Sample records for aliphatic alco hol

  1. Wadi el-Hol

    E-Print Network [OSTI]

    Darnell, John C

    2013-01-01T23:59:59.000Z

    deposit in Figure 21). Wadi el-Hol, Darnell, UEE 2013of Oxford Short Citation: Darnell, 2013, Wadi el-Hol. UEE.John Coleman, 2013, Wadi el-Hol. In Willeke Wendrich (ed. ),

  2. Isabelle/HOL and SMT Sascha Bohme

    E-Print Network [OSTI]

    Cengarle, María Victoria

    Isabelle/HOL and SMT Sascha B¨ohme Technische Universit¨at M¨unchen September 10, 2009 #12;Outline Introduction From Isabelle/HOL to SMT ... ... and back again Conclusion 1 Introduction Isabelle/HOL SMT Isabelle/HOL and SMT 2 From Isabelle/HOL to SMT ... Supported SMT Solvers Preprocessing 3 ... and back

  3. Verifying Test Hypotheses -HOL/TestGen Verifying Test Hypotheses -HOL/TestGen

    E-Print Network [OSTI]

    Verifying Test Hypotheses - HOL/TestGen Verifying Test Hypotheses - HOL/TestGen An Experiment in Test and Proof Thomas Malcher January 20, 2014 1 / 20 #12;Verifying Test Hypotheses - HOL/TestGen HOL/TestGen Outline Introduction Test Hypotheses HOL/TestGen - Demo Verifying Test Hypotheses Conclusion 2 / 20 #12

  4. The Economics of HOl1icultural Biotechnology

    E-Print Network [OSTI]

    Bradford, Kent

    The Economics of HOl1icultural Biotechnology Julian M. Alston Kent J. Bradford Nicholas Kalaitzandonakes SUMMARY. Technological change has driven economic progress in agIiculture and will continue, Department of Agricultural and Resource Econom- ics, University of California, Davis and Associate Director

  5. Available online at www.sciencedirect.com Electrochemical conversion of CO2 to useful chemicals: current

    E-Print Network [OSTI]

    Kenis, Paul J. A.

    -propanol, allyl alco- hol, acetaldehyde, propionaldehyde, acetate, methanol, ethylene glycol, glycolaldehyde

  6. The conversion of corn stover and pig manure to carboxylic acids with the MixAlco process 

    E-Print Network [OSTI]

    Black, Amanda Spring

    2013-02-22T23:59:59.000Z

    The MixAlco process, developed by Dr. Mark T. Holtzapple, uses anaerobic fermentation to convert waste biomass into carboxylate salts which can then be manipulated into carboxylic acids, ketones and alcohols. This project focuses on the application...

  7. Conversion of MixAlco Process Sludge to Liquid Transportation Fuels

    E-Print Network [OSTI]

    Teiseh, Eliasu 1973-

    2012-02-15T23:59:59.000Z

    of iron instead of cobalt is validated by the fact that the hydrogen production potential of biomass feedstock is low compared to steam reforming of methane which is usually accompanied by the WGS reaction. Since iron catalyst catalyzes the WGS...,33]. The pyrolysis of the MixAlco process sludge and other biomass feedstocks will generate syngas (H2 and CO) together with methane. External modification of the final syngas composition for use in the FTS catalyst may involve the steam reforming of the 3 CH...

  8. DOI: 10.1002/cctc.201200311 Low-Temperature Chemoselective Gold-Surface-Mediated Hydrogenation of

    E-Print Network [OSTI]

    Henkelman, Graeme

    .[9] Claus found that, in the production of allyl alco- hol from the hydrogenation of acrolein, gold

  9. Introduction Aliphatic polyesters derived from renewable

    E-Print Network [OSTI]

    Introduction Aliphatic polyesters derived from renewable resources are of increasing interest, there are also opportunities to derive lactones from biomass, which can then be converted to a wide range

  10. Quantitative textural analysis of packings of elongate crystals John F. Rudge Marian B. Holness Graham C. Smith

    E-Print Network [OSTI]

    Rudge, John

    · Graham C. Smith February 18, 2008 Abstract The spatial distribution of grains in a solidifying igneous: +44-1223-360779. M. B. Holness · G. C. Smith Department of Earth Sciences, Downing Street, Cambridge

  11. Development of aliphatic biodegradable photoluminescent polymers

    E-Print Network [OSTI]

    Yang, Jian

    , 2009 (received for review January 8, 2009) None of the current biodegradable polymers can function monomers including citric acid, aliphatic diols, and various amino acids via a convenient and cost/nano- fabrication. We demonstrate the feasibility of using BPLP-Ser nanoparticles (``biodegradable quantum dots

  12. aplikasi panas nuklir: Topics by E-print Network

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

    Claus found that, in the production of allyl alco- hol from the hydrogenation of acrolein, gold. By employing propionaldehyde and acetone as representa- tive probe molecules...

  13. approach aliphatic monoesters: Topics by E-print Network

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

    in treating a variety of electrostatic Jayaram, Bhyravabotla 6 Far infrared spectra of solid state aliphatic amino acids in different protonation states Physics Websites Summary:...

  14. aliphatic secondary alcohols: Topics by E-print Network

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

    for conversion of biomass derived feedstocks to fuels and fuel additives. Synthesis of ethanol and higher aliphatic alcohols from syngas (CO + H2... Baksh, Faisal 2010-04-19 3 The...

  15. aliphatic alkyl quaternaries: Topics by E-print Network

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

    for conversion of biomass derived feedstocks to fuels and fuel additives. Synthesis of ethanol and higher aliphatic alcohols from syngas (CO + H2... Baksh, Faisal 2010-04-19 45...

  16. aliphatic copolyester films: Topics by E-print Network

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

    Release: Refer to the SAMPLE INDEX for a list of validated samples. Refer to the DATA 20 Synthesis and Self-Assembly of Amphiphilic Dendrimers Based on Aliphatic Polyether-Type...

  17. Process for producing peracids from aliphatic hydroxy carboxylic acids

    DOE Patents [OSTI]

    Chum, H.L.; Palasz, P.D.; Ratcliff, M.A.

    1984-12-20T23:59:59.000Z

    A process is described for producing peracids from lactic acid-containing solutions derived from biomass processing systems. It consists of adjusting the pH of the solution to about 8 to 9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids. The solution is oxidized to produce volatile lower aliphatic aldehydes. The aldehydes are removed as they are generated and converted to peracids.

  18. Synthesis of Aliphatic-Aromatic Copolyesters by a High Temperature

    E-Print Network [OSTI]

    Khan, Saad A.

    -aromatic polyesters. #12;Full Paper: Reverse-selective polymer membranes exhibiting high CO2 affinity can be used for purification of H2 in industrial gasification processes. In this work, the phy- sical properties of CO2Synthesis of Aliphatic-Aromatic Copolyesters by a High Temperature Bulk Reaction Between Poly

  19. Aerobic microorganism for the degradation of chlorinated aliphatic hydrocarbons

    DOE Patents [OSTI]

    Fliermans, Carl B. (Augusta, GA)

    1989-01-01T23:59:59.000Z

    A chlorinated aliphatic hydrocarbon-degrading microorganism, having American Type Culture Collection accession numbers ATCC 53570 and 53571, in a biologically pure culture aseptically collected from a deep subsurface habitat and enhanced, mineralizes trichloroethylene and tetrachloroethylene to HCl, H.sub.2 O and Co.sub.2 under aerobic conditions stimulated by methane, acetate, methanol, tryptone-yeast extract, propane and propane-methane.

  20. Process for producing peracids from aliphatic hydroxy carboxylic acids

    SciTech Connect (OSTI)

    Chum, H.L.; Ratcliff, M.A.; Palasz, P.D.

    1986-10-14T23:59:59.000Z

    This patent describes a wood pulp processing system of the type producing both pulp and a stream of lactic acid-containing black liquor solution, the processor for production of peracid bleaching agents from hydroxy acid contained in the black liquor solution, comprising: adjusting the pH of the black liquor solution to the range of about 8-9 by exposing the solution to CO/sub 2/ carbon dioxide to form an alkaline precipitate; separating solids from the black liquor solution to produce a residual solution containing lower aliphatic hydroxy acids selected from the group consisting of lactic acid, glycolic acid, 2-hydroxybutanoic acid, xyloisosaccharinic acid, and glucoisosaccharinic acid; decarboxylating the lower aliphatic hydroxy acids to corresponding gaseous aliphatic aldehydes by admixing a powdered semiconductor with the residual solution to form a slurry; removing the gaseous aldehydes from the residual solution by sweeping gas flow as soon as they are generated to prevent further oxidation to carboxylic acids; reacting the gaseous aldehydes with oxygen to form corresponding peracids; and applying the peracids as bleaching agents to the pulp produced in the pulp processing system.

  1. ORGANIC GEOCHEMICAL STUDIES. II. THE DISTRIBUTION OF ALIPHATIC HYDROCARBONS IN ALGAE, BACTERIA, AND IN A RECENT LAKE SEDIMENT: A PRELIMINARY REPORT

    E-Print Network [OSTI]

    Han, Jerry; McCarthy, E.D.; Van Hoeven Jr., William; Calvin, Melvin; Bradley, W. H.

    2008-01-01T23:59:59.000Z

    significantly to the hydrocarbons of higher molecular weightDISTRIBUTION OF ALIPHATIC HYDROCARBONS IN ALGAE, BACTERIA,T E DISTRIBUTION O ALIPHATIC HYDROCARBONS H F A PRELIMINARY

  2. Metal Catalyzed Formation of Aliphatic Polycarbonates Involving Oxetanes and Carbon Dioxide as Monomers

    E-Print Network [OSTI]

    Moncada, Adriana I.

    2011-08-08T23:59:59.000Z

    including phosgene and its derivatives. Therefore, it has been of great interest to investigate greener routes for the production of this important class of polymers. Toward this goal, the synthesis of aliphatic polycarbonates via the metal catalyzed...

  3. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOE Patents [OSTI]

    Greene, M.I.; Gelbein, A.P.

    1984-10-16T23:59:59.000Z

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200 to 450 C and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  4. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOE Patents [OSTI]

    Greene, Marvin I. (Oradell, NJ); Gelbein, Abraham P. (Morristown, NJ)

    1984-01-01T23:59:59.000Z

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200.degree. to 450.degree. C. and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  5. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    DOE Patents [OSTI]

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1983-09-20T23:59:59.000Z

    A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

  6. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    DOE Patents [OSTI]

    Googin, John M. (Oak Ridge, TN); Napier, John M. (Oak Ridge, TN); Travaglini, Michael A. (Oliver Springs, TN)

    1983-01-01T23:59:59.000Z

    A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced.

  7. aliphatic hydrocarbons constitute the largest fraction of cuticular wax in bees and cover

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    aliphatic hydrocarbons constitute the largest fraction of cuticular wax in bees and cover a highly hydrocarbons in the cuticular waxes of bees are widely assumed to func- tion as recognition cues (for nestmate hydrocarbons may label individuals in colonies according to the tasks they under- take and that the compounds

  8. Metal Catalyzed Formation of Aliphatic Polycarbonates Involving Oxetanes and Carbon Dioxide as Monomers 

    E-Print Network [OSTI]

    Moncada, Adriana I.

    2011-08-08T23:59:59.000Z

    Catalysts for Ring-Opening Polymerization of Six-Membered Cyclic Carbonates .......................................................................... 8 Aliphatic Polycarbonates from Oxetanes and Carbon Dioxide...... 15 Metal Salen Complexes... in TCE. Slope = -8910.7 with R2 = 0.9997 ......................................................................................... 56 II-15 1H NMR spectrum in CDCl3 of poly(TMC) obtained by way of oxetane/CO2 in the presence of (salen...

  9. Matrixassisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers

    E-Print Network [OSTI]

    Yang, Jian

    photoluminescent polymers using new ionic liquid matrices Carlos A. Serrano1 , Yi Zhang2 , Jian Yang2 and Kevin A elucidation of recently developed aliphatic biodegradable polymers by matrixassisted laser desorption/ionization mass spectrometry (MALDIMS). The polymers, formed by a condensation reaction of three components

  10. Wadi el-Hol

    E-Print Network [OSTI]

    Darnell, John C

    2013-01-01T23:59:59.000Z

    1 and 13 - 16) for the Htp-nTr of Amun at Karnak (Darnell154 [WHRI 39]—a mention of the Htp-nTr nj Jmn ). Epigraphic

  11. Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

    DOE Patents [OSTI]

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1982-03-31T23:59:59.000Z

    A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contracting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible polyhydroxy compound, such as, water, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds in the low polar or nonpolar solvent by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered for recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 2 tables.

