) thermocouple settled inside the enclosure and ranged from 700 K close to the burner up to 1850 K. In order to model these new results, some improvements have been made to a mechanism previously developed in our laboratory for the reactions of C{sub 3}-C{sub 4} unsaturated hydrocarbons. The main reaction pathways of consumption of allene and propyne and of formation of C{sub 6} aromatic species have been derived from flow rate analyses. (author)

  3. Cl atom initiated oxidation of 1-alkenes under atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Walavalkar, M.; Sharma, A.; Alwe, H. D.; Pushpa, K. K.; Dhanya, S.; Naik, P. D.; Bajaj, P. N.

    2013-03-01

    In view of the importance of the oxidation pathways of alkenes in the troposphere, and the significance of Cl atom as an oxidant in marine boundary layer (MBL) and polluted industrial atmosphere, the reactions of four 1-alkenes (C6-C9) with Cl atoms are investigated. The rate coefficients at 298 K are measured to be (4.0 ± 0.5), (4.4 ± 0.7), (5.5 ± 0.9) and (5.9 ± 1.7) × 10-10 cm3 molecule-1 s-1 for 1-hexene, 1-heptene, 1-octene and 1-nonene, respectively. The quoted errors include the experimental 2σ, along with the error in the reference rate coefficients. From the systematic increase in the rate coefficients with the number of carbon atoms, an approximate value for the average rate coefficient for hydrogen abstraction per CH2 group in alkenes is estimated to be (4.9 ± 0.3) × 10-11 cm3 molecule-1 s-1. Based on these rate coefficients, the contribution of Cl atom reactions towards the degradation of these molecules is found to be comparable to that of OH radical reactions, under MBL conditions. The products identified in gas phase indicate that Cl atom addition occurs mainly at the terminal carbon, leading to the formation of 1-chloro-2-ketones and 1-chloro-2-ols. The major gas phase products from the alkenyl radicals (formed by H atom abstraction) are different positional isomers of long chain enols and enones. A preference for dissociation leading to an allyl radical, resulting in aldehydes, lower by three carbon atoms, is indicated. The observed relative yields suggest that in general, the increased contribution of the reactions of Cl atoms towards degradation of 1-alkenes in NOx free air does not result in an increase in the generation of small aldehydes (carbon number < 4), including chloroethanal, as compared to that in the reaction of 1-butene.

  4. Characteristics of volatile organic compounds (VOCs) emitted from a petroleum refinery in Beijing, China

    NASA Astrophysics Data System (ADS)

    Wei, Wei; Cheng, Shuiyuan; Li, Guohao; Wang, Gang; Wang, Haiyan

    2014-06-01

    This study made a field VOCs (volatile organic compounds) measurement for a petroleum refinery in Beijing by determining 56 PAMS VOCs, which are demanded for photochemical assessment in US, and obtained the characteristics of VOCs emitted from the whole refinery and from its inner main devices. During the monitoring period, this refinery brought about an average increase of 61 ppbv in the ambient TVOCs (sum of the PAMS VOCs) at the refinery surrounding area, while the background of TVOCs there was only 10-30 ppbv. In chemical profile, the VOCs emitted from the whole refinery was characteristic by isobutane (8.7%), n-butane (7.9%), isopentane (6.3%), n-pentane (4.9%%), n-hexane (7.6%), C6 branched alkanes (6.0%), propene (12.7%), 1-butene (4.1%), benzene (7.8%), and toluene (5.9%). On the other hand, the measurement for the inner 5 devices, catalytic cracking units (CCU2 and CCU3), catalytic reforming unit (CRU), tank farm (TF), and wastewater treatment(WT), revealed the higher level of VOCs pollutions (about several hundred ppbv of TVOCs), and the individual differences in VOCs chemical profiles. Based on the measured speciated VOCs data at the surrounding downwind area, PMF receptor model was applied to identify the VOCs sources in the refinery. Then, coupling with the VOCs chemical profiles measured at the device areas, we concluded that CCU1/3 contributes to 25.9% of the TVOCs at the surrounding downwind area by volume, followed by CCU2 (24.7%), CRU (18.9%), TF (18.3%) and WT (12.0%), which was accordant with the research of US EPA (2008). Finally, ozone formation potentials of the 5 devices were also calculated by MIR technique, which showed that catalytic cracking units, accounting for about 55.6% to photochemical ozone formation, should be given the consideration of VOCs control firstly.

  5. Characterizations of volatile organic compounds during high ozone episodes in Beijing, China.

    PubMed

    An, Jun-lin; Wang, Yue-si; Wu, Fang-kun; Zhu, Bin

    2012-04-01

    Air samples were collected in Beijing from June through August 2008, and concentrations of volatile organic compounds (VOCs) in those samples are here discussed. This sampling was performed to increase understanding of the distributions of their compositions, illustrate the overall characteristics of different classes of VOCs, assess the ages of air masses, and apportion sources of VOCs using principal compound analysis/absolute principal component scores (PCA/APCS). During the sampling periods, the relative abundance of the four classes of VOCs as determined by the concentration-based method was different from that determined by the reactivity approach. Alkanes were found to be most abundant (44.3-50.1%) by the concentration-based method, but aromatic compounds were most abundant (38.2-44.5%) by the reactivity approach. Aromatics and alkenes contributed most (73-84%) to the ozone formation potential. Toluene was the most abundant compound (11.8-12.7%) during every sampling period. When the maximum incremental reactivity approach was used, propene, toluene, m,p-xylene, 1-butene, and 1,2,4-trimethylbenzene were the five most abundant compounds during two sampling periods. X/B, T/B, and E/B ratios in this study were lower than those found in other cities, possibly due to the aging of the air mass at this site. Four components were extracted from application of PCA to the data. It was found that the contribution of vehicle exhaust to total VOCs accounted for 53% of VOCs, while emissions due to the solvent use contributed 33% of the total VOCs. Industrial sources contributed 3% and biogenic sources contributed 11%. The results showed that vehicle exhausts (i.e., unburned vehicle emissions + vehicle internal engine combustion) were dominant in VOC emissions during the experimental period. The solvent use made the second most significant contribution to ambient VOCs. PMID:21552987

  6. Gas-phase chemistry of bare and oxo-ligated protactinium ions: a contribution to a systematic understanding of actinide chemistry.

    PubMed

    Gibson, John K; Haire, Richard G

    2002-11-01

    Gas-phase chemistry of bare and oxo-ligated protactinium ions has been studied for the first time. Comparisons were made with thorium, uranium, and neptunium ion chemistry to further the systematic understanding of 5f elements. The rates of oxidation of Pa(+) and PaO(+) by ethylene oxide compared with those of the homologous uranium ions indicate that the first and second bond dissociation energies, BDE[Pa(+)-O] and BDE[OPa(+)-O], are approximately 800 kJ mol(-1). The relatively facile fluorination of Pa(+) to PaF(4)(+) by SF(6) is consistent with the high stability of the pentavalent oxidation state of Pa. Reactions with ethene, propene, 1-butene, and iso-butene revealed that Pa(+) is a very reactive metal ion. In analogy with U(+) chemistry, ethene was trimerized by Pa(+) to give PaC(6)H(6)(+). Reactions of Pa(+) with larger alkenes resulted in secondary and tertiary products not observed for U(+) or Np(+). The bare protactinium ion is significantly more reactive with organic substrates than are heavier actinide ions. The greatest difference between Pa and heavier actinide congeners was the exceptional dehydrogenation activity of PaO(+) with alkenes; UO(+) and NpO(+) were comparatively inert. The striking reactivity of PaO(+) is attributed to the distinctive electronic structure at the metal center in this oxide, which is considered to reflect the greater availability of the 5f electrons for participation in bonding, either directly or by promotion/hybridization with higher-energy valence orbitals. PMID:12401099

  7. The carbon kinetic isotope effects of ozone-alkene reactions in the gas-phase and the impact of ozone reactions on the stable carbon isotope ratios of alkenes in the atmosphere

    NASA Astrophysics Data System (ADS)

    Iannone, R.; Anderson, R. S.; Rudolph, J.; Huang, L.; Ernst, D.