  12. A quantitative study of the effect of structure on the saponification rates of aliphatic esters

    E-Print Network [OSTI]

    Gonzalez, Federico P

    1961-01-01T23:59:59.000Z

    of aliphatic ~sters&" (H? ST 'I'basis& The agricul- tural and Hechanicul dolls~", e of Texas, iugust, 1960) ~ J 6 6 11, '. 9. , t 9 ' ~tt ', 10, 41 (199&). APPENDIX 41 TABLE Ssponificstion of Ethyl Acetate st 35 Ca Run 1 Run 2 Time, Resistance Nin... Bennyl Propiona te 14. 55 5. 477 4+041 Oi9992 )o219 Z ~ 420 0. 4604 Oe04956 9i553 TABLE Seoond Order Rate Constants for n-Butyrates Ester h35 2 ~ 1 -1 li aole sino Nethyl n Sutyrate Ethyl a-Butyrate a Propyl n Sutyrate Isopropyl n...

  13. IEEE TRANSACTIONS ON VEHICULAR TECHNOLOGY, VOL. 50, NO. 1, JANUARY 2001 125 The Application of Neural Networks to Fuel

    E-Print Network [OSTI]

    Stengel, Robert F.

    of Neural Networks to Fuel Processors for Fuel-Cell Vehicles Laura C. Iwan and Robert F. Stengel, Fellow, IEEE Abstract--Passenger vehicles fueled by hydrocarbons or alco- hols and powered by proton exchange membrane (PEM) fuel cells address world air quality and fuel supply concerns while avoiding hydrogen

  14. Branched aliphatic alkanes with quaternary substituted carbon atoms in modern and ancient geologic samples.

    SciTech Connect (OSTI)

    Kenig, F.; Simons, D.-J. H.; Crich, D.; Cowen, J. P.; Ventura, G. T.; Rehbein-Khalily, T.; Brown, T. C.; Anderson, K. B.; Chemistry; Univ. of Illinois at Chicago; Univ. of Hawaii

    2003-01-01T23:59:59.000Z

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-di-methylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65{sup o}C) deep-sea hydrothermal waters and Late Cretaceous black shales. 5,5-Diethylalkanes were also observed in modern and Holocene marine shelf sediments and in shales spanning the last 800 million years of the geological record. The carbon number distribution of BAQCs indicates a biological origin. These compounds were observed but not identified in previous studies of 2.0 billion- to 2.2 billion-year-old metasediments and were commonly misidentified in other sediment samples, indicating that BAQCs are widespread in the geological record. The source organisms of BAQCs are unknown, but their paleobiogeographic distribution suggests that they have an affinity for sulfides and might be nonphotosynthetic sulfide oxidizers.

  15. Spatial variations and chronologies of aliphatic hydrocarbons in Lake Michigan sediments.

    SciTech Connect (OSTI)

    Doskey, P. V.; Environmental Research

    2001-01-15T23:59:59.000Z

    Four sediment cores were collected in fine-grained depositional areas of the southern basin of Lake Michigan. Spatial variations of aliphatic hydrocarbons in surficial sediments were consistent with a lakeward movement of riverine sediments in a series of resuspension-settling cycles in which an unresolved complex mixture (UCM) of hydrocarbons associated with dense sediments is deposited in nearshore areas, fine-grained sediments of terrestrial origin accumulate in the deep basin, and planktonic hydrocarbons are depleted by microbial degradation during transport to the deep basin. The rate of accumulation of the UCM (a marker of petroleum residues) in deep basin sediments has increased by more than an order of magnitude since 1880, from 60 {mu}g m{sup -2}{center_dot}a{sup -1} to approximately 960 {mu}g m{sup -2}{center_dot}a{sup -1} in 1980. Crude estimates of the atmospheric loading of the UCM (1100 {mu}g m{sup -2}{center_dot}a{sup -1}) indicate that accumulations in deep-basin sediments might be supported by atmospheric deposition. Agreement was poor between the atmospheric flux of the terrestrial n-alkanes ({Sigma}C{sub 25}, C{sub 27}, C{sub 29}, C{sub 31}) to the deep basin (3200 {mu}g m{sup -2}{center_dot}a{sup -1}) and the sediment accumulation rate (660 {mu}g m{sup -2}{center_dot}a{sup -1}). Understanding of atmospheric fluxes, estimated from the very few available data, would be improved by more frequent measurement of the levels of aliphatic hydrocarbons in air and precipitation and a better knowledge of the particle deposition velocities and precipitation scavenging coefficients.

  16. ORGANIC GEOCHEMICAL STUDIES. II. THE DISTRIBUTION OF ALIPHATIC HYDROCARBONS IN ALGAE, BACTERIA, AND IN A RECENT LAKE SEDIMENT: A PRELIMINARY REPORT

    E-Print Network [OSTI]

    Han, Jerry; McCarthy, E.D.; Van Hoeven Jr., William; Calvin, Melvin; Bradley, W. H.

    2008-01-01T23:59:59.000Z

    ALIPHATIC HYDROCARBONS IN ALGAE, BACTERIA, AND IN A RECENTH F A PRELIMINARY REPORT IN ALGAE, BACTERIA, AKD IN A RECENTrests on the finding that algae have less cellulose and a

  17. Interactions of chlorosulfonated polyethylene geomembranes with aliphatic esters: Sorption and diffusion phenomena

    SciTech Connect (OSTI)

    Aminabhavi, T.M.; Munnolli, R.S. [Karnatak Univ. (India). Dept. of Chemistry] [Karnatak Univ. (India). Dept. of Chemistry; Ortego, J.D. [Lamar Univ., Beaumont, TX (United States)] [Lamar Univ., Beaumont, TX (United States)

    1995-07-01T23:59:59.000Z

    The resistance of chlorosulfonated polyethylene geomembranes to nine aliphatic esters viz., methyl acetate, ethyl acetate, methyl acetoacetate, n-butyl acetate, diethyl oxalate, iso-amyl acetate, diethyl malonate, and diethyl succinate was investigated in the temperature interval 25--60 C by measuring the liquid sorption using a gravimetric method. A Fickian diffusion equation was used to calculate the diffusion coefficients, and these data were dependent on the type of ester molecules and their interactions with the geomembrane in additions to temperature and solvent concentration. The activation energy values for the diffusion process were in the range 18--41 kJ/mole and the heat of sorption varied from 0.61 to 18.50 kJ/mole. the sorption/swelling results were found to follow the first order kinetics. Solvent front velocities were calculated from the sorption data. The statistical error analysis has been presented in order to judge the reliability of the technique used. The experimental data and calculated parameters were used to discuss transport results in terms of membrane-solvent interactions. None of the esters showed any degradative effects on the geomembrane used.

  18. Modification of alkaline pulping to facilitate the isolation of aliphatic acids. Part 1. Sodium hydroxide pretreatment of pine wood

    SciTech Connect (OSTI)

    Alen, R.; Niemelae, K.; Sjoestroem, E.

    1984-01-01T23:59:59.000Z

    Pretreating pine chips (Pinus sylvestris) with sodium hydroxide prior to the alkaline delignification kraft, kraft-anthraquinone, and soda-anthraquinone) can facilitate the recovery of the carbohydrate degradation products from alkaline pulping liquors. Under suitable pretreatment conditions large amounts of carbohydrate degradation products (alipahtic acids) were formed relative to lignin. The lignin fraction was composed of comparatively low-molecular-weight fragments. Although the delignification was considerably retarded and the yield (based on wood) was decreased by 1-3%, the properties of the resulting pulp were essentially maintained despite pretreatment. Finally, data are given for the composition of aliphatic acids in liquors resulting from pretreatments.

  19. http://hol.sagepub.com The Holocene

    E-Print Network [OSTI]

    Pisaric, Michael

    ; revised manuscript accepted 30 January 2002 Abstract: Changes in pollen and stomata assemblages Columbia re ect vegetation and inferred climatic change throughout the Holocene. Pollen and stomata records elevation of subalpine treeline. The pollen and stomata records from BC2 indicate that an ephemeral shrub

  20. http://hol.sagepub.com/ The Holocene

    E-Print Network [OSTI]

    Gilli, Adrian

    November 2011The Holocene Ariztegui, Marian Fujak and Yvonne Hamann Julie Elbert, Martin Grosjean, Lucien

  1. http://hol.sagepub.com/ The Holocene

    E-Print Network [OSTI]

    in Laguna Potrok Aike, southern Patagonia, since the Published by: http://www.sagepublications.com can in southern Patagonia are relatively scarce though essential for understanding paleocli- matic evolution.g. Ariz- tegui et al., 2008). Previous paleolimnological investigations in southern Patagonia include

  2. http://hol.sagepub.com/ The Holocene

    E-Print Network [OSTI]

    Gilli, Adrian

    of decadal-scale variability of Mediterranean vegetation and climate at Pantelleria Island, Published by, it is difficult to ascribe the importance of climatic change for vegetation dynamics in heavily disturbed disturbances such as grazing and fire. Vegetation change in the Mediterranean region is widely ascribed

  3. Interactive Proof Discover: An Empirical Study of HOL Users

    E-Print Network [OSTI]

    Aitken, S.; Gray, P.; Melham, T.F.

    Aitken,S. Gray,P. Melham,T.F. Thomas,M. User Interface Design for Theorem Proving Systems: an International Workshop University of Glasgow

  4. Analysis of low-cost building material for the MixAlco process

    E-Print Network [OSTI]

    Titzman, L. Clinton

    2009-05-15T23:59:59.000Z

    and tensile strengths that were too weak to build an economical structure. The identification of a hybrid papercrete-concrete structure produced results and economics within acceptable ranges. The papercrete-concrete alternative was tested on the same... ...................................................................................... 42 8.2 Concrete Testing ..................................................................................... 44 8.3 Layered Quonset Analysis ...................................................................... 48 IX BUILDING TECHNIQUES...

  5. Conversion of MixAlco Process Sludge to Liquid Transportation Fuels 

    E-Print Network [OSTI]

    Teiseh, Eliasu 1973-

    2012-02-15T23:59:59.000Z

    =heating value of syngas (MJ/kg) BO=bio-oil Mf=mass of sludge pyrolyzed (kg) Ws=auger shafting work (J) P.dV=work done on system (J) Q=thermal energy supplied (J) ?Eg=total energy of syngas (J) Eb=energy of bio-oil (J) Ec=energy of char (J) ?Mg...=total energy of syngas (J) Mb=mass of bio-oil (kg) Mc=mass of char (kg) Vt=total volume of syngas (L) Cg=concentration of syngas (v %) P=P*=1 atm tbr=breakthrough time (minutes) ?=density of H2 at standard conditions (g/L) ?= mol fraction of H2 in feed...

  6. Cite this: RSC Advances, 2013, 3, Synthesis of nano-sized spherical Mg3AlCO3 layered

    E-Print Network [OSTI]

    Guo, John Zhanhu

    properties and can potentially be used in a wide range of applications such as high-temperature CO2 capture,8 hydroxide as a high-temperature CO2 adsorbent Received 23rd October 2012, Accepted 19th December 2012 DOI amines, which are good low-temperature CO2 adsorbents, are normally supported on the mesoporous

  7. The conversion of corn stover and pig manure to carboxylic acids with the MixAlco process

    E-Print Network [OSTI]

    Black, Amanda Spring

    2013-02-22T23:59:59.000Z

    of these processes to a feedstock of corn stover and pig manure. During fermentation, corn stover was the energy source (carbohydrates) and pig manure was the nutrient source (vitamins, minerals, and growth factors). A countercurrent fermentation procedure...

  8. FuzzySetsandSystems33(1989)201-212 201 No~h-Hol|and

    E-Print Network [OSTI]

    de Campos, Luis M.

    1989-01-01T23:59:59.000Z

    EXPECTATION AND ITS APPL|CA'E[ON TO THE EXTENSION OF FUZZY MEASURES Manuel J. BOLAHOS CARMONA Facul~dde Med

  9. Formalizing a Framework for Dynamic Slicing of Program Dependence Graphs in Isabelle/HOL

    E-Print Network [OSTI]

    Snelting, Gregor

    *i; 6 i := i-1; } 7 out:=sum; CFG: Entry 1 2 3 4 5 6 7 Exit False True sum:=0 prod:=1 i>0 i0 sum sum := sum+i; 5 prod := prod*i; 6 i := i-1; } 7 out:=sum; CFG: Entry 1 2 3 4 5 6Exit 7 False True sum sum := sum+i; 5 prod := prod*i; 6 i := i-1; } 7 out:=sum; CFG: Entry 1 2 3 4 5 6Exit 7 False True sum

  10. Quantitative temperature effects on the saponification rates of aliphatic esters

    E-Print Network [OSTI]

    Schreck, James Otto

    1962-01-01T23:59:59.000Z

    . Heat of Activation Entro of Activati an Free Ener o t vat on Using Eyring's basic equation40 40. S. Glasstone K. J. Laidler, H. Eyring, "The Theory of, Rate Processes, " NcGraw-Hill Book Company, Inc. , New York, N. Y. , 1941: p. 195. k = K -2 (18...

  11. aliphatic unsaturated unconjugated: Topics by E-print Network

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

    3.3, 6.2, 7.7, 8.6, and 11.3 micrometer, commonly attributed to polycyclic aromatic hydrocarbon (PAH) molecules, have been recently ascribed to coal- or kerogen-like organic...

  12. aliphatic saturated primary: Topics by E-print Network

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

    3.3, 6.2, 7.7, 8.6, and 11.3 micrometer, commonly attributed to polycyclic aromatic hydrocarbon (PAH) molecules, have been recently ascribed to coal- or kerogen-like organic...