    2003-07-01

    The kinetic isotope effects (KIEs) for several ozone-alkene reactions in the gas phase were studied in a 30 L PTFE reaction chamber. The time dependence of the stable carbon isotope ratios and the concentrations were determined using a gas chromatography combustion isotope ratio mass spectrometry (GCC-IRMS) system. The following average KIE values were obtained: 18.9 +/- 2.8 (ethene), 9.5 +/- 2.5 (propene), 8.7 +/- 1 (1-butene), 8.1 +/- 0.4 (E-2-butene), 7.9 +/- 0.4 (1,3-butadiene), 6.7 +/- 0.9 (1-pentene), 7.3 +/- 0.2 (Z-2-pentene), 6.7 +/- 0.7 (cyclopentene), 6.1 +/- 1 (isoprene), 5.0 +/- 0.7 (1-hexene), 5.6 +/- 0.5 (cyclohexene), and 4.3 +/- 0.7 (1-heptene). These data are the first of their kind to be reported in the literature. The ozone-alkene KIE values show a systematic inverse dependence from alkene carbon number. Based on the observed KIEs, the contribution of ozone-alkene reactions to the isotopic fractionation of alkenes in the atmosphere can be estimated. On average this contribution is generally small compared to the impact of reaction with OH radicals. However, when OH-concentrations are very low, e.g. during nighttime and at high latitudes in winter, the contribution of the ozone reaction dominates and under these conditions the ozone-alkene reaction will have a clearly visible impact on the stable carbon isotope ratio of atmospheric alkenes.

  8. Photochemical cycloaddition reactions of cyanoacetylene and dicyanoacetylene

    NASA Technical Reports Server (NTRS)

    Ferris, J. P.; Guillemin, J. C.

    1990-01-01

    Photolysis of cyanoacetylene with 185- or 206-nm light yields 1,3,5-tricyanobenzene while 254-nm radiation yields a mixture of tetracyanocyclooctatetraenes, 1,2,4- and 1,3,5-tricyanobenzene. A polymer of cyanoacetylene is the major photoproduct. 1,3,5-Tricarbomethoxybenzene was the only photoproduct identified from the irradiation of methyl propiolate at 254 nm. Mono-, di-, and tricyanobenzenes are formed by irradiation of mixtures of acetylene and cyanoacetylene at 185, 206, and 254 nm along with trace amounts of cyclooctatetraenes. No photoadducts were detected on photolysis of mixtures of cyanoacetylene and CO or HCN. The tetracyanocyclooctatetraene structures were established by UV, MS, and NMR analyses. The 1H NMR of the product mixture exhibited a singlet at delta 7.028 consistent with either 1 or 2 and two singlets at delta 6.85 and 6.91 assigned to 3. Photolysis of mixtures of dicyanoacetylene and acetylene with either 185- or 206-nm light yielded 1,2-dicyanobenzene and (E,Z)-1-buten-3-yne-1,4-dicarbonitrile. These products were also obtained using 254-nm light along with a mixture of tetracyanocyclooctatetraenes. The same three singlets were observed in this product mixture as were observed in the tetracyanocyclooctatetraenes obtained from cyanoacetylene. From this observation it was concluded that the delta 7.02 signal is due to 2 and not 1. The photolysis of cyanoacetylene and dicyanoacetylene in the presence of ethylene with 185-nm light yields 1-cyanocylobutene and 1,2-dicyanocyclobutene, respectively. 2-Cyanobutadiene and 2,3-dicyanobutadiene are the photoproducts with 254-nm light. Reaction pathways are proposed to explain these findings.

  9. Use of ferric sulfate: acid media for the desulfurization of model compounds of coal. [Dibenzothiophene, diphenyl sulfide, di-n-butyl sulfide

    SciTech Connect

    Clary, L.R.; Vermeulen, T.; Lynn, S.

    1980-12-01

    The objective of this work has been to investigate the ability of ferric sulfate-acid leach systems to oxidize the sulfur in model compounds of coal. Ferric iron-acid leach systems have been shown to be quite effective at removal of inorganic sulfur in coal. In this study, the oxidative effect of ferric iron in acid-leach systems was studied using dibenzothiophene, diphenyl sulfide, and di-n-butyl sulfide as models of organic sulfur groups in coal. Nitrogen and oxygen, as well as various transition metal catalysts and oxidants, were utilized in this investigation. Dibenzothiophene was found to be quite refractory to oxidation, except in the case where metavanadate was added, where it appears that 40% oxidation to sulfone could have occurred per hour at 150/sup 0/C and mild oxygen pressure. Diphenyl sulfide was selectively oxidized to sulfoxide and sulfone in an iron and oxygen system. Approximately 15% conversion to sulfone occurred per hour under these conditions. Some of the di-n-butyl sulfide was cracked to 1-butene and 1-butanethiol under similar conditions. Zinc chloride and ferric iron were used at 200/sup 0/C in an attempt to desulfonate dibenzothiophene sulfone, diphenyl sulfone, and di-n-butyl sulfone. Di-n-butyl sulfone was completely desulfurized on one hour and fragmented to oxidized parafins, while dibenzothiophene sulfone and diphenyl sulfone were unaffected. These results suggest that an iron-acid leach process could only selectively oxidize aryl sulfides under mild conditions, representing only 20% of the organic sulfur in coal (8% of the total sulfur). Removal through desulfonation once selective sulfur oxidation had occurred was only demonstrated for alkyl sulfones, with severe oxidation of the fragmented paraffins also occurring in one hour.

  10. Alcohol Dehydrogenase- and Rat Liver Cytosol-Dependent Bioactivation of 1-Chloro-2-hydroxy-3-butene to 1-Chloro-3-buten-2-one, a Bifunctional Alkylating Agent

    PubMed Central

    Elfarra, Adnan A.; Zhang, Xin-Yu

    2012-01-01

    1,3-Butadiene (BD) is an air pollutant whose toxicity and carcinogenicity have been considered primarily mediated by its reactive metabolites, 3,4-epoxy-1-butene and 1,2,3,4-diepoxybutane formed in liver and extrahepatic tissues by cytochromes P450. A possible alternative metabolic pathway in bone marrow and immune cells is the conversion of BD to the chlorinated allylic alcohol 1-chloro-2-hydroxy-3-butene (CHB) by myeloperoxidase in the presence of hydrogen peroxide and chloride ion. In the present study, we investigated the in vitro bioactivation of CHB by alcohol dehydrogenases (ADH) under in vitro physiological conditions (pH 7.4, 37 °C). The results provide clear evidence for CHB being converted to 1-chloro-3-buten-2-one (CBO) by purified horse liver ADH and rat liver cytosol. CBO readily reacted with glutathione (GSH) under assay conditions to form three products: two CBO-mono-GSH conjugates [1-chloro-4-(S-glutathionyl)butan-2-one (3) and 1-(S-glutathionyl)-3-buten-2-one (4)], and one CBO-di-GSH conjugate [1,4-bis(S-glutathionyl)butan-2-one (5)]. CHB bioactivation and the ratios of the three GSH conjugates formed were dependent upon incubation time, GSH and CHB concentrations, and the presence of ADH or rat liver cytosol. The ADH enzymatic reaction followed Michaelis-Menten kinetics with a Km at 3.5 mM and a kcat at 0.033 s−1. After CBO was incubated with freshly isolated mouse erythrocytes, globin dimers were detected using SDS-PAGE and silver staining, providing evidence that CBO can act as a protein cross-linking agent. Collectively, the results provide clear evidence for CHB bioactivation by ADH and rat liver cytosol to yield CBO. The bifunctional alkylating ability of CBO suggests that it may play a role in BD toxicity and/or carcinogenicity. PMID:23110628

  11. High throughput HPLC-ESI(-)-MS/MS methodology for mercapturic acid metabolites of 1,3-butadiene: Biomarkers of exposure and bioactivation.

    PubMed

    Kotapati, Srikanth; Esades, Amanda; Matter, Brock; Le, Chap; Tretyakova, Natalia

    2015-11-01

    1,3-Butadiene (BD) is an important industrial and environmental carcinogen present in cigarette smoke, automobile exhaust, and urban air. The major urinary metabolites of BD in humans are 2-(N-acetyl-l-cystein-S-yl)-1-hydroxybut-3-ene/1-(N-acetyl-l-cystein-S-yl)-2-hydroxybut-3-ene (MHBMA), 4-(N-acetyl-l-cystein-S-yl)-1,2-dihydroxybutane (DHBMA), and 4-(N-acetyl-l-cystein-S-yl)-1,2,3-trihydroxybutyl mercapturic acid (THBMA), which are formed from the electrophilic metabolites of BD, 3,4-epoxy-1-butene (EB), hydroxymethyl vinyl ketone (HMVK), and 3,4-epoxy-1,2-diol (EBD), respectively. In the present work, a sensitive high-throughput HPLC-ESI(-)-MS/MS method was developed for simultaneous quantification of MHBMA and DHBMA in small volumes of human urine (200?l). The method employs a 96 well Oasis HLB SPE enrichment step, followed by isotope dilution HPLC-ESI(-)-MS/MS analysis on a triple quadrupole mass spectrometer. The validated method was used to quantify MHBMA and DHBMA in urine of workers from a BD monomer and styrene-butadiene rubber production facility (40 controls and 32 occupationally exposed to BD). Urinary THBMA concentrations were also determined in the same samples. The concentrations of all three BD-mercapturic acids and the metabolic ratio (MHBMA/(MHBMA+DHBMA+THBMA)) were significantly higher in the occupationally exposed group as compared to controls and correlated with BD exposure, with each other, and with BD-hemoglobin biomarkers. This improved high throughput methodology for MHBMA and DHBMA will be useful for future epidemiological studies in smokers and occupationally exposed workers. PMID:25727266

  12. Development and application of FI catalysts for olefin polymerization: unique catalysis and distinctive polymer formation.

    PubMed

    Makio, Haruyuki; Fujita, Terunori

    2009-10-20

    Catalysts contribute to the efficient production of chemicals and materials in almost all processes in the chemical industry. The polyolefin industry is one prominent example of the importance of catalysts. The discovery of Ziegler-Natta catalysts in the 1950s resulted in the production of high-density polyethylenes (PEs) and isotactic polypropylenes (iPPs). Since then, further catalyst development has led to the production of a new series of polyolefins, including linear low-density PEs, amorphous ethylene/1-butene copolymers, ethylene/propylene/diene elastomers, and syndiotactic PPs (sPPs). Polyolefins are now the most important and the most produced synthetic polymers. This Account describes a family of next-generation olefin polymerization catalysts (FI catalysts) that are currently being used in the commercial production of value-added olefin-based materials. An FI catalyst is a heteroatom-coordinated early transition metal complex that combines a pair of nonsymmetric phenoxy-imine [O(-), N] chelating ligands with a group 4 transition metal. The catalytically active species derived from FI catalysts is highly electrophilic and can assume up to five isomeric structures based on the coordination of the phenoxy-imine ligand. In addition, the accessibility of the ligands of the FI catalysts and their amenability to modification offers an opportunity for the design of diverse catalytic structures. FI catalysts exhibit many unique chemical characteristics: precise control over chain transfers (including highly controlled living ethylene and propylene polymerizations), extremely high selectivity for ethylene, high functional group tolerance, MAO- and borate-free polymerization catalysis, significant morphology polymer formation, controlled multimodal behavior, high incorporation ability for higher alpha-olefins and norbornene, and highly syndiospecific and isospecific polymerizations of both propylene and styrene. These reactions also occur with very high catalyst efficiency. The reaction products include a wide variety of unique olefin-based materials, many of which were previously unavailable via other means of polymerization. We have produced selective vinyl- and Al-terminated PEs, ultrahigh molecular weight linear PEs, regio- and stereoirregular high molecular weight poly(higher alpha-olefin)s, ethylene- and propylene-based telechelic polymers, a wide array of polyolefinic block copolymers from ethylene, propylene, and higher alpha-olefins, and ultrafine noncoherent PE particles. FI catalysts are important from the organometallic, catalytic, and polymer science points of view, and the chemical industry is now using them for the production of value-added olefin-based materials. We anticipate that future research on FI catalysts will produce additional olefin-based materials with unique architectures and material properties and will offer scientists the chance to further study olefin polymerization catalysis and related reaction mechanisms. PMID:19588950

  13. Preparation and reactions of tantalum alkylidene complexes containing bulky phenoxide or thiolate ligands. Controlling ring-opening metathesis polymerization activity and mechanism through choice of anionic ligand

    SciTech Connect

    Wallace, K.C.; Liu, A.H.; Dewan, J.C.; Schrock, R.R. )

    1988-07-20

    Addition of LiDIPP = O-2,6-C{sub 6}H{sub 3}-i-Pr{sub 2} to Ta(CH-t-Bu)(THF){sub 2}Cl{sub 3} yields Ta(CH-t-Bu)(DIPP){sub 3}(THF) (1) in high yield. Ta(CH-t-Bu)(DMP){sub 3}(THF) (3; DMP = O-2,6-C{sub 6}H{sub 3}Me{sub 2}) and Ta(CH-t-Bu)(TIPT){sub 3}(THF) (5; TIPT = S-,2,4,6-C{sub 6}H{sub 2}i-Pr{sub 3}) can be prepared by analogous methods. 1 reacts rapidly with 1 equiv of styrene to give the tantalacyclobutane complex Ta(CH(Ph)CH(t-Bu)CH{sub 2})(DIPP){sub 3}. The crystal and molecular structure of the complex are reported. An analogous reaction between 1 and vinyltrimethylsilane gives Ta(CHSiMe{sub 3})(DIPP){sub 3}(THF) or Ta(CH(SiMe{sub 3})CH(SiMe{sub 3})CH{sub 2})(DIPP){sub 3} depending upon reaction conditions; the two are in ready equilibrium. 1 reacts smoothly with ethylene to give Ta(CH{sub 2}CH{sub 2}CH{sub 2})(DIPP){sub 3} in high yield, but treatment of 1 with olefins such as propylene or 1-butene did not lead to any characterizable species. Addition of excess cis-2-pentene to 1 results in rapid metathesis (100 equiv to equilibrium in < 15 min), but activity is short-lived. In contrast to reactions between 1 and olefins, Ta(CH-t-Bu)(TIPT){sub 3}(THF) does not react with ordinary olefins and will not metathesize them. Tantalacyclobutane complexes containing the DIPP ligand react with the carbonyl functionality to give a mixture of insertion chemistry (oxytantalacyclohexane complexes) and Wittig-like reactivity, depending upon the carbonyl compound, the tantalacycle, and the temperature. 1 reacts with norbornene to give an isolable tantalacyclobutane complex, Ta(CH(C{sub 5}H{sub 8})CHCH(t-Bu))(DIPP){sub 3}, whose crystal structure is reported. 25 references, 9 figures, 7 tables.

  14. Transferable Anisotropic United-Atom Force Field Based on the Mie Potential for Phase Equilibrium Calculations: n-Alkanes and n-Olefins.

    PubMed

    Hemmen, Andrea; Gross, Joachim

    2015-09-01

    A new transferable force field parametrization for n-alkanes and n-olefins is proposed in this work. A united-atom approach is taken, where hydrogen atoms are lumped with neighboring atoms to single interaction sites. A comprehensive study is conducted for alkanes, optimizing van der Waals force field parameters in 6 dimensions. A Mie n-6 potential is considered for the van der Waals interaction, where for n-alkanes we simultaneously optimize the energy parameters ?CH3 and ?CH2 as well as the size parameters ?CH3 and ?CH2 of the CH3(sp(3)) and CH2(sp(3)) groups. Further, the repulsive exponent n of the Mie n-6 potential is varied. Moreover, we investigate the bond length toward the terminal CH3 group as a degree of freedom. According to the AUA (anisotropic united-atom) force field, the bond length between the terminal CH3 group and the neighboring interaction site should be increased by ?l compared with the carbon-carbon distance in order to better account for the hydrogen atoms. The parameter ?l is considered as a degree of freedom. The intramolecular force field parametrization is taken from existing force fields. A single objective function for the optimization is defined as squared relative deviations in vapor pressure and in liquid density of propane, n-butane, n-hexane, and n-octane. A similar study is also done for olefins, where the objective function includes 1-butene, 1-hexene, 1-octene, cis-2-pentene, and trans-2-pentene. Molecular simulations are performed in the grand canonical ensemble with transition-matrix sampling where the phase equilibrium properties are obtained with the histogram reweighting technique. The 6-dimensional optimization of strongly correlated parameters is possible, because the analytic PC-SAFT equation of state is used to locally correlate simulation results. The procedure is iterative but leads to very efficient convergence. An implementation is proposed, where the converged result is not affected (disturbed) by the analytic equation of state. The resulting transferable anisotropic Mie-potential (TAMie) force field shows average relative deviations in vapor pressure of 1.1% and in liquid density of 0.9% for alkanes, and 2% and 1.5% for olefins, respectively, in a wide range of (reduced) temperature, Tr = 0.55-0.97. For substances that were not members of the objective function, the TAMie force field enables predictions of phase equilibrium properties with good accuracy. PMID:26274900