  13. Quantitative relationships between structure and reactivity of aliphatic esters

    E-Print Network [OSTI]

    Yager, Billy Joe

    1960-01-01T23:59:59.000Z

    ~rity of' cstor and bsso s~lution (100 nl. ), 0. 02/76 ii &ol~rfty of nixture of' base and ester solution, 0. 01186 '! t, R& "inutco Qhm 1176 1/d x 10 (1/R 1/R ) x 10 1/t (1/2 - 1 ~Rt} x 1(P o 0 0, (~90' 7 9, 0 11. 0 1': 6 Q, ypCQ 1 940 Jg.... 210 1. 1$ 0, y~? -l. r4 0, 215 -O. g Wtc on i'. ethyl a b 0 1' 0. 00 -0. 'V -0, 67 1, 06 -0, 70 -1. 24 -1. 74 -2. 46 -0 69 (n-y) loC ~k 1 ~ 2iFgG 1, 169' d. 87l7 &47100 O. -fPjO 0. 1752 -0. 1700 a b a, :al'erenoe 5', roI'orenoo 9...

  14. aliphatic alcohols studies: Topics by E-print Network

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

    second, the efficacy of three psychotherapies for alcoholism in treating extreme West, Mike 393 Characterization of Catalysts for the Synthesis of Higher Alcohols using...

  15. aliphatic tertiary amines: Topics by E-print Network

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

    of the system. If so, all close binaries should be members of triple (or higher-order) systems. As a test of this prediction, we present a search for the signature of third...

  16. aliphatic ch bonds: Topics by E-print Network

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

    2015-01-01 39 H-atom high-n Rydberg time-of-flight spectroscopy of CH bond fission in acrolein dissociated at 193 nm Chemistry Websites Summary: H-atom high-n Rydberg...

  17. aromatic aliphatic copolyester: Topics by E-print Network

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

    Based on studies of PAH destruction, we argue that a size distribution shifted towards sm... Sandstrom, Karin M; Bot, Caroline; Draine, B T; Ingalls, James G; Israel, Frank P;...

  18. Low-Temperature Photoelectron Spectroscopy of Aliphatic Dicarboxylate...

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

    anions are cyclic due to strong intramolecular hydrogen bonding between the terminal –CO2H and –CO2 - groups. The measured electron binding energies are...

  19. Competitive Oxidation and Reduction of Aliphatic Alcohols over...

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

    bond to give alkoxy (RO ) bound to W(VI) centers and a proton (H+) attached to the terminal oxygen atom of a tungstyl group (WO). Two protons adsorbed onto the cluster readily...

  20. aliphatic hydrocarbons separacion: Topics by E-print Network

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

    Technologies and Information Sciences Websites Summary: by the Spanish Ministry: TITLE: Gestion de la movilidad basada en la separacion de identificadores. (NAME: Naming:...

  1. aliphatic carboxylic acids: Topics by E-print Network

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

    and spot selling price of various carboxylic acids. 1-3 Names used for biomass feedstocks. . 1-4 2-1 Sample processing. Rinsing scheme for precipitated solids. 12 3-1...

  2. aliphatic carboxylic acid: Topics by E-print Network

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

    and spot selling price of various carboxylic acids. 1-3 Names used for biomass feedstocks. . 1-4 2-1 Sample processing. Rinsing scheme for precipitated solids. 12 3-1...

  3. aliphatic primary diamines: Topics by E-print Network

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

    STUDY OF DNA DOUBLE-STRAND BREAKS IN BYSTANDER PRIMARY HUMAN FIBROBLASTS L. B. Smilenov-or-nothing manner(7) . Bystander cells exhibit a variety of characteristics of...

  4. aliphatic chains affects: Topics by E-print Network

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

    Harvard Medical School, 200 Longwood Avenue, Boston, MA 02115; b Department, maximum entropy reconstruction, non-uniform sampling, reduced-dimensionality, side-chain...

  5. aliphatic biodegradable photoluminescent: Topics by E-print Network

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

    oxide phosphors. Furthermore, strong photoluminescence (PL) in Zn SiO doped with rare earths such as Eu Steckl, Andrew J. 295 Circularly Polarized Photoluminescence as a...

  6. Characterization of a Saturated and Flexible Aliphatic Polyol Anion Receptor

    SciTech Connect (OSTI)

    Shokri, Alireza; Schmidt, Jacob C.; Wang, Xue B.; Kass, Steven R.

    2012-10-17T23:59:59.000Z

    Nature employs flexible molecules to bind anions in a variety of physiologically important processes whereas supramolecular chemists have been designing rigid substrates that minimize or eliminate intramolecular hydrogen bond interactions to carry out anion recogni-tion. Herein, the association of a flexible polyhydroxy alkane with chloride ion is described and the bound re-ceptor is characterized by infrared and photoelectron spectroscopy in the gas phase, computations, and its bind-ing constant as a function of temperature in acetonitrile.

  7. J. Camilleri and T. Melham, `Reasoning with Inductively Defined Relations in the HOL Theorem Prover', Technical Report No. 265,

    E-Print Network [OSTI]

    Melham, Tom

    University of Malta University Heights Msida, Malta G.C. Tom Melham University of Cambridge Computer

  8. Photochemistry and Photobiology, 2014, 90: 338343 Aliphatic b-Nitroalcohols for Therapeutic Corneoscleral Cross-Linking

    E-Print Network [OSTI]

    Turro, Nicholas J.

    are relevant to the translation of this technol- ogy into clinical use. INTRODUCTION Riboflavin layer followed by the application of a 0.1% riboflavin-containing solution to the exposed underlying corneal stromal bed. After confirming ade- quate infiltration of the riboflavin photosensitizer, a 360 nm

  9. aliphatic solvent n-hexane: Topics by E-print Network

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

    n-hexane crystallized in silicon nanochannels: A combined x-ray diffraction and sorption isotherm study CERN Preprints Summary: We present an x-ray diffraction study on n-hexane...

  10. Alteration and release of aliphatic compounds by the polychaete Nereis virens (Sars) experimentally fed with

    E-Print Network [OSTI]

    Boyer, Edmond

    with time and no microbial hydrocarbon biodegradation were evidenced. Our results suggest that marine worm an important role with regard to the fate of hydrocarbon pollutants (Lee and Swartz, 1980). Previous works their bioavailability (Mihelcic and Luthy, 1991; Madsen et al., 1997) and resulting bacterial biodegradation (Gordon et

  11. Alteration and release of aliphatic compounds by the polychaete Nereis virens (Sars) experimentally fed with

    E-Print Network [OSTI]

    Mailhes, Corinne

    with time and no microbial hydrocarbon biodegradation were evidenced. Our results suggest that marine worm `bioturbation' play an important role with regard to the fate of hydrocarbon pollutants (Lee and Swartz, 1980 biodegradation (Gordon et al., 1978; Bauer et al., 1988; McElroy et al., 1990). In areas of intensive reworking

  12. Synthesis Gas Conversion to Aliphatic Alcohols: Study of MoS2 catalytic systems

    E-Print Network [OSTI]

    Baksh, Faisal

    2010-04-19T23:59:59.000Z

    . 1-butanol is considered by many to be the most suitable alcohol replacement for gasoline. Plans for conversion of existing bioethanol facilities to biobutanol are already being drawn up. Early on, methanol-gasoline blends were extensively tested...

  13. Binary Phases of Aliphatic N-Oxides and Water: Force Field Development and Molecular Dynamics Simulation

    E-Print Network [OSTI]

    Berry, R. Stephen

    the reactivity of the swollen cellulose material for further derivatization in pollution-free industrial fiber future parametrization of other species. By construction, the force field is compatible with widely used play an increasingly important role for industrial applications, e.g., for tuning solubility

  14. Divergent Mechanistic Avenues to an Aliphatic Polyesteracetal or Polyester from a Single Cyclic Esteracetal

    E-Print Network [OSTI]

    Kokkoli, Efie

    , a statistical copolymer of 1,3-dioxolan-4-one (DOX) and lactide was reported. While the patent provided little the synthesis of a variety of copolymers of DOX and lactide and reports up to 36% DOX incorporation. A computational study of the ring strain in DOX suggests that DOX is slightly less strained than -butyrolactone

  15. aliphatic carbon-centered radicals: Topics by E-print Network

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

    organizational transformation, new organizational forms and the new public management (NPM) in a novel way. Data reveal important limits to intended organizational transformation...

  16. Reductive dechlorination of chlorinated aliphatic hydrocarbons by Fe(ii) in degradative solidification/stabilization

    E-Print Network [OSTI]

    Jung, Bahng Mi

    2007-04-25T23:59:59.000Z

    ............................................................................................7 2.1 Degradative Solidification/Stabilization...................................................7 2.2 Cement Chemistry.....................................................................................8 2.2.1 Portland Cement... of typical cements . .........................9 Table 2.2 Portland cement compound transformation................................................15 Table 2.3 The oxides, hydroxides, and oxyhydroxides of Fe.....................................16 Table 2...

  17. A kinetic study of the reactions of diphenyldiazomethane with some aliphatic carboxylic acids

    E-Print Network [OSTI]

    Hoefelmeyer, Albert Bernard

    1954-01-01T23:59:59.000Z

    (a) C. K. Ingold, J. Chem. Soc., 1032 (1930). (b) S. W. Timm and C. N. Iiinshelwood, J. Chem. Soc., 862 (1933). (c) C. K. Ingold et al., J. Chem. Soc., 3^27?(l 9^3). 13 ?. A. Waters, "Physical Aspects of Organic Chemistry," D. Van Nostrand Co., Inc...., New York, N. Y., 1950# Chapter XI. nil (a) I. Dostrovsky, E. D. Hughes, and K. Ingold, J.Chem. Soc., 173 (19U6). (b) K. A. Cooper, S. D. Hughes, C. K. Ingold, and B. J. Mac Nulty, J. Chem. Soc., 2038 (l 9 l|8). (c) P. M. Dunbar and L. P. Hammett, J...

  18. aliphatic c-h bond: Topics by E-print Network

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

    activation of functionalized hydrocarbons. II. CH and CCN bond activation of acetonitrile and benzonitrile. Open Access Theses and Dissertations Summary: ??Several...

  19. Reactor Analysis and Process Synthesis for a Class of Complex Sequential Reactions

    E-Print Network [OSTI]

    Maccabi, Omid A

    2012-01-01T23:59:59.000Z

    Design, AIChE, 1995, 52–67 [Hol79] Holland and Anthony, Fundamentals of Chemical Reaction Engineering,

  20. Pretreatment and Fermentation of Sugarcane Trash to Carboxylic Acids

    E-Print Network [OSTI]

    Nachiappan, Balasubraman

    2010-01-14T23:59:59.000Z

    resource. The patented MixAlco process is a cost-effective solution, which does not require sterility or the addition of expensive enzymes to convert lignocellulosic biomass to transportation fuels and valuable chemicals. In this study, the MixAlco process...

  1. Application of organolithium compounds for the preparation of some aliphatic and alicyclic phosphines, phosphine oxides and phosphine sulfides

    E-Print Network [OSTI]

    Screttas, Constantinos G

    1961-01-01T23:59:59.000Z

    @? ~?? Qg) 23h2? 19? Oelkie? N?? pygmy? Qgg? ~i? @ 636)71h(1486)? 2o. te?L~. 4. w. , Net, a. m Isg?14. a. I. , g. ~. ~. , gg. g9. RL ~ heal& 0? Lh?? @g? Q~Q Qgg? ~ g? 326(1932) TL?Q? $? g? 966(1933) ~ 22? 9?fs??a? ??, y? ~. ~? @g, ?, g, 1684(1921) ~ 23...? Oaf fs?ay D? D? ??4 Watt?1 ~ C? 4 ~ ~ QQ?? Q? 3696(1999) ~ 2$? LLL?h?elis, ??, ~?? ~? 63(1901) ~ l5eh?elis, k? a?4 Oleishs?sa? L? ~ ~?? g? 801?1961(lw)2) ~ 26? ICeh?olio/ I? ??4 Ileeee? ?? ~ Q@?? gy 1610(1842)? 27 ~ Herr?LL ~ D? I?? g? AS...

  2. THE CHEMISTRY OF COAL MODEL COMPOUNDS -CLEAVAGE OF ALIPHATIC BRIDGES BETWEEN AROMATIC NUCLEI CATALYSED BY LEWIS ACIDS

    E-Print Network [OSTI]

    Taylor, Newell D.

    2011-01-01T23:59:59.000Z

    and Background I. II. III. IV. II. Coal Liquefaction . •Coal Structure • • . Lewis Acid Catalysts. Scope andOrganic Structure of Bituminous Coal", Proceedings, Stanford

  3. INTRODUCTION Asphalt is a mixture of a wide variety of chemical compounds that include aliphatic hydrocarbons and highly fused

    E-Print Network [OSTI]

    Harms, Kyle E.

    hydrocarbons and highly fused aromatic ring systems.They are classified as asphaltenes (medium molecular weight

  4. THE CHEMISTRY OF COAL MODEL COMPOUNDS -CLEAVAGE OF ALIPHATIC BRIDGES BETWEEN AROMATIC NUCLEI CATALYSED BY LEWIS ACIDS

    E-Print Network [OSTI]

    Taylor, Newell D.