  15. Synthesis of X-Ray Sensitive Polymers and Their Applications as Resists

    NASA Astrophysics Data System (ADS)

    Davies, Jack Dean

    Aliphatic polycarbonates were synthesized by condensation of the bischloroformate of 2,2,4,4-tetramethyl-1,3-cyclobutanediol with cyclic aliphatic diols. Polycarbonates that lacked flexible methylene units in the backbone processed T _{rm g} > 139 ^circC. Copolycarbonates acted as resists when combined with cobalt(III)-am(m)ine tetraphenylborate complexes which act as photointiators, with tetraphenylborate serving as counter anion. The photoinitiator liberates either ammonia or ethylene diamine base upon UV exposure and the polycarbonate backbone is subject to nucleophilic attack at the carbonyl linkage by the base. Image tone was dependent on the base used. Amine complexes, Co(NH _3)_6^{3+} effected a positive tone due to ammonia induced main chain degradation at the carbonate linkage. Cobalt ethylenediamine complex, Co(en)_3^{3+} , en is ethylenediamine, effected a negative tone. The released ethylenediamine acted as a tetrafunctional crosslinking agent forming carbamate linkages. Resolution studies determined linewidths to 20 mum. The amine complex, under low intensity UV radiation, >0.35 mW/cm^2, and elevated temperatures, >40^circC, promoted vapor developed positive tone images in the resists layer. 1-Butene, 2-methyl-1-pentene, cyclohexene, and norbornene were copolymerized with sulfur dioxide. Thermal characterization revealed that these copolymers possess low T_{rm g}, i.e., <35^circC, and two degradation transitions between 110-200 ^circC. They undergo main chain degradation forming positive tone images when exposed to synchrotron radiation and base development. Sensitivities were determined to be <25 mJ/cm^2 for poly (2-methyl pentene-1 sulfone). This copolymer vapor develops upon exposure of ?m thick films to doses >800 mJ/cm ^2. Features to 0.4muM were obtained in this manner using a test mask. Novel polysulfones were prepared by the polymerization of SO_2 with conjugated dienes. Polymerizations were perfonned at -78^circ C in nitropropane as solvent using t-butyl hydroperoxide as initiator. The T_{rm g} of these polymers are >70 ^circC with similar degradation transitions seen for the poly (olefin sulfone) copolymers. These polymers are soluble in a common solvent, nitromethane. Poly(hexadiene -1,3 sulfone) acted as a positive tone resist when exposed to synchrotron radiation and developed in nitropropane. Sensivities <50 mJ/cm^2 were determined for this polymer, vapor development was not achieved. Resolution studies revealed line widths to 0.25 muM, the feature limits of the test mask used.

  16. Plasma discharge in N2 + CH4 at low pressures: experimental results and applications to Titan.

    PubMed

    Thompson, W R; Henry, T J; Schwartz, J M; Khare, B N; Sagan, C

    1991-01-01

    We report the yields of gaseous hydrocarbons and nitriles produced in a continuous flow, low-dose, cold plasma discharge excited in a 10% CH4, 90% N2 atmosphere at 295 K and pressures p of 17 and 0.24 mbar, and use the results to compute expected abundances of minor constituents in Titan's atmosphere. These experiments are, by design, relevant to the atmospheric chemistry induced by cosmic rays in Titan's troposphere and (at the lower pressure) to chemistry initiated by Saturnian magnetospheric electrons and other charged particle sources which excite stratospheric aurorae. At p = 17 mbar, 59 gaseous species including 27 nitriles are detected in overall yield 4.0 (C + N) atoms incorporated into products per 100 eV (heV). At p = 0.24 mbar, 19 species are detected, including six nitriles and three other unidentified N-bearing compounds; the yield is 0.79 (C + N)/heV, a mild decrease with pressure. The types of molecules formed change more markedly, with high degrees of multiple bonding at 0.24 mbar prevailing over more H-saturated molecules at 17 mbar. The molecules and yields at 0.24 mbar bear a striking resemblance to the minor constituents found in Titan's atmosphere, all of which are abundant products in the laboratory experiment. Using the altitude-integrated flux of charged particle energy deposition at Titan, the laboratory yields at p = 0.24 mb, and a simple eddy mixing model, we compute absolute stratospheric column abundances and mole fractions. These are found to be in very good agreement with the Voyager IRIS observations. Except for the primarily photochemical products, C2H6 and C3H8, the match is much better than that obtained by photochemical-kinetic models, demonstrating that properly designed laboratory experiments are directly applicable to modeling radiation-chemical processes in planetary atmospheres. On the basis of this agreement we expect CH3-C triple bond N (ethanenitrile = acetonitrile) CH2=CH-CH=CH2 (1,3-butadiene), CH2=C=CH2 (1,2-propadiene = allene), and CH2=CH-C triple bond CH (1-buten-3-yne) to be present at mol fractions X > 10(-9), and CH2=CH-C triple bond N (propenenitrile), CH3-CH=CH2 (propene), and CH3-CH2-C triple bond N (propanenitrile) at X > 10(-10) in Titan's atmosphere. PMID:11538099

  17. The interactions between microphase separation and crystallization in block copolymers containing polyethylene

    NASA Astrophysics Data System (ADS)

    Quiram, Daniel Jonathan

    The interactions between microphase separation and crystallization were examined in block copolymers containing polyethylene of varying chemistry, composition (fsb{E} = 0.26-0.88, where fsb{E} is weight fraction polyethylene), and molecular weight. Block copolymer compositions were altered to explore crystallization from three distinct melt morphologies: body-centered cubic spheres, hexagonally-packed cylinders, and alternating lamellae. Polymer morphology was investigated on a size-scale ranging from angstroms to microns, employing wide-angle and small-angle x-ray scattering (WAXS and SAXS), small-angle light scattering, and differential scanning calorimetry. The primary series of diblock copolymers investigated were polyethylene-b-poly(3-methyl-1-butene) (E/MB, where MB is an olefinic rubber; fsb{E} = 0.26-0.27). This composition led to a cylindrical morphology when the melt microphase separated. Molecular weights were varied to obtain differing degrees of melt incompatibility, ranging from disordered to strongly segregated. Crystallization from strongly segregated melts was confined to the cylindrical microdomains, essentially independent of thermal history. In contrast, the morphology produced by crystallization from weakly segregated melts was highly dependent upon thermal history. Several block copolymers with microphase-separated melts containing an E block and either polystyrene (glass transition temperature, Tsb{g}? 100spC) or poly(vinylcyclohexane) (Tsb{g}? 135spC) were investigated to determine the effect of a vitreous component on crystallization. SAXS experiments showed that vitrification of the amorphous material effectively confined E crystallization to its melt domain phase: cylinders in a glassy matrix, lamellae, and matrices surrounding both glassy cylinders and spheres. Crystalline chain orientation within cylinders was examined through WAXS. The chains aligned preferentially and this orientation varied depending on chain diffusion during the crystallization process. When chain diffusion was rapid, alignment with the crystalline chain axis perpendicular to the cylinder axis was observed. The crystallization behavior of the E/MB series was investigated via simultaneous, time-resolved SAXS/WAXS. For crystallization from a strongly segregated melt, differences in intercylinder spacing between the high temperature melt and low temperature solid resulted from the temperature dependence of the intercylinder spacing in the melt. Remarkably, despite differences in final structure when crystallization was constrained to cylinders and when it led to lamellae, the crystallization kinetics were quite similar.

  18. Ab initio/RRKM-ME study on the mechanism and kinetics of the reaction of phenyl radical with 1,2-butadiene.

    PubMed

    Kislov, V V; Mebel, A M

    2010-07-29

    Ab initio G3(MP2,CC)//B3LYP/6-311G** calculations have been performed to investigate the potential energy surface and mechanism of the reaction of phenyl radical with 1,2-butadiene followed by kinetic RRKM-ME calculations of the reaction rate constants and product branching ratios at various temperatures and pressures. The results show that the reaction can proceed by direct hydrogen abstraction to produce benzene and C(4)H(5) radicals or by addition of phenyl to different carbon atoms in CH(2)CCHCH(3) followed by isomerizations of C(10)H(11) adducts and their dissociation by H or CH(3) losses. The H abstraction channels are found to be kinetically preferable and to contribute 70-90% to the total product yield in the 300-2500 K temperature range, with the products including C(6)H(6) + CH(2)CHCCH(2) (approximately 40%), C(6)H(6) + CH(3)CHCCH (5-31%), and C(6)H(6) + CH(2)CCCH(3) (24-20%). The phenyl addition channels are calculated to be responsible for 10-30% of the total product yield, with their contribution decreasing as the temperature increases. The products of the addition channels include collisionally stabilized C(10)H(11) adducts, 1-phenyl-2-buten-2-yl, 3-phenyl-2-buten-2-yl, and 2-phenyl-2-buten-1-yl/2-phenyl-1-buten-3-yl, which are favored under low temperatures, as well as their dissociation products, 1-phenyl-propyne + CH(3), phenylallene + CH(3), and 2-phenyl-1,3-butadiene + H, preferred at higher temperatures. Indene is predicted to be a very minor reaction product at the temperatures relevant to combustion, with the maximal calculated yield of only 2% at 700 K and 7.6 Torr. Our calculations showed that at typical combustion temperatures product branching ratios are practically independent of pressure, and collisional stabilization of reaction intermediates does not play a significant role. Three-parameter modified Arrhenius expressions have been generated for the total reaction rate constants and rate constants for the most important product channels, which can be utilized in future kinetic modeling of reaction networks related to the growth of hydrocarbons in combustion processes. PMID:20593856

  19. Quantitation of DNA Adducts Induced by 1,3-Butadiene

    NASA Astrophysics Data System (ADS)

    Sangaraju, Dewakar; Villalta, Peter W.; Wickramaratne, Susith; Swenberg, James; Tretyakova, Natalia

    2014-07-01

    Human exposure to 1,3-butadiene (BD) present in automobile exhaust, cigarette smoke, and forest fires is of great concern because of its potent carcinogenicity. The adverse health effects of BD are mediated by its epoxide metabolites such as 3,4-epoxy-1-butene (EB), which covalently modify genomic DNA to form promutagenic nucleobase adducts. Because of their direct role in cancer, BD-DNA adducts can be used as mechanism-based biomarkers of BD exposure. In the present work, a mass spectrometry-based methodology was developed for accurate, sensitive, and precise quantification of EB-induced N-7-(1-hydroxy-3-buten-2-yl) guanine (EB-GII) DNA adducts in vivo. In our approach, EB-GII adducts are selectively released from DNA backbone by neutral thermal hydrolysis, followed by ultrafiltration, offline HPLC purification, and isotope dilution nanoLC/ESI+-HRMS3 analysis on an Orbitrap Velos mass spectrometer. Following method validation, EB-GII lesions were quantified in human fibrosarcoma (HT1080) cells treated with micromolar concentrations of EB and in liver tissues of rats exposed to sub-ppm concentrations of BD (0.5-1.5 ppm). EB-GII concentrations increased linearly from 1.15 0.23 to 10.11 0.45 adducts per 106 nucleotides in HT1080 cells treated with 0.5-10 ?M DEB. EB-GII concentrations in DNA of laboratory rats exposed to 0.5, 1.0, and 1.5 ppm BD were 0.17 0.05, 0.33 0.08, and 0.50 0.04 adducts per 106 nucleotides, respectively. We also used the new method to determine the in vivo half-life of EB-GII adducts in rat liver DNA (2.20 0.12 d) and to detect EB-GII in human blood DNA. To our knowledge, this is the first application of nanoLC/ESI+-HRMS3 Orbitrap methodology to quantitative analysis of DNA adducts in vivo.

  20. Electron-impact ionization of benzoic acid, nicotinic acid and their n-butyl esters

    NASA Astrophysics Data System (ADS)

    Opitz, Joachim

    2007-08-01

    Electron-impact ionization mass spectra, the decay of metastable ions, ionization and appearance energies and bond energies, as dissociation energies, are reported for the title compounds. An ionization energy of 9.47 eV was obtained for benzoic acid, 9.43 eV for benzoic acid n-butyl ester, 9.61 eV for nicotinic acid and 9.97 eV for nicotinic acid n-butyl ester. Molecular ions of both butyl esters show two common main fragmentation pathways: the first process is a McLafferty rearrangement, characterized by the transfer of one H-atom from the aliphatic ester chain, which leads to the ions of either the organic acid or 1-butene. From their appearance energies and known thermodynamic data, gas-phase formation enthalpies () of the parent n-butyl esters are calculated. Values of for benzoic acid n-butyl ester and for nicotinic acid n-butyl ester were obtained. The second process is characterized by the transfer of two H-atoms from the ester chain leading to a protonated form of the corresponding organic acids and C4H7 radicals. Good evidence is provided for the formation of methylallyl radicals. Appearance energies are used to calculate a proton affinity (PA) for benzoic acid. The obtained value of PA = (8.73 0.3) eV, corresponding to a protonation of the carbonyl group, is in close corroboration with published data (PA = 8.51 eV). Activation energies for the intermediate H-transfers were found to be insignificant. This methodic gateway is applied to the system of nicotinic acid and its butyl ester. Adopting the formation of a methylallyl radical, the obtained proton affinity of nicotinic acid, PA = 8.58 eV, is very near to the published data of benzoic acid. An alternative fragmentation mechanism leading to a value of PA [approximate] 9.5 eV (typical for a protonation of the pyridine-nitrogen) is very unlikely. It is concluded that this transfer of two H-atoms from the ester chain is controlled by a charge switching between the carboxylic oxygen atoms which leads to a regiospecific protonation site, in this case to the protonated carbonyl group. This is conform with a B3LYP DFT calculation with a corresponding proton affinity of PA = 8.29 eV.

  1. The pyrolysis of 2-methylfuran: a quantum chemical, statistical rate theory and kinetic modelling study.

    PubMed

    Somers, Kieran P; Simmie, John M; Metcalfe, Wayne K; Curran, Henry J

    2014-03-21

    Due to the rapidly growing interest in the use of biomass derived furanic compounds as potential platform chemicals and fossil fuel replacements, there is a simultaneous need to understand the pyrolysis and combustion properties of such molecules. To this end, the potential energy surfaces for the pyrolysis relevant reactions of the biofuel candidate 2-methylfuran have been characterized using quantum chemical methods (CBS-QB3, CBS-APNO and G3). Canonical transition state theory is employed to determine the high-pressure limiting kinetics, k(T), of elementary reactions. Rice-Ramsperger-Kassel-Marcus theory with an energy grained master equation is used to compute pressure-dependent rate constants, k(T,p), and product branching fractions for the multiple-well, multiple-channel reaction pathways which typify the pyrolysis reactions of the title species. The unimolecular decomposition of 2-methylfuran is shown to proceed via hydrogen atom transfer reactions through singlet carbene intermediates which readily undergo ring opening to form collisionally stabilised acyclic C5H6O isomers before further decomposition to C1-C4 species. Rate constants for abstraction by the hydrogen atom and methyl radical are reported, with abstraction from the alkyl side chain calculated to dominate. The fate of the primary abstraction product, 2-furanylmethyl radical, is shown to be thermal decomposition to the n-butadienyl radical and carbon monoxide through a series of ring opening and hydrogen atom transfer reactions. The dominant bimolecular products of hydrogen atom addition reactions are found to be furan and methyl radical, 1-butene-1-yl radical and carbon monoxide and vinyl ketene and methyl radical. A kinetic mechanism is assembled with computer simulations in good agreement with shock tube speciation profiles taken from the literature. The kinetic mechanism developed herein can be used in future chemical kinetic modelling studies on the pyrolysis and oxidation of 2-methylfuran, or the larger molecular structures for which it is a known pyrolysis/combustion intermediate (e.g. cellulose, coals, 2,5-dimethylfuran). PMID:24496403

  2. Pathway and Surface Mechanism Studies of 1,3-butadiene Selective Oxidation Over Vanadium-Molybdenum-Oxygen Catalysts

    SciTech Connect

    William David Schroeder

    2002-05-27

    The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m{sup 2}/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO{sub 3}/(MoO{sub 3} + V{sub 2}O{sub 5}). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V{sup +4} and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V{sub 2}O{sub 5}-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V{sub 2}O{sub 5}, solid solutions of Mo in V{sub 2}O{sub 5}, V{sub 9}Mo{sub 6}O{sub 40}, and other reduced VMoO compounds, characterized by laser Raman spectroscopy. The natural composition gradient imposed by the sputter deposition apparatus was used to create VMoO arrays containing 225 samples ranging from 7.0-42 mol% MoO{sub 3}/(V{sub 2}O{sub 5} + MoO{sub 3}), determined by EDS analysis.