    2011-01-01T23:59:59.000Z

    and at the Nature of Asphaltenes" , Preprints L Div. of Fuelcoal that the formation of asphaltenes might be ascribed to

  5. Investigations of Biomass Pretreatment and Submerged Fixed-bed Fermentation

    E-Print Network [OSTI]

    Meysing, Daniel

    2012-02-14T23:59:59.000Z

    To improve the MixAlco process and biomass pretreatment, five studies were conducted. Three studies related to fermentation, whereas the other two investigated the effectiveness of shock tube pretreatment (STP) coupled with oxidative lime...

  6. Characterization and CPDM modeling of volatile fatty acid fermentation with cotton gin trash and chicken manrure as substrates 

    E-Print Network [OSTI]

    Han, Joseph

    2013-02-22T23:59:59.000Z

    With literally tons of biomass produced annually, a process that uses this waste as a feedstock would help reduce the problem of disposal. The MixAlco process is one that does just that. It converts biomass through anaerobic fermentation...

  7. Characterization and CPDM modeling of volatile fatty acid fermentation with cotton gin trash and chicken manrure as substrates

    E-Print Network [OSTI]

    Han, Joseph

    2013-02-22T23:59:59.000Z

    With literally tons of biomass produced annually, a process that uses this waste as a feedstock would help reduce the problem of disposal. The MixAlco process is one that does just that. It converts biomass through anaerobic fermentation...

  8. Ketone Production from the Thermal Decomposition of Carboxylate Salts

    E-Print Network [OSTI]

    Landoll, Michael 1984-

    2012-08-15T23:59:59.000Z

    The MixAlco process uses an anaerobic, mixed-culture fermentation to convert lignocellulosic biomass to carboxylate salts. The fermentation broth must be clarified so that only carboxylate salts, water, and minimal impurities remain. Carboxylate...

  9. Classification of indefinite hyper-K"ahler symmetric spaces Dmitri V. Alekseevsky 1, Vicente Cort'es 2

    E-Print Network [OSTI]

    Cortés, Vicente

    ) if its holon- omy group Hol(M, g) is a subgroup of the pseudo-unitary group U(p, q) (respecti* *vely

  10. The Modern History of Ethiopia and the Horn of Africa: A Select and Annotated Bibliography. By Harold G. Marcus. Hoover Institution Bibliographical Series, Volume 56, Stanford, California: Hoover Institution Press, 1972.

    E-Print Network [OSTI]

    Amatruda, William T.

    1973-01-01T23:59:59.000Z

    The Model'YI History of Ethiopia and the Hol'YI of Africa: Athe extensive activi- ties in Ethiopia since the 1860s of

  11. UNIVERSITY VIEW GLENN L. MARTIN HALL

    E-Print Network [OSTI]

    Setiawan, Hendra

    PRESIDENTIAL DRIVE CHAPEL LANE ROSSBOROUGH LANE GREENHOUSEDRIVE SERVICE LANE YALEAVE COLLEGE AVE PREINKERTDRIVE other parking lots are for use by PERMIT HOL

  12. NMR Characterization of the Aliphatic / Pairing for Recognition of A,T/T,A Base Pairs in the Minor Groove of DNA

    E-Print Network [OSTI]

    Mrksich, Milan

    Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125 Recei been inserted to reset the register. Complexes of three pyrrole-imidazole polyamides of sequence

  13. A novel copper(II)-Schiff base complex containing pyrrole ring: Synthesis, characterization and its modified electrodes applied in oxidation of aliphatic alcohols

    E-Print Network [OSTI]

    Boyer, Edmond

    , ethanol and benzyl alcohol. The electro-reduction of carbon dioxide was also examined. Keywords: Copper] and carbon dioxide [9]. So, in continuation of our recent papers [10], we have undertaken a covalent grafting. Thus, conducting polymeric films of polypyrrole were obtained on the surfaces of glassy carbon and ITO

  14. Assessing the frictional and baroclinic contributions to stratified wake formation: a parameter space study 

    E-Print Network [OSTI]

    Smith, Jamie Brooke

    2006-08-16T23:59:59.000Z

    The baroclinic and surface-frictional contributions to stratified wake formation are considered as a function of the non-dimensional height ( = Nho/U) and aspect-ratio ( = ho/L) of the barrier. Numerical simulations are ...

  15. Silver/polystyrene-coated hollow glass waveguides for the transmission of terahertz radiation

    E-Print Network [OSTI]

    earlier work in- volved the deposition of Ag or Cu coatings inside polycarbonate tubing to form THz-coated hol- low polycarbonate waveguide. To reduce the loss, it is necessary to deposit a dielectric coating

  16. Formal Specification of Operating System Operations

    E-Print Network [OSTI]

    Black, Paul E.

    and Engineering Florida Atlantic University Boca Raton, FL 33431 dan@cse.fau.edu Paul E. Black National Institute system se­ curity policies in the higher­order logic theorem prover, HOL98 [Gordon (1987)]. Formal spec

  17. Influence of Al doping on the critical fields and gap values in magnesium diboride single crystals T. Klein,1,2 L. Lyard,1 J. Marcus,1 C. Marcenat,3 P. Szab,4 Z. Hol'anov,4 P. Samuely,4 B. W. Kang,5 H-J. Kim,5

    E-Print Network [OSTI]

    Boyer, Edmond

    that MgB2 belongs to an origi- nal class of superconductors in which two weakly coupled bands with very the existence of two distinct superconducting gaps. One of the main consequence of this two-band superconduc of the superconducting gaps with Al doping remains controversial. Whereas Gonnelli et al.15 sug- gested that the small

  18. Z .Journal of Power Sources 8182 1999 594598 www.elsevier.comrlocaterjpowsour

    E-Print Network [OSTI]

    Sadoway, Donald Robert

    microscopic characterization of electrochemically cycled z /LiCoO and Li Al,Co O battery cathodes2 2 Haifeng of lithium battery cathodes introduces large absolute changes in lithium concentration that can result in microstructural damage and cation disorder. This damage can influence the long-term performance of battery systems

  19. Organoselenium Chemistry. Conversion of Ketones to Enones by Selenoxide Syn Elimination

    E-Print Network [OSTI]

    Reich, Hans J.

    are direct selenenylation of ketone enolates using PhSeBr and the reaction of enol acetates%bdichlorodicyan- oquinone,2c periodic acid,2doxygen in the presence of tran- sition metal catalysts,2eand pyridine N-oxide-acetic eliminations synthetically in the conversion of epoxides to allyl alco- h o l ~ . ~ ~ , ~Several have explored

  20. Transformation of Acetone and Isopropanol to Hydrocarbons using HZSM-5 Catalyst 

    E-Print Network [OSTI]

    Taco Vasquez, Sebastian

    2010-07-14T23:59:59.000Z

    for more than 20 years to obtain fuels from biomass. Some biomass feedstocks studied in our group include municipal solid waste, animal manure, and energy crops. The new technology developed by the Holtzapple group is called the MixAlco Process (Figure 1...

  1. Oligomerization and Catalytic Ketonization in the Mixalco™ Process 

    E-Print Network [OSTI]

    Taco Vasquez, Sebastian

    2013-10-29T23:59:59.000Z

    –3 Depending how many steps are employed, the final product is ketones, alcohols, or hydrocarbons. Potential biomass feedstocks include municipal solid waste, animal manure, and energy crops.4–8 The MixAlco™ process is a version of the carboxylate platform...

  2. Assessing the Potential of Natural Microbial Communities to Improve a Second-Generation Biofuels Platform

    E-Print Network [OSTI]

    Hammett, Amy Jo Macbey

    2012-10-19T23:59:59.000Z

    Naturally occurring microbial communities from high-salt and/or high-temperature environments were collected from sites across the United States and Puerto Rico and screened for their efficacy in the MixAlco biofuel production platform. The Mix...

  3. Characterization of Extremophilic Bacteria for Potential in the Biofuel and Bioprocess Industries

    E-Print Network [OSTI]

    Haynes, Abria R

    2014-04-18T23:59:59.000Z

    , and Puerto Rico were used to inoculate fermentations in an effort to optimize the microbial communities for a biofuel process developed at Texas A&M (MixAlco™). A diverse bacterial isolate library (N= 1,866 isolates) was constructed by employing a variety...

  4. Continuous fermentation of food scraps with constant pH control to produce carboxylic acids

    E-Print Network [OSTI]

    Coleman Jr., Stanley Albert

    2008-10-10T23:59:59.000Z

    feedstock to the MixAlco process. Batch fermentation with various temperatures, buffers, and pH control methods elucidated the behavior of food scraps during fermentation. The pH and reactor configuration were limiting factors when maximizing production. A...

  5. Continuous fermentation of food scraps with constant pH control to produce carboxylic acids

    E-Print Network [OSTI]

    Coleman Jr., Stanley Albert

    2009-05-15T23:59:59.000Z

    feedstock to the MixAlco process. Batch fermentation with various temperatures, buffers, and pH control methods elucidated the behavior of food scraps during fermentation. The pH and reactor configuration were limiting factors when maximizing production. A...

  6. Sugarcane juice extraction and preservation, and long-term lime pretreatment of bagasse 

    E-Print Network [OSTI]

    Granda Cotlear, Cesar Benigno

    2005-02-17T23:59:59.000Z

    New technologies, such as an efficient vapor-compression evaporator, a stationary lime kiln (SLK), and the MixAlco process, compelled us to re-evaluate methods for producing sugar from cane. These technologies allow more water and lime to be used...

  7. Aluminum monocarbonyl and aluminum isocarbonyl Steve S. Wesolowski,a)

    E-Print Network [OSTI]

    Crawford, T. Daniel

    Aluminum monocarbonyl and aluminum isocarbonyl Steve S. Wesolowski,a) T. Daniel Crawford,b) Justin of the aluminum monocarbonyl species AlCO and AlOC have been performed to predict the geometries, fragmentation, Ogden, and Oswald6 first isolated aluminum dicarbonyls in solid krypton and identified the species

  8. Oligomerization and Catalytic Ketonization in the Mixalco™ Process

    E-Print Network [OSTI]

    Taco Vasquez, Sebastian

    2013-10-29T23:59:59.000Z

    –3 Depending how many steps are employed, the final product is ketones, alcohols, or hydrocarbons. Potential biomass feedstocks include municipal solid waste, animal manure, and energy crops.4–8 The MixAlco™ process is a version of the carboxylate platform...

  9. Transformation of Acetone and Isopropanol to Hydrocarbons using HZSM-5 Catalyst

    E-Print Network [OSTI]

    Taco Vasquez, Sebastian

    2010-07-14T23:59:59.000Z

    for more than 20 years to obtain fuels from biomass. Some biomass feedstocks studied in our group include municipal solid waste, animal manure, and energy crops. The new technology developed by the Holtzapple group is called the MixAlco Process (Figure 1...

  10. Chain Conformation of Poly(dimethyl siloxane) at the Air/Water Interface by Sum Frequency Generation

    E-Print Network [OSTI]

    those based on aliphatic fluorocarbon moieties. Its glass transition temperature of -123 °C is among

  11. Conversion of sugarcane bagasse to carboxylic acids under thermophilic conditions

    E-Print Network [OSTI]

    Fu, Zhihong

    2009-05-15T23:59:59.000Z

    ?????????????. 17 1.4 Project description????????????..?... 25 II MATERIALS AND METHODS???????????? 27 2.1 Biomass feedstock??????????????. 27 2.2 Biomass pretreatment????????????? 29 2.3 Fermentation material and methods.... This is followed by introducing promising lignocellulosic biomass feedstocks and challenges in lignocellulosic biomass conversion. Subsequently, it presents the process description and recent advances of the MixAlco process, a novel and promising biomass...

  12. Submission 04 Nov 2004 Space perception for tele-operation tasks 1/7 Space perception for tele-operation tasks

    E-Print Network [OSTI]

    and representation easier for the operator is to give him natural feedback information about the environment operator is far from the area where the action takes place. Operator Barrier (Environment,distance, time of automatic modes by the operator ([VAN94]). The notion of joint cognitive systems, introduced in [HOL83

  13. Univerzita Karlova v Praze Zpis ze 3. zasedn vdeck rady Matematicko-fyzikln fakulty

    E-Print Network [OSTI]

    Cerveny, Vlastislav

    . Jií Neustupa, CSc. prof. RNDr. Jan Palous, DrSc., OMLUVENI clenové vdecké rady: prof. RNDr. V. Holý, pracovala v následujícím slození: pedseda ­ prof. RNDr. Jan Palous, DrSc., (

  14. Linkping studies in science and technology. Thesis. Pose Estimation and Calibration Algorithms

    E-Print Network [OSTI]

    Schön, Thomas

    http://www.control.isy.liu.se hol@isy.liu.se Linköping 2008 #12;This is a Swedish Licentiate's Thesis. Swedish postgraduate education leads to a Doctor's degree and/or a Licentiate's degree. A Doctor's Degree comprises 240 ECTS credits (4 years of full-time studies). A Licentiate's degree comprises 120 ECTS credits

  15. [1] J. H. Ahrens. Paving the chessboard. Journal of Combinatorial Theory, Series A, 31:277--288, 1981.