  3. Radical Yields from the Ozonolysis of Small (C2-C6) Alkenes

    NASA Astrophysics Data System (ADS)

    Alam, Mohammed; Camredon, Marie; Carr, Timo; Wyche, Kevin; Hornsby, Karen; Monks, Paul; Rickard, Andrew; Bloss, William

    2010-05-01

    Unsaturated VOCs, alkenes, are emitted to the atmosphere from a wide range of anthropogenic and natural sources. They are significant primary pollutants in the boundary layer, contributing to total VOC emissions in urban air, where they may account for up to 30% of the total OH sink, however a key fate for alkenes is reaction with ozone, which may form the dominant loss pathway depending on local conditions, and leads to the non-photolytic production of OH, HO2 and RO2 radicals. Radical formation via ozonolysis is of interest as it may substantially influence the radical budget in urban and rural environments. While there are a number of quantitative indirect OH yield measurements from ozonolysis in the literature, obtained for example through the use of radical tracers / scavenger species, very few direct observations have been reported. Moreover, reported yields for HO2 and RO2 production have been largely inferred through the observation of associated stable products using assumed mechanisms. Gas-phase alkene-ozone reactions also generate a range of degradation products, notably secondary organic aerosol precursors, which together with many other products remain largely unidentified for biogenic alkenes. We present a comprehensive analysis of detailed simulation chamber experiments in which the total radical production and degradation products of alkene ozonolysis reactions have been directly observed for ethene, propene, methylpropene, 1-butene, trans/cis-2-butene and 2,3-dimethyl-2-butene. The experiments were carried out in the European photoreactor EUPHORE (Valencia, Spain), with instrumentation including chemical-ionization-reaction time-of-flight mass-spectrometer (CIR-TOF-MS) and laser-induced fluorescence (LIF) to measure stable VOC and radical products respectively. Alkene/ozone reactions were investigated with and without the presence of a radical scavenger, in order to suppress side reactions and to obtain reaction rate coefficients, primary carbonyl and stabilized Criegee yields. Radical concentrations were measured directly, and interpreted through detailed chemical box modelling drawing upon the Master Chemical Mechanism (MCMv3.1) with mechanistic updates from the recent literature and our results. Reaction rate coefficients, radical yields and stable product yields are compared with those simulated, and the implications for atmospheric oxidant levels are presented.

  4. Isomerization of neopentyl chloride and neopentyl bromide by a 1,2-interchange of a halogen atom and a methyl group.

    PubMed

    Lisowski, Carmen E; Duncan, Juliana R; Ranieri, Anthony J; Heard, George L; Setser, D W; Holmes, Bert E

    2010-09-30

    The recombination of chloromethyl and t-butyl radicals at room temperature was used to generate neopentyl chloride molecules with 89 kcal mol(-1) of internal energy. The observed unimolecular reactions, which give 2-methyl-2-butene and 2-methyl-1-butene plus HCl, as products, are explained by a mechanism that involves the interchange of a methyl group and the chlorine atom to yield 2-chloro-2-methylbutane, which subsequently eliminates hydrogen chloride by the usual four-centered mechanism to give the observed products. The interchange isomerization process is the rate-limiting step. Similar experiments were done with CD(2)Cl and C(CH(3))(3) radicals to measure the kinetic-isotope effect to help corroborate the proposed mechanism. Density functional theory was employed at the B3PW91/6-31G(d',p') level to verify the Cl/CH(3) interchange mechanism and to characterize the interchange transition state. These calculations, which provide vibrational frequencies and moments of inertia of the molecule and transition state, were used to evaluate the statistical unimolecular rate constants. Matching the calculated and experimental rate constants, gave 62 2 kcal mol(-1) as the threshold energy for interchange of the Cl atom and a methyl group. The calculated models also were used to reinterpret the thermal unimolecular reactions of neopentyl chloride and neopentyl bromide. The previously assumed Wagner-Meerwein rearrangement mechanism for these reactions can be replaced by a mechanism that involves the interchange of the halogen atom and a methyl group followed by HCl or HBr elimination from 2-chloro-2-methylbutane and 2-bromo-2-methylbutane. Electronic structure calculations also were done to find threshold energies for several related molecules, including 2-chloro-3,3-dimethylbutane, 1-chloro-2-methyl-2-phenylpropane, and 1-chloro-2-methyl-2-vinylpropane, to demonstrate the generality of the interchange reaction involving a methyl, or other hydrocarbon groups, and a chlorine atom. The interchange of a halogen atom and a methyl group located on adjacent carbon atoms can be viewed as an extension of the halogen atom interchange mechanisms that is common in 1,2-dihaloalkanes. PMID:20809644

  5. Adsorption and desorption kinetics of alkanethiols on gold(100) and silver(111)

    NASA Astrophysics Data System (ADS)

    Yu, Yan

    The work reported here is concerned with the adsorption and desorption kinetics of short chain-length alkanethiols and hydrogen sulfide on the Au(100) and Ag(111) substrates. A combination of temperature programmed desorption/reaction (TPD/R), low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and molecular beam (MB) methods were used in a UHV system. This study has given insight in to the kinetic mechanism of thiol self-assembled monolayers (SAMs) formation. Similar adsorption and desorption kinetics were observed for methanethiol, ethanethiol, propanethiol, butanethiol, and pentanethiol on Au(100). The TPD/R results clearly show that these short chain-length alkanethiols adsorbs into both a chemisorbed and a physisorbed state. A detail study was performed for butanethiol on the Au(100) substrate. Desorption of physisorbed butanethiol occurs molecularly at 38 K. By contrast, desorption of the chemisorbed butanethiolate species occurs with decomposition at 500 K to yield primarily 1-butene; the thiol sulfur remained adsorbed on the surface and either desorbed or possibly dissolved into the bulk of the gold sample at above 700 K. The substrate temperature dependence of the chemisorption process suggests a precursor mechanism for the chemisorption kinetics. The TPD results also show that chemisorption does not occur on a very clean and ordered Au(100)-(5x20) surface at 100 K, and that low coverages of pre-adsorbed sulfur atoms facilitate the chemisorption process, suggesting a defect-mediated precursor mechanism. Precursor-mediated adsorption kinetics were observed for the adsorption of H2S on the Au(100)-(5x20) and Ag(111) between 80 and 100 K, while Langmuir adsorption kinetics were observed for the adsorption of H 2S on the sulfide covered Au(100)-(1x1)-SH and Ag(111). The TPD/R of H2S from Au(100)-(1x1)-SH showed additional features at higher temperatures which were associated with the disproportionation of chemisorbed HS(ad). Those features were not observed for H2S from sulfide Ag(111).

  6. Pressure Effects on Product Channels of the Allyl Radical Reactions; C3H5+C3H5 and C3H5+CH3

    NASA Astrophysics Data System (ADS)

    Halpern, J. B.; N'Doumi, M.; Fahr, A.

    2011-12-01

    Relatively large hydrocarbon molecules (C4, C6 and larger) have been detected in several planetary environments. The mechanism for the formation of such large molecular species and detailed mechanism for their potential destruction are not well understood and are of considerable current interest. Previously we have studied the kinetics and product channels of small unsaturated hydrocarbon radical (C2 and C3s) reactions relevant to planetary atmospheric modeling. Reactions of C2 radicals (such as vinyl, H2CCH and ethynyl C2H) and C3 radicals (such as propargyl, HCCCH2) can affect the abundances of a large number of stable observable C3, C4, C5, C6 and larger molecules, including linear, aromatic and even poly aromatic molecules. Pressure-dependent product yields have been determined experimentally for the self- and cross-radical reactions performed at 298 K and at pressures between ~4 Torr (0.5 kPa) and 760 Torr (101 kPa). Final reaction products were quantitatively determined using a gas chromatograph with mass spectrometry/flame ionization detection (GC/MS/FID). In some cases complementary computational studies extended the pressure and temperature range of the experiments and provided valuable information on the complex reaction mechanisms. Theses studies provide a systematic framework so that important energetic and structural parameters for radical-radical reactions can be assessed. Here we report recent results for the allyl radical reactions H2CCCH3+ H2CCCH3 and H2CCCH3+CH3. For the allyl radical self-reaction, at high pressures the "head -to-head", combination channel forming 1,5-hexadiene is dominant with a combination/disproportionation = 1,5-hexadiene/propyne ratio of about 24 at 500 Torr (67 kPa, T=298K). At low pressures the ratio is substantially reduced to about 1.2 (at 0.3 kPa) and other major products are observed including allene, propene, 1-butene and propyne.