    E-Print Network [OSTI]

    Merlini, Donatella

    . Petreschi. LEONARDO: a soft­ ware visualization system. Proceedings of the 1­st Workshop on Algorithm¨utzenberger methodology and solving for A; we get the following gener­ ating function: Hol(t; w) = wt 2 (2 + t + 2w 2 t 2

  16. Utilizing spatial technologies to understand and model wildlife species distributions

    E-Print Network [OSTI]

    Daugherty, Brad Ellis

    2000-01-01T23:59:59.000Z

    Locus t (Gleditsia triacanthos) 7 10 9 G reen A s h (Fraxinus pennsylvanica) - Ceda r Elm - Suga r Hackbe r ry 2 2 3 Honey Locus t - C e d a r E lm - Haw tho rne (Crataegus laevigata) - Dec iduous Hol ly (Ilex verticillata) 7 7 8 P laner T ree...

  17. Calibration of a magnetometer in combination with inertial sensors

    E-Print Network [OSTI]

    Schön, Thomas

    Calibration of a magnetometer in combination with inertial sensors Manon Kok, Jeroen D. Hol, Thomas are aligned and that the magnetometer is properly calibrated for both sensor errors as well as presence of magnetic distortions. In this work we derive an easy-to-use calibration algorithm that can be used

  18. Combining treatment for written and spoken naming PLAGIE M. BEESON and HEATHER EGNOR

    E-Print Network [OSTI]

    there is some residual phonological ability and the treatment serves to stimulate links between orthography., 2001). Behavioral treatments also may stimulate interactive use of residual knowledge across seman- tic production (Bruce & Howard, 1987; Hol- land, 1998). In a series of writing treatment studies directed toward

  19. Int. J. , Vol. x, No. x, xxxx 1 Modelling and Analysis of Service Parts Logistics Systems

    E-Print Network [OSTI]

    Rossetti, Manuel D.

    Int. J. , Vol. x, No. x, xxxx 1 Modelling and Analysis of Service Parts Logistics Systems Fernando, the behaviour of the service parts logistics system (SPLS) is approximated with a modified M/G/1 HOL queuing policy. Keywords: Service parts logistics, optimisation, genetic algorithms, M/G/1 queuing model

  20. Printed on: Thu, Oct 19, 1995 12:54:25 Document: iee_bm_synth

    E-Print Network [OSTI]

    Newcastle upon Tyne, University of

    Laboratory University of Newcastle upon Tyne NE1 7RU United Kingdom F.P. BURNS D.J. KINNIMENT Department interactive design tool that integrates the Boyer Moore theorem prover into the design process. We describe shown great promise in the area of hardware design: HOL [Go87] and the Boyer Moore theorem prover [Bo88

  1. Broadband Carbon-13 Correlation Spectra of Microcrystalline Proteins in Very High Magnetic Fields

    E-Print Network [OSTI]

    avoiding excessive sample heating. This opens up new possibilities for efficient dipolar recoupling. Both aliphatic nuclei with closely spaced chemical shifts and spectrally remote nuclei give rise

  2. Molybdenum alkylidene complexes : syntheses and applications to olefin metathesis reactions

    E-Print Network [OSTI]

    Pilyugina, Tatiana

    2007-01-01T23:59:59.000Z

    Chapter 1. Alkylimido Molybdenum Complexes: Synthesis, Characterization and Activity as Chiral Olefin Metathesis Catalysts. Molybdenum olefin metathesis catalysts that contain previously unexplored aliphatic 1- ...

  3. A Case for Safer Building Materials: Lifecycle Concerns, Data Gaps, and

    E-Print Network [OSTI]

    Lee, Seung-Wuk

    ;Conventional Building Materials · Wood · Stone · Cement · Metal · Glass · Straw · Ceramics #12;Synthetic;Volatile organic compounds (VOCs) · Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons

  4. UHM/HNEI EV test and evaluation program

    SciTech Connect (OSTI)

    Not Available

    1992-03-01T23:59:59.000Z

    The electric vehicle (EV) program of the Hawaii Natural Energy Institute (HNEI) focuses primarily on the field testing of promising EV/traction batteries. The intent is to utilize typical driving cycles to develop information that verifies or refutes what is obtained in the laboratory. Three different types of battery were assigned by the US DOE for testing in this program: Sonnenschein Dryfit 6V-160, Exide GC-5, Trojan T-145. We added the following battery to the test program: ALCO2200. HNEI's existing EVs were utilized as test beds. The following EVs were chosen in our program: Converted Ford Escort station wagon, Converted Ford Escort two-door sedan, Converted Ford Escort two-door sedan, Converted Dodge van (typically daily driving distances, 10--30 miles). Capacity testing is a very effective way of monitoring the status of battery modules. Based on capacity tests, corrective action such as battery replacement, additional charging, adjusting terminal connections, etc., may be taken to maintain good performance. About 15,500 miles and 600 cycles have been accumulated on the Sonnenschein Dryfit 6V-160 battery pack. Five of its 18 modules have been changed. Based on DOE's standard, the battery has reached the end of its useful life. Nevertheless, the battery pack is still operational and its operating range is still greater than 40 miles per charge. It is too early to evaluate the life expectancy of the other three batteries, the Trojan T-145, Exide GC-5, and Alco 2200. No module has been replaced in these three packs. The Trojan T-145 battery is a very promising EV traction battery in terms of quality and reliability versus price. HNEI will keep the Trojan and Exide battery packs in operation. The Alco 2200 batteries will be transferred to another vehicle. The Additional Charging Method seems to be an effective way of restoring weak modules. The Smart Voltmeter'' developed by HNEI is a promising way of monitoring the remaining range for an EV.

  5. Texas Rice, Volume VI, Number 5 

    E-Print Network [OSTI]

    2006-01-01T23:59:59.000Z

    by processing these crops is produced more efficiently than the ethanol produced by corn. Water hyacinth, a weed that chokes waterways if left to grow uncontrolled, is even more energy efficient as a biomass feedstock,” Holtzapple said. In the MixAlco process..., the biomass feedstock, with added mi- croorganisms from sources such as dirt, compost piles and swamps, is treated with lime and then fer- mented to form organic salts. Wa- ter is removed and then the mixture is heated to form ketones, such as acetone, which...

  6. ***This MSDS covers part#s 30004P, 30016P, 30128P, 30640P, 33840P & 37040P Page 1 of 2 MATERIAL SAFETY DATA SHEET

    E-Print Network [OSTI]

    Rollins, Andrew M.

    on quantity HMIS/NFPA CODE Health 0; Fire 1; Reactivity 0 MANUFACTURING CODE NO.: 8358 COMMODITY CODE NO.: 332. II. INGREDIENTS Aliphatic Organic Acid : CAS# 112-80-1 >75% mixture Aliphatic Organic Ester : CAS/gal VAPOR PRESSURE (mm of Mercury) @ 75° F : Less Than 1 VAPOR DENSITY (Air = 1) : Greater Than 5 SOLUBILITY

  7. Inhibition of Trichoderma reesei cellulase by cellobiose, glucose, ethanol and butanol

    E-Print Network [OSTI]

    Cognata, Mona Beth

    1988-01-01T23:59:59.000Z

    INHIBITION OF TRICHODERMA REESEI CELLULASE BY CELLOBIOSE, GLUCOSE, ETHANOL AND BUTANOL A Thesis by MONA BETH COGNATA Submitted to the Graduate College of Texas A&M University in partial fulfillment of the requirement for the degree... of MASTER OF SCIENCE December 1988 Major Subject: Chemical Engineering INHIBITION OF TRICHODERMA REESEI CELLULASE BY CELLOBIOSE, GLUCOSE, ETHANOL AND BUTANOL A Thesis by MONA BETH COGNATA Approved as to style and content by: Mark T. Hol a (Chair...

  8. UNIDENTIFIED INFRARED EMISSION BANDS: PAHs or MAONs?

    SciTech Connect (OSTI)

    Sun Kwok; Yong Zhang, E-mail: sunkwok@hku.hk [Department of Physics, University of Hong Kong, Pokfulam Road, Hong Kong (Hong Kong)

    2013-07-01T23:59:59.000Z

    We suggest that the carrier of the unidentified infrared emission (UIE) bands is an amorphous carbonaceous solid with mixed aromatic/aliphatic structures, rather than free-flying polycyclic aromatic hydrocarbon molecules. Through spectral fittings of the astronomical spectra of the UIE bands, we show that a significant amount of the energy is emitted by the aliphatic component, implying that aliphatic groups are an essential part of the chemical structure. Arguments in favor of an amorphous, solid-state structure rather than a gas-phase molecule as a carrier of the UIE are also presented.

  9. Improving fatty acids production by engineering dynamic pathway regulation and metabolic control

    E-Print Network [OSTI]

    Stephanopoulos, Gregory

    Global energy demand and environmental concerns have stimulated increasing efforts to produce carbon-neutral fuels directly from renewable resources. Microbially derived aliphatic hydrocarbons, the petroleum-replica fuels, ...

  10. Nickel-catalyzed preparation of acrylamides from alpha olefins and isocyanates ; Synthetic studies toward ripostatin A

    E-Print Network [OSTI]

    Schleicher, Kristin D. (Kristin Diann)

    2010-01-01T23:59:59.000Z

    Chapter I. In the presence of the N-heterocyclic carbene ligand IPr, the nickel(0)-catalyzed coupling reaction of a-olefins and branched aliphatic isocyanates provides c,-unsaturated amides arising from preferential C-C ...

  11. Microbial dynamics during intrinsic remediation of oil contaminated coastal wetland sediments (a microcosm study) 

    E-Print Network [OSTI]

    Thornburg, Nathaniel David

    2001-01-01T23:59:59.000Z

    and aromatic-degrading bacteria. Petroleum chemistry demonstrated a concomitant decrease of aliphatic and aromatic hydrocarbon fractions. Therefore, an inverse relationship between hydrocarbon-degrading bacterial populations and hydrocarbon concentrations...

  12. Observation of Entropic Effect on Conformation Changes of Complex...

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

    entropic effect in determining the folding of a linear dicarboxylate dianion with a flexible aliphatic chain –O2C-(CH2)6-CO2– by photoelectron spectroscopy as a...

  13. Process for reducing organic compounds with calcium, amine, and alcohol

    DOE Patents [OSTI]

    Benkeser, R.A.; Laugal, J.A.; Rappa, A.

    1985-08-06T23:59:59.000Z

    Olefins are produced by contacting an organic compound having at least one benzene ring with calcium metal, ethylenediamine, a low molecular weight aliphatic alcohol, and optionally a low molecular weight aliphatic primary amine, and/or an inert, abrasive particulate substance. The reduction is conducted at temperatures ranging from about [minus]10 C to about 30 C or somewhat higher. Substantially all of the organic compounds are converted to corresponding cyclic olefins, primarily diolefins.

  14. Process for reducing organic compounds with calcium, amine, and alcohol

    DOE Patents [OSTI]

    Benkeser, Robert A. (West Lafayette, IN); Laugal, James A. (Lostant, IL); Rappa, Angela (Baltimore, MD)

    1985-01-01T23:59:59.000Z

    Olefins are produced by contacting an organic compound having at least one benzene ring with calcium metal, ethylenediamine, a low molecular weight aliphatic alcohol, and optionally a low molecular weight aliphatic primary amine, and/or an inert, abrasive particulate substance. The reduction is conducted at temperatures ranging from about -10.degree. C. to about 30.degree. C. or somewhat higher. Substantially all of the organic compounds are converted to corresponding cyclic olefins, primarily diolefins.

  15. UHM/HNEI EV test and evaluation program. Final report

    SciTech Connect (OSTI)

    Not Available

    1992-03-01T23:59:59.000Z

    The electric vehicle (EV) program of the Hawaii Natural Energy Institute (HNEI) focuses primarily on the field testing of promising EV/traction batteries. The intent is to utilize typical driving cycles to develop information that verifies or refutes what is obtained in the laboratory. Three different types of battery were assigned by the US DOE for testing in this program: Sonnenschein Dryfit 6V-160, Exide GC-5, Trojan T-145. We added the following battery to the test program: ALCO2200. HNEI`s existing EVs were utilized as test beds. The following EVs were chosen in our program: Converted Ford Escort station wagon, Converted Ford Escort two-door sedan, Converted Ford Escort two-door sedan, Converted Dodge van (typically daily driving distances, 10--30 miles). Capacity testing is a very effective way of monitoring the status of battery modules. Based on capacity tests, corrective action such as battery replacement, additional charging, adjusting terminal connections, etc., may be taken to maintain good performance. About 15,500 miles and 600 cycles have been accumulated on the Sonnenschein Dryfit 6V-160 battery pack. Five of its 18 modules have been changed. Based on DOE`s standard, the battery has reached the end of its useful life. Nevertheless, the battery pack is still operational and its operating range is still greater than 40 miles per charge. It is too early to evaluate the life expectancy of the other three batteries, the Trojan T-145, Exide GC-5, and Alco 2200. No module has been replaced in these three packs. The Trojan T-145 battery is a very promising EV traction battery in terms of quality and reliability versus price. HNEI will keep the Trojan and Exide battery packs in operation. The Alco 2200 batteries will be transferred to another vehicle. The Additional Charging Method seems to be an effective way of restoring weak modules. The ``Smart Voltmeter`` developed by HNEI is a promising way of monitoring the remaining range for an EV.