  7. A Unique Equation to Estimate Flash Points of Selected Pure Liquids Application to the Correction of Probably Erroneous Flash Point Values

    NASA Astrophysics Data System (ADS)

    Catoire, Laurent; Naudet, Valrie

    2004-12-01

    A simple empirical equation is presented for the estimation of closed-cup flash points for pure organic liquids. Data needed for the estimation of a flash point (FP) are the normal boiling point (Teb), the standard enthalpy of vaporization at 298.15 K [?vapH(298.15 K)] of the compound, and the number of carbon atoms (n) in the molecule. The bounds for this equation are: -100?FP(C)?+200; 250?Teb(K)?650; 20??vap H(298.15 K)/(kJ mol-1)?110; 1?n?21. Compared to other methods (empirical equations, structural group contribution methods, and neural network quantitative structure-property relationships), this simple equation is shown to predict accurately the flash points for a variety of compounds, whatever their chemical groups (monofunctional compounds and polyfunctional compounds) and whatever their structure (linear, branched, cyclic). The same equation is shown to be valid for hydrocarbons, organic nitrogen compounds, organic oxygen compounds, organic sulfur compounds, organic halogen compounds, and organic silicone compounds. It seems that the flash points of organic deuterium compounds, organic tin compounds, organic nickel compounds, organic phosphorus compounds, organic boron compounds, and organic germanium compounds can also be predicted accurately by this equation. A mean absolute deviation of about 3 C, a standard deviation of about 2 C, and a maximum absolute deviation of 10 C are obtained when predictions are compared to experimental data for more than 600 compounds. For all these compounds, the absolute deviation is equal or lower than the reproductibility expected at a 95% confidence level for closed-cup flash point measurement. This estimation technique has its limitations concerning the polyhalogenated compounds for which the equation should be used with caution. The mean absolute deviation and maximum absolute deviation observed and the fact that the equation provides unbiaised predictions lead to the conclusion that several flash points have been reported erroneously, whatever the reason, in one or several reference compilations. In the following lists, the currently accepted flash points for bold compounds err, or probably err, on the hazardous side by at least 10 C and for the nonbolded compounds, the currently accepted flash points err, or probably err, on the nonhazardous side by at least 10 C: bicyclohexyl, sec-butylamine, tert-butylamine, 2-cyclohexen-1-one, ethanethiol, 1,3-cyclohexadiene, 1,4-pentadiene, methyl formate, acetonitrile, cinnamaldehyde, 1-pentanol, diethylene glycol, diethyl fumarate, diethyl phthalate, trimethylamine, dimethylamine, 1,6-hexanediol, propylamine, methanethiol, ethylamine, bromoethane, 1-bromopropane, tert-butylbenzene, 1-chloro-2-methylpropane, diacetone alcohol, diethanolamine, 2-ethylbutanal, and formic acid. For some other compounds, no other data than the currently accepted flash points are available. Therefore, it cannot be assessed that these flash point data are erroneous but it can be stated that they are probably erroneous. At least, they need experimental re-examination. They are probably erroneous by at least 15 C: 1,3-cyclopentadiene, di-tert-butyl sulfide, dimethyl ether, dipropyl ether, 4-heptanone, bis(2-chloroethyl)ether, 1-decanol, 1-phenyl-1-butanone, furan, ethylcyclopentane, 1-heptanethiol, 2,5-hexanediol, 3-hexanone, hexanoic acid methyl ester, 4-methyl-1,3-pentadiene, propanoyl chloride, tetramethylsilane, thiacyclopentane, 1-chloro-2-methyl-1-propene, trans-1,3-pentadiene, 2,3-dimethylheptane, triethylenetetramine, methylal, N-ethylisopropylamine, 3-methyl-2-pentene, and 2,3-dimethyl-1-butene.

  8. I. Synthesis, characterization, and base catalysis of novel zeolite supported super-basic materials II. Oxidative dehydrogenation of ethane over reduced heteropolyanion catalysts

    NASA Astrophysics Data System (ADS)

    Galownia, Jonathan M.

    This thesis is composed of two separate and unrelated projects. The first part of this thesis outlines an investigation into the synthesis and characterization of a novel zeolite supported super-base capable of carbon-carbon olefin addition to alkyl aromatics. A zeolite supported basic material capable of such reactions would benefit many fine chemical syntheses, as well as vastly improve the economics associated with production of the high performance thermoplastic polyester polyethylene naphthalate. The thermal decomposition of alkali---metal azides impregnated in zeolite X is investigated as a novel route to the synthesis of a zeolite supported super-base. Impregnation of the alkali---metal azide precursor is shown to result in azide species occluded within the pores of the zeolite support by using high speed, solid-state 23Na MAS and 2D MQMAS NMR, FTIR, and TGA characterization methods. Addition of alkali---metal azides to the zeolite results in redistribution of the extra-lattice cations in the zeolite framework. Thermal decomposition of impregnated azide species produces further cation redistribution, but no neutral metallic clusters are detected by high speed, solid-state 23Na MAS NMR following thermal activation of the materials. Instead, it is possible that inactive ionic clusters are formed. The thermally activated materials do not promote base catalysis for the isomerization of 1-butene, the ethylation of toluene and o-xylene, and the alkenylation of o-xylene with 1,3-butadiene to produce 5-ortho-tolyl-pent-2-ene (5-OTP). The lack of catalytic activity in the materials is attributed to failure of the materials to form neutral metallic clusters during thermal treatment, possibly due to preferential formation of NMR silent ionic clusters. The formation of neutral metallic clusters is found to be insensitive to synthesis technique and activation procedure. It is concluded that the impregnation of alkali---metal azides in zeolite X does not provide a reliable precursor for the formation of zeolite supported super-basic materials. The second part of this thesis describes the oxidative dehydrogenation of ethane over partially reduced heteropolyanions. Niobium and pyridine exchanged salts of phosphomolybdic (NbPMo12Pyr) and phosphovanadomolybdic (NbPMo11VPyr) acids are investigated as catalyst precursors to prepare materials for catalyzing the oxidative dehydrogenation of ethane to ethylene and acetic acid at atmospheric pressure. The effects of feed composition, steam flow, temperature, and precursor composition on catalytic activity and selectivity are presented for both ethane and ethylene oxidation. Production of ethylene and acetic acid from ethane using the catalytic materials exceeds that reported in the literature for Mo-V-Nb-Ox systems under atmospheric or elevated pressure. Production of acetic acid from ethylene is also greater than that observed for Mo-V-Nb-Ox systems. Addition of vanadium reduces catalytic activity and selectivity to both ethylene and acetic acid while niobium is essential for the formation of acetic acid from ethane. Other metals such as antimony, iron, and gallium do not provide the same beneficial effect as niobium. Molybdenum in close proximity to niobium is the active site for ethane activation while niobium is directly involved in the transformation of ethylene to acetic acid. A balance of niobium and protonated pyridine is required to produce an active catalyst. Water is found to aid in desorption of acetic acid, thereby limiting deep oxidation to carbon oxides. A reaction scheme is proposed for the production of acetic acid from ethane over the catalytic materials.

  9. Investigation of potential interferences in the detection of atmospheric ROx radicals by laser-induced fluorescence under dark conditions

    NASA Astrophysics Data System (ADS)

    Fuchs, H.; Tan, Z.; Hofzumahaus, A.; Broch, S.; Dorn, H.-P.; Holland, F.; Künstler, C.; Gomm, S.; Rohrer, F.; Schrade, S.; Tillmann, R.; Wahner, A.