  16. Electrical Energy Conservation and Peak Demand Reduction Potential for Buildings in Texas: Preliminary Results

    E-Print Network [OSTI]

    Hunn, B. D.; Baughman, M. L.; Silver, S. C.; Rosenfeld, A. H.; Akbari, H.

    1985-01-01T23:59:59.000Z

    Zone 2 (Fort Worth) only SWPLY CURE LEGEND BASE COYSWIPIIOYI 15885 KYH IAll-rlecl I9414 KHI 16rc hat) BASE PEAK: 5.3 KY Srvlnqr are crlculrted lrol ClRA runs EN0 USE UITEBORY: Hert~nq md hol~nq COST 10 LIFE SRVIN6S CCE lR1TROFITl... -- for All Single and Multifamily Residences, All Climate Zones SUPPLY CURVE LEGEND EASE COYSUIPIIDH: See notes belor LhD USE CATEGORY: Relrlqerrtors COST Ill LIFE WlVlN6S --------- ----- ------------ LABEL DESCRIPIIOY HEY RE1 IVRSl KlH KY Relr...

  17. Pollution error in the h-version of the finite-element method and the local quality of a-posteriori error estimators

    E-Print Network [OSTI]

    Mathur, Anuj

    1994-01-01T23:59:59.000Z

    in the L-shaped domain shown in Figs. la-ld. We applied boundary condi- 1 tions consistent with the singular solution u(r, 8) = rr sin(-) in the infinite wedge (see also Chapter II) and we assumed that we are interested only in the solution in the hol...-element solution in the subdomain. In Fig. l. la we show an adaptive finite-element mesh which was gener- ated using remeshing and linear elements, over the L-shaped domain fl. For this mesh an accuracy of 1. 09% for the relative error in the energy-norm over...

  18. Private trucking costs and records

    E-Print Network [OSTI]

    Haning, Charles R

    1959-01-01T23:59:59.000Z

    Ccaystieoa of Ls?sl L?hot Rsyoa?s to See-L?hot Rsyoaeo Coot-hHOL? daslyoio xoc?L Disco coot y?~LLL? kaalyoi? lstseoitg Cost-y?~LL? daelgeio LeeaL Co?C~LNLL? ka?LXaie C?eyeeieoa Roteess Looal sad 1atcmoitg %la-Lstcac Coot-SeHNlo 9 9 Ll LX 14 19 Xi... s aired fleet of trucks was 29 seats psr nile. Of this figure& 14 cents was attributable co tho driver expenses whish included ths wages of tha drivers and helpers. Thoro wes epproxinacaly a 51 cent difference becwesa the per nile costs fot...

  19. Bulletin of Tibetology: Volume 30, Number 2 : Full issue

    E-Print Network [OSTI]

    Namgyal Institute of Tibetology

    1994-07-12T23:59:59.000Z

    consistent with the ritualistic disciplines. He composed many philosophical works on Buddhism for the preservation and continuity of doctrines till posterity, besides holding both the spiritual and temporal power over Tibet(Chos-srid gnyis -ldan... -po. Autobiography ofVth Dalai Lama. Vol. V. 730 Folio. Dkar-chag (Index) Za-hol' !"'Yi ban-de ngag-dbang blo-bzang l'gya-mtaho'i 'di-:mang 'khrul-pa'i rol-rtsed rto!,,'S-bljod kyi tshul-du bkod-pa du-ku-Ia'i gos-bzang las glegs-bam gnyis-pa. Autobiography of...

  20. The late Victorian and Edwardian intellectual influence on the Wolfenden Report of 1957

    E-Print Network [OSTI]

    McIntosh, Craig Lee

    1972-01-01T23:59:59.000Z

    in 1903 in an obscure literary Journal, Zhe ~Tem le mr. In it r'or ster dealt w1th the rel?tionship between two young friends, Tommy and Ha old, The story opened with a letter from Harold, who was at the time Ln i'Japles, which begged Tommy, a... student at one of the universities, to come with h1m and his f1*ncee and her family for a hol1day in Sicily. Tommy did not go. Harold suddenly lost his mind in the ruins of an old Greek city, a city 1n wnich Harold decided that he had lived before...

  1. Breed and environmental factors influencing the performance of crossbred cattle for milk production in a tropical environment 

    E-Print Network [OSTI]

    Contreras Duran, Ricardo Eligio

    1977-01-01T23:59:59.000Z

    'ber on lactation performance. Plain dairy- ing characterist'c= of these farms are: most of the cows are Bos . indicos-Bos taurus crossbreds, , cows a!0 '1~cd-m. Ikcd and no concentrate is fed to the animals. The experimental material consisted of 1888 lactation... records from Hol. tein, Brown Hwiss, Criollo, Zebu and Brahman crossbred cows. 1'dil k yield was estimated from monthly weights. Calvir!g number, lactation length, calving interval and previous dry pe iod were also recorded. Analyses we e conducted...

  2. Synthesis of pore-variable mesoporous CdS and evaluation of its photocatalytic activity in degrading methylene blue

    SciTech Connect (OSTI)

    Zhang, Wei-Min, E-mail: chm_zhangwm@ujn.edu.cn [School of Chemistry and Chemical Engineering, University of Jinan (China); Jiang, Yao-Quan [School of Chemistry and Chemical Engineering, University of Jinan (China); Cao, Xiao-Yan [Key Laboratory of Marine Chemistry Theory and Technology, Ocean University of China, Ministry of Education (China); Chen, Meng; Ge, Dong-Lai [School of Chemistry and Chemical Engineering, University of Jinan (China); Sun, Zhong-Xi, E-mail: sunzx@ujn.edu.cn [School of Chemistry and Chemical Engineering, University of Jinan (China)

    2013-10-15T23:59:59.000Z

    Graphical abstract: - Highlights: • Self-templated synthesis of tubular CdS. • Cadmium complexes of aliphatic acids sustain the network of mesoporous structures. • Aliphatic acids affect the phase composition and particle size. • Pore size and volume vary with aliphatic acids having different hydrocarbonyl. - Abstract: In this study, mesoporous CdS polycrystallites have been synthesized using aliphatic acids of hexanoic acid, octanoic acid, and oleic acid as coordinating and capping agents, respectively. The fibrous Cd–fatty acid salts act as a template to form the tubular CdS. The organic species are found to be necessary for maintaining the network of mesoporous CdS. The characterization results indicate that the shorter carbon chain length in aliphatic acids favors the wurtzite phase and particle size growth the specific surface area, pore diameter and pore volume show a monotonic raise with increasing carbon chain. The photocatalytic activities of mesoporous CdS tubes exhibit much higher efficiency than those of nanosized CdS powders in decolorizing methylene blue under simulated visible light.

  3. Novel, resistant microalgal polyethers: An important sink of organic carbon in the marine environment?

    SciTech Connect (OSTI)

    Gelin, F.; Boogers, I.; Noordeloos, A.A.M. [Netherlands Institute for Sea Research, Den Burg (Netherlands)] [and others] [Netherlands Institute for Sea Research, Den Burg (Netherlands); and others

    1996-04-01T23:59:59.000Z

    Five out of seven marine microalgal species investigated were found to biosynthesize nonhydrolysable, mainly aliphatic, biomacromolecules (algaenans). The molecular structure of the algaenan isolated from the microalga Nannochloropsis salina of the class Eustigmatophyceae was determined by solid state {sup 13}C NMR spectroscopy, Curie point pyrolysis-gas chromatography-mass spectrometry, and chemical degradations with HI and RuO{sub 4}. The structure is predominantly composed of C{sub 28}-C{sub 34} linear chins linked by ether bridges. The algaenan isolated from a second eustigmatophyte (Nannochloropsis sp.) was structurally similar. Algaenans isolated from two chlorophytes also possess a strongly aliphatic nature, as revealed by the dominance of alkenes/alkanes in their pyrolysates. Accordingly, we proposed that the aliphatic character of numerous Recent and ancient marine kerogens reflects selectively preserved algaenans and that these algaenans may act as a source of n-alkanes in marine crude oils.

  4. Composition of the wax fraction of bitumen from methylated brown coals

    SciTech Connect (OSTI)

    S.I. Zherebtsov; A.I. Moiseev [Russian Academy of Sciences, Kemerovo (Russian Federation). Institute of Coal and Coal Chemistry

    2009-04-15T23:59:59.000Z

    Changes in the group and individual compositions of the wax fractions of bitumen in the course of brown coal methylation were studied. With the use of IR and NMR spectroscopy and chromatography-mass spectrometry, it was found that the esters of methylated coal waxes consisted of the native esters of fatty acids and the methyl esters of these acids formed as a result of an alkylation treatment. Esterification and transesterification were predominant among the reactions of aliphatic fraction components. A positive effect of methanol alkylation on an increase in the yield of the aliphatic fractions was found.

  5. IUPAC-NIST Solubility Data Series. 81. Hydrocarbons with Water and Seawater Revised and Updated. Part 7. C8H12C8H18 Hydrocarbons

    E-Print Network [OSTI]

    IUPAC-NIST Solubility Data Series. 81. Hydrocarbons with Water and Seawater Revised and Updated. Part 7. C8H12­C8H18 Hydrocarbons with Water Volume Editors David G. Shawa... University of Alaska on the evaluation of the all experimental data for a given homologous series of aliphatic and aromatic hydrocarbons

  6. Synthetic aircraft turbine oil

    SciTech Connect (OSTI)

    Yaffe, R.

    1982-03-16T23:59:59.000Z

    Synthetic lubricating oil composition having improved oxidation stability comprising a major portion of an aliphatic ester base oil having lubricating properties, formed by the reaction of pentaerythritol and an organic monocarboxylic acid and containing a phenylnaphthylamine, a dialkyldiphenylamine, a polyhydroxy anthraquinone, a hydrocarbyl phosphate ester and a dialkyldisulfide.

  7. PHONON DISPERSION CURVES OF ORDERED PHASES OF T.B.B.A. Abstract. --The lattice dynamics of a deuterated single crystal of T.B.B.A. have been measured

    E-Print Network [OSTI]

    Boyer, Edmond

    of a deuterated single crystal of T.B.B.A. have been measured by mean of inelastic neutron scattering of the molecules. Previous neutron inelastic scattering measurements have been done on non-deuterated single of a melting of the terminal aliphatic chains. So neutron coherent inelastic scattering measure- ments have

  8. X-ray photoelectron emission spectromicroscopic analysis of arborescent lycopsid cell wall composition and Carboniferous coal ball preservation

    E-Print Network [OSTI]

    Boyce, C. Kevin

    composition and Carboniferous coal ball preservation C. Kevin Boyce a, , Mike Abrecht b , Dong Zhou b , P that were canopy dominants of many Pennsylvanian coal swamp forests. Its periderm or bark--the single greatest biomass contributor to many Late Paleozoic coals--is found to have a greater aliphatic content

  9. Process for the extraction of strontium from acidic solutions

    DOE Patents [OSTI]

    Horwitz, E.P.; Dietz, M.L.

    1993-01-01T23:59:59.000Z

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid.

  10. Process for the extraction of strontium from acidic solutions

    DOE Patents [OSTI]

    Horwitz, E.P.; Dietz, M.L.

    1994-09-06T23:59:59.000Z

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid. 4 figs.

  11. Atmos. Chem. Phys., 4, 17591769, 2004 www.atmos-chem-phys.org/acp/4/1759/

    E-Print Network [OSTI]

    Meskhidze, Nicholas

    for pyruvic, pinonic, benzoic and phthalic acid. To cover a wide range of conditions we have investigated of organic acids relevant to tropospheric aerosols C. E. Lund Myhre and C. J. Nielsen Department of Chemistry organic acids relevant to tropospheric aerosols are reported. The acids investigated are the aliphatic

  12. Surface chemistry control for selective fossil resin flotation

    DOE Patents [OSTI]

    Miller, Jan D. (1886 Atkin Ave., Salt Lake City, UT 84106); Yi, Ye (2875 E. Wander Way, Salt Lake City, UT 84117); Yu, Qiang (224 University Village, Salt Lake City, UT 84108)

    1994-01-01T23:59:59.000Z

    A froth flotation method is disclosed for separating fine particles of fossil resin from by use of frothing reagents which include an aliphatic organic compound having a polar group and containing not more than four carbon atoms. Butanol is an effective frothing reagent in this method.

  13. Coal liquefaction process using pretreatment with a binary solvent mixture

    DOE Patents [OSTI]

    Miller, Robert N. (Allentown, PA)

    1986-01-01T23:59:59.000Z

    An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300.degree. C. before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil.

  14. Environ. Sci. Technol. M92, 26,2454-2461 In-Situ Transformation of Carbon Tetrachloride and Other Halogenated

    E-Print Network [OSTI]

    Semprini, Lewis

    Environ. Sci. Technol. M92, 26,2454-2461 In-Situ Transformation of Carbon Tetrachloride and Other, California 94305-4020 Enhanced in-situ transformation of carbon tetrachloride (CT) was observed under anoxic Chlorinated aliphatic hydrocarbons (CAHs)with one or two carbon atoms are widely used as solvents, degreasing

  15. ELSEVIER Journal of Hazardous Materials 41 (1995)205-216 HIIZIIRDOUS

    E-Print Network [OSTI]

    Alvarez, Pedro J.

    dechlorination of carbon tetrachloride with elemental iron Bradley R. Helland, Pedro J.J. Alvarez*, Jerald L-1527, USA Received 3 August 1994;accepted in revised form 15 November 1994 Abstract Carbon tetrachloride (CC aliphatics such as carbon tetrachloride (CC14) are common environ- mental contaminants due

  16. Nanoparticles designed from low pressure plasmas as identification tool for astrophysical observations

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    interstellar media. The particles were polymerised in a low pressure capacitively coupled radio-frequency molecule production and reprocesses UV and optical radiation. The C-H stretch vibration of aliphatic coupled the radiofrequency discharge in argon/acetylene mixtures [Kovacevic submitted]. The particles

  17. The effect of bioremediation on microbial populations in an oil-contaminated coastal wetland

    E-Print Network [OSTI]

    Townsend, Richard Todd

    1999-01-01T23:59:59.000Z

    hydrocarbon and polycyclic aromatic hydrocarbon (PAH)-degrading microorganisms. These increases were observed at 0-5 cm and 5- 10 cm depths. For the first application, the average numbers of aliphatic-degrading and PAH-degrading microorganisms on nutrient...

  18. On the formation of ethynylbiphenyl (C14D5H5; C6D5C6H4CCH) isomers in the reaction of D5-phenyl radicals (C6D5; X2

    E-Print Network [OSTI]

    Kaiser, Ralf I.

    of aliphatic hydrocar- bons to (polycyclic) aromatic hydrocarbons (PAHs) from their acy- clic precursors,2] and envi- ronmental effects of PAHs [3]. Ideally, a stoichiometric combustion of fossil and bio fuel results in the release of solely water and car- bon dioxide, however, the high temperatures and pressures

  19. A KINETIC STUDY OF AEROBIC PROPANE UPTAKE AND COMETABOLIC DEGRADATION OF CHLOROFORM,

    E-Print Network [OSTI]

    Semprini, Lewis

    A KINETIC STUDY OF AEROBIC PROPANE UPTAKE AND COMETABOLIC DEGRADATION OF CHLOROFORM, CIS the behavior of different consortiums of aerobic propane-utilizing microorganisms, with respect to both the lag time for growth after exposure to propane, and their ability to transform three chlorinated aliphatic

  20. Process and catalyst for carbonylating olefins

    SciTech Connect (OSTI)

    Zoeller, J.R.

    1998-06-02T23:59:59.000Z

    Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

  1. Identification of the Wax Ester Synthase/Acyl-Coenzyme A:Diacylglycerol Acyltransferase WSD1 Required for

    E-Print Network [OSTI]

    Kunst, Ljerka

    Identification of the Wax Ester Synthase/Acyl-Coenzyme A:Diacylglycerol Acyltransferase WSD1 Required for Stem Wax Ester Biosynthesis in Arabidopsis1,2[W][OA] Fengling Li, Xuemin Wu, Patricia Lam Columbia, Canada V6T 1Z1 (R.J.) Wax esters are neutral lipids composed of aliphatic alcohols and acids

  2. Midterm Exam: Chemistry 223 McGill University

    E-Print Network [OSTI]

    Ronis, David M.

    Midterm Exam: Chemistry 223 McGill University INSTRUCTIONS 1. No books or notes are permitted. 2;Midterm Exam -2- Chemistry 223 1. (20%) Derive the the expression for ZA,B the number of collisions and to define any sym- bols. 5. (20%) Gasoline is a mixture of various aliphatic hydrocarbons, however, here we

  3. Organic electroanalysis with chemically modified electrodes

    SciTech Connect (OSTI)

    Guadalupe, A.R.; Abruna, H.D.

    1986-01-01T23:59:59.000Z

    The analytical utility of electrodes modified with functionalized polymer films for the determination of aromatic amines is demonstrated. The analysis is based on the preconcentration of the protonated amines into a functionalized polymer film that contains styrene sulfonate groups. Good sensitivity and high reproducibility were obtained for concentrations down to 10/sup -5/ M. Aliphatic amines do not interfere in the determination.

  4. CHEMISTRY COURSE OFFERINGS, FALL, 2012 (Last Updated 4/13/2012)

    E-Print Network [OSTI]

    Kounaves, Samuel P.

    , spectroscopy, and reactivity studies. Applications of inorganic compounds in synthesis, catalysis, materials of materials. Three lectures, one laboratory, one recitation. Only one of Chemistry 1, 11, or 16 may be counted compounds. Mono- and polyfunctional compounds, aliphatic and aromatic structures. Synthesis, reaction

  5. 1224 Mol. BioSyst., 2011, 7, 12241231 This journal is c The Royal Society of Chemistry 2011 Cite this: Mol. BioSyst., 2011, 7, 12241231

    E-Print Network [OSTI]

    Tsai, Ming-Daw

    vancomycin against MRSA as they carry an extra aliphatic acyl side chain on glucosamine (Glm) at residue 4 (r the drugs of the last resort to treat methicillin-resistant Staphylococcus aureus (MRSA) infections. Lipoglycopeptides, Tei and A40926 (3, Fig. 1) were reported to be more effective than vancomycin against MRSA

  6. PREPARATION AND IMPLANTATION ALZET OSMOTIC PUMPS (SOP-9) Osmotic pumps manufactured by ALZA Corporation (Palo Alto, CA) are

    E-Print Network [OSTI]

    Kleinfeld, David

    is compatible with most drugs and drug diluents, except aliphatic and aromatic hydrocarbons and natural oils oils on the pump #12;surface may interfere with proper pump performance. If a pump becomes contaminated depress the plunger of the syringe. When solution appears at the pump outlet, stop injecting and slowly

  7. Surface chemistry control for selective fossil resin flotation

    DOE Patents [OSTI]

    Miller, J.D.; Yi, Y.; Yu, Q.

    1994-06-07T23:59:59.000Z

    A froth flotation method is disclosed for separating fine particles of fossil resin by use of frothing reagents which include an aliphatic organic compound having a polar group and containing not more than four carbon atoms. Butanol is an effective frothing reagent in this method. 12 figs.

  8. Flexible moldable conductive current-limiting materials

    SciTech Connect (OSTI)

    Shea, John Joseph (Pittsburgh, PA); Djordjevic, Miomir B. (Milwaukee, WI); Hanna, William Kingston (Pittsburgh, PA)

    2002-01-01T23:59:59.000Z

    A current limiting PTC device (10) has two electrodes (14) with a thin film of electric conducting polymer material (20) disposed between the electrodes, the polymer material (20) having superior flexibility and short circuit performance, where the polymer material contains short chain aliphatic diepoxide, conductive filler particles, curing agent, and, preferably, a minor amount of bisphenol A epoxy resin.

  9. New insights into the chemical composition of chitinozoans Jrmy Jacob1,

    E-Print Network [OSTI]

    Boyer, Edmond

    1 New insights into the chemical composition of chitinozoans Jérémy Jacob1, , Florentin Paris2 dominated by aromatic groups with a low contribution of aliphatics and oxygen- or nitrogen-bearing compounds-GC/MS, chitin, Lower Palaeozoic Corresponding author: jeremy.jacob@univ-orleans.fr #12;2 1. Introduction

  10. Theoretical kinetic study of thermal unimolecular decomposition of cyclic alkyl radicals

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    : While many studies have been reported on the reactions of aliphatic hydrocarbons, the chemistry of cyclic hydrocarbons has not been explored extensively. In the present work, a theoretical study However, cycloalkanes and alkylcycloalkanes (in particular C5 and C6) are usually present in conventional

  11. ORIGINAL CONTRIBUTION Rheological characterization of asphalt

    E-Print Network [OSTI]

    Mather, Patrick T.

    compared favorably with those obtained using conventional parallel-plate torsional flow in a commercial and are aggregates of polar aromatic compounds (Maruska and Rao 1987). Maltenes are nonpolar aliphatic hydrocarbons time (Anderson and Marasteanu 1999). Because of their codification, the conventional tests

  12. Molecular Characterization of Organic Content of Soot along the Centerline of a Coflow Diffusion Flame

    SciTech Connect (OSTI)

    Cain, Jeremy P.; Laskin, Alexander; Kholghy, Mohammad Reza; Thomson, Murray; Wang, Hai

    2014-10-29T23:59:59.000Z

    High-resolution mass spectrometry coupled with nanospray desorption electrospray ionization was used to probe chemical constituents of young soot particles sampled along the centerline of a coflow diffusion flame of a three-component Jet-A1 surrogate. In lower positions where particles are transparent to light extinction (n= 632.8 nm), peri-condensed polycyclic aromatic hydrocarbons (PAHs) are found to be the major components of the particle material. These particles become enriched with aliphatic components as they grow in mass and size. Before carbonization occurs, the constituent species in young soot particles are aliphatic and aromatic compounds 200-600 amu in mass, some of which are oxygenated. Particles dominated by PAHs or mixtures of PAHs and aliphatics can both exhibit liquid-like appearance observed by electron microscopy and be transparent to visible light. The variations in chemical composition observed here indicate that the molecular processes of soot formation in coflow diffusion flames may be more complex than previously thought. For example, the mass growth and enrichment of aliphatic components in an initially, mostly aromatic structure region of the flame that is absent of H atoms or other free radicals indicates that there must exist at least another mechanism of soot mass growth in addition to the hydrogen-abstraction-carbon addition mechanism currently considered in fundamental models of soot formation.

  13. Life of His Holiness the Vth Dalai Lama, Ngag-dbang blo-bzang rgya-mtsho (1617-1682 A.D.)

    E-Print Network [OSTI]

    Gyatso, Acharya Samten

    1994-01-01T23:59:59.000Z

    power over Tibet(Chos-srid gnyis -ldan). In the Water-Dog year corresponding to 1682 A.D at the age of sixty six, he departed from the world of mortal existence, to rest peacefully in the abode of purity. WORKS OFVTHDAUU LAMA NGAG-DBANG BLO BZANG... -pa du-ku-Ia'i gos-bzang las glegs-bam dang-po. Autobiography ofVth Dalai Lama. Vol. V. 730 Folio. Dkar-chag (Index) Za-hol' !"'Yi ban-de ngag-dbang blo-bzang l'gya-mtaho'i 'di-:mang 'khrul-pa'i rol-rtsed rto!,,'S-bljod kyi tshul-du bkod-pa du...

  14. Performance test results for the Eaton dc developmental power train in an electric test bed vehicle

    SciTech Connect (OSTI)

    Crumley, R.L.; Donaldson, M.R.

    1987-09-01T23:59:59.000Z

    This report presents the results of the tests performed on a direct current (dc) power train in a test bed vehicle developed by the Eaton Corporation for the US Department of Energy (DOE). The tests were performed by EG and G Idaho, Inc. at the Idaho National Engineering Laboratory (INEL). The purpose of the INEL testing was to provide test results from which an evaluation of the performance capabilities of the Eaton dc power train could be made and compared with other vehicle propulsion systems. The planned tests were primarily oriented toward road testing, chassis dynamometer testing, and associated dynamometer coastdown tests for road loss determination. Range tests of the Eaton dc test bed vehicle using an ALCO 2200 lead acid battery pack, produced ranges of 97 km at 56 km/h (60 miles at 35 mph), 79 km at 72 km/h (49 miles at 45 mph), and 47 km at 88 km/h (29 miles at 55 mph). The corresponding net dc energy consumptions are 135 Wh/km (217 Wh/mile), 145 Wh/km (233 Wh/mile), and 178 Wh/km (287 Wh/mile). The energy consumption for the D-cycle test was 241 Wh/km (387 Wh/mile). 8 refs., 11 figs., 16 tabs.

  15. Cleaning method for removing sulfur containing deposits from coke oven gas lines

    SciTech Connect (OSTI)

    Sumansky, L.W.

    1985-04-09T23:59:59.000Z

    Process for removing hard to remove deposits containing elemental sulfur and multivalent compounds from a surface comprising contacting the deposits with a cleaning composition comprising (a) a major portion of aliphatic amine, (b) water, and (c) an oxidizing or reducing agent, allowing the cleaning composition to remain in contact with the deposits for sufficient time to allow sufficient dissolution of said solid to take place to allow removal of the deposits to take place, and applying such force as is necessary to remove these partially dissolved deposits from the surface. A preferred cleaning composition comprises from about 60 to about 90 volume percent aliphatic amine, from about 10 to about 40 volume percent water, and from about 1 to about 3 weight percent of a moderate oxidizing or reducing agent, such percentages based on the total composition.