    2015-11-01

    Direct detection of highly reactive, atmospheric hydroxyl radicals (OH) is widely accomplished by laser-induced fluorescence (LIF) instruments. The technique is also suitable for the indirect measurement of HO2 and RO2 peroxy radicals by chemical conversion to OH. It requires sampling of ambient air into a low pressure cell, where OH fluorescence is detected after excitation by 308 nm laser radiation. Although the residence time of air inside the fluorescence cell is typically only on the order of milliseconds, there is potential that additional OH is internally produced, which would artificially increase the measured OH concentration. Here, we present experimental studies investigating potential interferences in the detection of OH and peroxy radicals for the LIF instruments of Forschungszentrum Jülich for nighttime conditions. For laboratory experiments, the inlet of the instrument was overflown by excess synthetic air containing one or more reactants. In order to distinguish between OH produced by reactions upstream of the inlet and artificial signals produced inside the instrument, a chemical titration for OH was applied. Additional experiments were performed in the simulation chamber SAPHIR where simultaneous measurements by an open-path differential optical absorption spectrometer (DOAS) served as reference for OH to quantify potential artifacts in the LIF instrument. Experiments included the investigation of potential interferences related to the nitrate radical (NO3, N2O5), related to the ozonolysis of alkenes (ethene, propene, 1-butene, 2,3-dimethyl-2-butene, α-pinene, limonene, isoprene), and the laser photolysis of acetone. Experiments studying the laser photolysis of acetone yield OH signals in the fluorescence cell, which are equivalent to 0.05 × 106 cm-3 OH for a mixing ratio of 5 ppbv acetone. Under most atmospheric conditions, this interference is negligible. No significant interferences were found for atmospheric concentrations of reactants during ozonolysis experiments. Only for α-pinene, limonene, and isoprene at reactant concentrations which are orders of magnitude higher than in the atmosphere artificial OH could be detected. The value of the interference depends on the turnover rate of the ozonolysis reaction. For example, an apparent OH concentration of approximately 1 × 106 cm-3 is observed, if 5.8 ppbv limonene reacts with 600 ppbv ozone. Experiments with the nitrate radical NO3 reveal a small interference signal in the OH, HO2 and RO2 detection. Dependencies on experimental parameters point to artificial OH formation by surface reactions at the chamber walls or in molecular clusters in the gas expansion. The signal scales with the presence of NO3 giving equivalent radical concentrations of 1.1 × 105 cm-3 OH, 1 × 107 cm-3 HO2, and 1.7 × 107 cm-3 RO2 per 10 pptv NO3.

  10. Chromatography and mass spectrometry of prebiological and biological molecules

    NASA Astrophysics Data System (ADS)

    Navale, Vivek

    The detection and identification of prebiological and biological molecules are of importance for understanding chemical and biological processes occurring within the solar system. Molecular mass measurements, peptide mapping, and disulfide bond analysis of enzymes and recombinant proteins are important in the development of therapeutic drugs for human diseases. Separation of hydrocarbons (C1 to C6) and nitriles was achieved by 14%-cyanopropylphenyl-86%- dimethylpolysiloxane (CPPS-DMPS) stationary phase in a narrow bore metal capillary column. The calculation of modeling numbers enabled the differentiation of the C4 hydrocarbon isomers of 1-butene (cis and trans). The modeled retention time values for benzene, toluene, xylene, acetonitrile, propane, and propene nitriles were in good agreement with the measurements. The separation of C2 hydrocarbons (ethane and ethene) from predominantly N2 matrix was demonstrated for the first time on wall coated narrow bore low temperature glassy carbon column. Identification and accurate mass measurements of pepsin, an enzymatic protein with less number of basic amino acid residues were successfully demonstrated by matrix- assisted laser desorption ionization mass spectrometry (MALDI-MS). The molecular mass of pepsin was found to be 34,787 Da. Several decomposition products of pepsin, in m/z range of 3,500 to 4,700 were identified. Trypsin, an important endopeptidase enzyme had a mass of 46829.7 Da. Lower mass components with m/z 8047.5, 7776.6, 5722, 5446.2 and 5185 Da were also observed in trypsin spectrum. Both chemokine and growth factor recombinant proteins were mass analyzed as 8848.1 3.5 and 16178.52 4.1 Da, respectively. The accuracy of the measurements was in the range of 0.01 to 0.02%. Reduction and alkylation experiments on the chemokine showed the presence of six cysteines and three disulfide bonds. The two cysteines of the growth factor contained the free sulfhydryl groups and the accurate average mass of the growth factor protein was 16175.6 Da. MALDI analysis of trypsin digest of Myeloid progenitor inhibitory factor chemokine verified the disulfide bridging among cysteine residues. Several partially digested trypsin and V8 peptides were detected that verified significant portions of the primary structure of the chemokine. Mass difference amounting to the loss of a single amino acid, serine was also identified. The cyanogen bromide (CNBr) treated chemokine produced three peptides 7051, 6910.1 and 1492 Da. The analysis of Keratinocyte growth factor (KGF) peptide mixtures showed suppression effects during the MALDI ionization process. Several partially digested peptides with mass values 3214, 9980, 10325 and 10497 Da were identified. Direct MALDI-MS analysis of cyanogen bromide treated KGF molecule demonstrated the formation of peptides with mass 7567.3, 4992.6 and 3118.6 Da. The high sensitivity of MALDI-MS provided a rapid method for confirming the fidelity of gene expression in the host system. The present work showed that the combined methods of chromatography and mass spectrometry are efficient means for identification and characterization of prebiological and biological molecules.

  11. The Low Temperature Oxidation of 2,7-Dimethyloctane in a Pressurized Flow Reactor

    NASA Astrophysics Data System (ADS)

    Farid, Farinaz

    The complexity of real fuels has fostered the use of simple mixtures of hydrocarbons whose combustion behavior approximates that of real fuels in both experimental and computational studies to develop models of the combustion of the real fuel. These simple mixtures have been called surrogates. Lightly branched paraffins are an important class of constituents in gasoline, diesel and aviation turbine fuels and therefore are primary candidates for use as a component in a surrogate. Unfortunately, fundamental studies on combustion characteristics of high molecular weight mono- and di-methylated iso-paraffins are scarce. Therefore, this study was designed to investigate the low-temperature oxidation of 2,7-dimethyloctane (2,7-DMO) (C10H22), a lightly branched isomer of decane. Replicate 2,7-DMO oxidation experiments were conducted in a pressurized flow reactor (PFR) over the temperature range of 550 -- 850 K, at a pressure of 8 atm and an equivalence ratio of 0.3 in 4.21% oxygen / nitrogen. The reactivity was mapped by continuous monitoring of CO, CO 2, and O2 using a non-dispersive infrared (NDIR) carbon monoxide / carbon dioxide analyzer and an electrochemical oxygen sensor. For examining the underlying reaction chemistry, detailed speciation of samples was performed at selected temperatures using a gas chromatograph with a flame ionization detector coupled to a mass spectrometer. Comparable oxidation experiments for n-decane were carried out to examine the unique effects of branching on fuel reactivity and distribution of major stable intermediates. For both isomers, the onset of negative temperature coefficient (NTC) region was observed near 700 K, with the reactivity decreasing with increasing the temperature. The flow reactor study of n-decane oxidation confirmed that the isomerization reduces the amount of CO produced at peak reactivity. In addition to reaction inhibition, branching affected the distribution of C2-C 4 olefin intermediates. While the oxidation of n-decane resulted primarily in the formation of ethene near the NTC start, propene and isobutene were the major olefins produced from 2,7-DMO. A comparative analysis of experimental data with respect to a detailed chemical kinetic model for 2,7-DMO was performed and discrepancies were noted. Based on these results, a collaborative effort with Dr. Charles Westbrook (Lawrence Livermore National Laboratory) was initiated to refine the model predictions in the low temperature and NTC regimes. The effort resulted in an updated version of the 2,7-DMO mechanism, improving some of the key features such as calculated CO2 profile and final yields of iso-butene over the studied range of temperature. Fuel pyrolysis in the intermediate temperature regime, 850 -- 1000 K, also was investigated for the first time in the PFR facility. However, preliminary n-decane experiments measured only a small amount of fuel decomposition, indicating that higher temperature operation would be beneficial. The major species produced from n-decane decomposition, in descending order of molar fraction, were ethene, propene, and 1-butene. These results were compared with the predictions of two existing chemical kinetic models and the sources of variations between the experiments and the models as well as among the mechanisms were investigated. At 1000 K, the mechanisms predicted higher levels of fuel depletion and ethene production. Also, while the mechanisms were similar in their predicted pathways for fuel depletion and formation of ethene, inconsistencies were observed in relative contribution of these pathways to the final yields as well as the rate parameter determination for several sensitive reactions with respect to n-decane and ethene. Overall, the research aided in achieving a data set quantifying the oxidation characteristics of 2,7-DMO (and n-decane for comparison) as well as an elucidation of critical reaction pathways based on experimental results. Preliminary pyrolysis experiments were carried out using n-decane and the limitations on companion 2,7-DMO pyrolysis experiments were established. The data was compared with the predictions of several chemical kinetic mechanisms and, using tools such as rate of production analysis and sensitivity analysis, the sources of deviations from experimental data as well as possible areas of improvement were identified. The findings from 2,7-DMO study was directly used to refine an existing chemical kinetic model for 2,7-DMO, in line with the ultimate goal of feeding the much needed experimental database for validation and refinement of kinetic models of jet fuel surrogates.