  16. sup 13 C, sup 17 O, and sup 14 N NMR spectroscopic studies of a series of mixed isocyanide/carbonyl complexes of tungsten: W(CO) sub 6-n (CNR) sub n (R = tert-butyl, p tolyl; n = 1-3)

    SciTech Connect (OSTI)

    Guy, M.P.; Coffer, J.L.; Rommel, J.S.; Bennett, D.W. (Univ. of Wisconsin, Milwaukee (USA))

    1988-08-24T23:59:59.000Z

    {sup 13}C, {sup 17}O, and {sup 14}N NMR spectra for the tungsten isocyanide complexes W(CO){sub 6-n}(CNR){sub n} (R = tert-butyl, p-tolyl; n = 1-3) have been obtained and the magnitudes of the corresponding chemical shifts utilized as a probe of differences in electronic structure. Comparisons of {delta}({sup 17}O) with {delta}({sup 13}CO) and of {delta}(C{sup 14}N) with {nu}(CN), or {delta}({sup 13}CO) are shown to confirm the better net donor ability of the aliphatic isocyanide over the aromatic isocyanide and illustrate an increased amount of charge density available at the metal center when CO is successively replaced with CNR. Marked differences in {sup 14}N quadrupolar relaxation times are observed between aromatic and aliphatic isocyanides, suggesting that the aromatic ring is involved in the M-L {pi} system. 19 references, 5 figures, 3 tables.

  17. Chemical differences are observed in children's versus adults' laten fingerprints as a function of time

    SciTech Connect (OSTI)

    Antoine, K.M.; Miller, L.; Mortazavi, S.; Miller, A.D.

    2010-03-01T23:59:59.000Z

    The identification of aged latent fingerprints is often difficult, especially for those of children. To understand this phenomenon, the chemical composition of children's versus adults latent fingerprints was examined over time using Fourier transform infrared microscopy. Hierarchical cluster analysis revealed that children's and adults prints were distinguishable for up to 4 weeks after deposition, based on differences in sebum composition. Specifically, adults had a higher lipid content than children, but both decreased over time, attributable to the volatility of free fatty acids. The aliphatic CH{sub 3}, aliphatic CH{sub 2}, and carbonyl ester compositions changed differently in adults versus children over time, consistent with higher cholesterol and cholesteryl esters in children's prints and wax esters and glycerides in adults prints. Thus, fingerprint composition changes with time differently in children versus adults, making it a sensitive metric to estimate the age of an individual, especially when the age of the print is known.

  18. Influence of Methionine on Growth and Nitrogen Balance in Weanling Quarter Horses

    E-Print Network [OSTI]

    Winsco, Kelly Nicole

    2011-02-22T23:59:59.000Z

    of chains of individual amino acids linked together by peptide bonds. It is these individual amino acids that are used to form body tissues, enzymes, antibodies, and hormones, and must be present in order for growth or production to occur. There are 30... breaking down into the classifications of aliphatic, aromatic, and sulfur based amino acids (Ellis and Hill, 2005). These individual amino acids link 4 together by means of peptide bonds to form proteins, which also have varying structure...

  19. Catalytic hydrogenation of an aromatic sulfonyl chloride into thiophenol

    E-Print Network [OSTI]

    Rouckout, Nicolas Julien

    2009-05-15T23:59:59.000Z

    to the facile oxidation by air into disulfides [3]. Many aliphatic thiols are important starting materials for the synthesis of crop- protection agents, pharmaceuticals, agrochemicals and polysulfides. They are also widely used as polymerization regulators... for the preparation of pharmaceuticals, agrochemicals, dyes, pigments, rubber, plastics and metal finishing [3]. The current market volume for aromatic thiols was determined to be more than 10 million pounds per year [4]. Aromatic thiols are commonly synthesized...

  20. Coal liquefaction process using pretreatment with a binary solvent mixture

    DOE Patents [OSTI]

    Miller, R.N.

    1986-10-14T23:59:59.000Z

    An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300 C before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil. 1 fig.

  1. Nanofluids and a method of making nanofluids for ground source heat pumps and other applications

    DOE Patents [OSTI]

    Olson, John Melvin

    2013-11-12T23:59:59.000Z

    This invention covers nanofluids. Nanofluids are a combination of particles between 1 and 100 nanometers, a surfactant and the base fluid. The nanoparticles for this invention are either pyrogenic nanoparticles or carbon nanotubes. These nanofluids improve the heat transfer of the base fluids. The base fluid can be ethylene glycol, or propylene glycol, or an aliphatic-hydrocarbon based heat transfer fluid. This invention also includes a method of making nanofluids. No surfactant is used to suspend the pyrogenic nanoparticles in glycols.

  2. Effects of shipment on diffusive dosimetry recovery efficiency for pentane, hexane and heptane

    E-Print Network [OSTI]

    Read, Ronald Bruce

    1981-01-01T23:59:59.000Z

    Sciences College of Pharmacy Chairman of' Advisory Committee: Mr. Charles L. Gilmore The effects of' shipment on recovery was investigated for three aliphatic hydrocarbons adsorbed on the 3M Company's $3500 Organic Vapor Monitor and the Scientific Kit... Combination Vs. Contaminant INTRODUCTION The Occupational Safety and Health Adminsitration (OSHA) has promulgated standards including permissible exposure limits (PEL) for humans based on eight hour time-weighted average (TWA) exposures for approximately...

  3. Polyestercarbonates which exhibit improved processibility

    DOE Patents [OSTI]

    Krabbenhoft, Herman Otto (Scotia, NY)

    1999-01-01T23:59:59.000Z

    The invention relates to a polyestercarbonate polymer which comprises repeating units of a mono-unsaturated aliphatic dicarboxylic acid having about 12 to about 20 carbon atoms. Preferred dicarboxylic acids for incorporation into the polymer are cis-octadec-9-enedioic acid or trans-octadec-9-enedioic acid. The use of these mono-unsaturated acids results in polymers with lower glass transition temperatures, and enhances processibility.

  4. Composition of the ozonolytic degradation products of the organic matter of Barzasskii sapromyxite coal

    SciTech Connect (OSTI)

    S.A. Semenova; Y.F.Patrakov [Russian Academy of Sciences, Kemerovo (Russian Federation). Institute of Coal and Coal Chemistry

    2009-04-15T23:59:59.000Z

    The ozonization of Barzasskii sapromyxite coal in chloroform and the composition of ozonolytic degradation products were studied. Water-insoluble high-molecular-weight products were predominant among the ozonization products. A half of water-soluble substances consisted of aliphatic C{sub 5}-C{sub 12} dicarboxylic acids and benzenedicarboxylic acid derivatives. Sapromyxite has been suggested as a substitute for crude petroleum in the manufacture of motor fuels.

  5. Stable carbon isotope ratio of polycyclic aromatic hydrocarbons (PAHs) in the environment: validation of isolation and stable carbon isotope analysis methods 

    E-Print Network [OSTI]

    Kim, Moon Koo

    2004-11-15T23:59:59.000Z

    , fluorene and chrysene, can be used to determine if the PAHs are pyrogenic or petrogenic in origin (Wang et al., 1999). Some PAHs are relatively resistant to degradation compared with aliphatic hydrocarbons, and the relative amounts can also reflect... INTRODUCTION Organic pollutants are an ever increasing concern as a stressor of ecosystems and an agent of degradation of the condition and health of natural resources. Many classes of industrial and combustion-derived chemicals are released...

  6. Synthesis of some 2-(3-butenyl) cyclohexanones 

    E-Print Network [OSTI]

    Wu, Tsi Chien

    1971-01-01T23:59:59.000Z

    as alkylating agent. The ketones were first treated with cyclohexylamine to form an imine. Subsequent reaction with ethylmagnesium bromide formed the corresponding magnesium salt, Treat- ment of the salt with 3-butenyl tosylate gave the 2-(3- butenyl... In a recent modification of the enamine alkylation procedure, an aldehyde or ketone was allowed to react 6 with an aliphatic amine (t-butylamine and cyclohexylamine were used) to form an imine. Subsequent reaction with ethyl-magnesium bromide formed...

  7. Structural features of Athabasca bitumen related to upgrading performance

    SciTech Connect (OSTI)

    Strausz, O.P. (Univ. of Alberta, Edmonton (Canada))

    1989-04-01T23:59:59.000Z

    Structural studies on asphaltenes and heavy ends have, until recently, only yielded information on some of the gross compositional features of these materials. Spectroscopic methods, for sample, are limited in the sense that even if several functional groups (e.g., aromatic or aliphatic carbon, carbonyl groups, etc.) can be identified, no information on the molecular environment can be deduced. Selective chemical degradative methods, on the other hand, offer more potential and this paper describes some of their recent results on the chemical degradation of asphaltene and heavy ends. Quantitative recoveries of alkyl side chains and bridging units attached to aromatic rings have been achieved, and some insights into the aliphatic framework have been gained. The results could be particularly helpful with regard to monitoring the dealkylation processes during thermal treatment of bitumens. The aliphatic framework of the asphaltene contains units of five- and six-membered ring sulfides and thermal breakdown of these units also contributes to depolymerization and the production of alkanes. Some of the heteroatom-containing classes of compounds identified in the asphaltene and resin fractions of Athabasca bitumen will be briefly discussed.

  8. Accurate measurements of {sup 13}C-{sup 13}C distances in uniformly {sup 13}C-labeled proteins using multi-dimensional four-oscillating field solid-state NMR spectroscopy

    SciTech Connect (OSTI)

    Straasř, Lasse Arnt; Nielsen, Jakob Toudahl; Bjerring, Morten; Nielsen, Niels Chr., E-mail: ncn@inano.au.dk [Center for Insoluble Protein Structures (inSPIN), Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, DK-8000 Aarhus C (Denmark); Khaneja, Navin [Division of Applied Sciences, Harvard University, Cambridge, Massachusetts 02138 (United States)

    2014-09-21T23:59:59.000Z

    Application of sets of {sup 13}C-{sup 13}C internuclear distance restraints constitutes a typical key element in determining the structure of peptides and proteins by magic-angle-spinning solid-state NMR spectroscopy. Accurate measurements of the structurally highly important {sup 13}C-{sup 13}C distances in uniformly {sup 13}C-labeled peptides and proteins, however, pose a big challenge due to the problem of dipolar truncation. Here, we present novel two-dimensional (2D) solid-state NMR experiments capable of extracting distances between carbonyl ({sup 13}C?) and aliphatic ({sup 13}C{sub aliphatic}) spins with high accuracy. The method is based on an improved version of the four-oscillating field (FOLD) technique [L. A. Straasř, M. Bjerring, N. Khaneja, and N. C. Nielsen, J. Chem. Phys. 130, 225103 (2009)] which circumvents the problem of dipolar truncation, thereby offering a base for accurate extraction of internuclear distances in many-spin systems. The ability to extract reliable accurate distances is demonstrated using one- and two-dimensional variants of the FOLD experiment on uniformly {sup 13}C,{sup 15}N-labeled-L-isoleucine. In a more challenging biological application, FOLD 2D experiments are used to determine a large number of {sup 13}C?-{sup 13}C{sub aliphatic} distances in amyloid fibrils formed by the SNNFGAILSS fibrillating core of the human islet amyloid polypeptide with uniform {sup 13}C,{sup 15}N-labeling on the FGAIL fragment.

  9. Molecular and crystal structure of n-hexyloxybenzoic anhydride at low and room temperatures

    SciTech Connect (OSTI)

    Konstantinov, I. I., E-mail: konst@ips.ac.ru [Russian Academy of Sciences, Topchiev Institute of Petrochemical Synthesis (Russian Federation); Churakov, A. V.; Kuz'mina, L. G. [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation)

    2010-09-15T23:59:59.000Z

    The crystal and molecular structures of n-hexyloxybenzoic anhydride, C{sub 6}H{sub 13}-O-C{sub 6}H{sub 4}-C(O)-O-C(O)-C{sub 6}H{sub 4}-C{sub 6}H{sub 13}, at low (120 K) and room (296 K) temperatures have been investigated. The molecule has an asymmetric bent structure. The dihedral angle between the benzene ring planes is 48.5 deg. The aliphatic chain on one side of the molecule has a transoid orientation with respect to the 'internal' C4 atom of the closest benzene ring, whereas the aliphatic chain on the other side has a cissoid orientation with respect to the analogous C(4A) atom. The crystal packing does not exhibit any pronounced separation of the crystal space into closely packed aromatic or loosely packed aliphatic regions. No weak directional interactions are observed in the packing; this fact explains the absence of liquid-crystal properties for this compound.

  10. The crystal and molecular structure of [alpha]-maltose

    E-Print Network [OSTI]

    Takusagawa, Fusao; Jacobson, R. A.

    1978-01-01T23:59:59.000Z

    -09 (5) H2(C6') 142 (3) 779 (3) 1130 (6) . 3-5 - 5 4 (4) 877 (3) 510(6) 5-0 0-95 (6) H(Ol') 460 (4) 654 (3) 826 (6) 5-0 89 (4) 1047 (4) 476 (6) 5-0 0-99 (6) H(02') 289 (4) 517(3) 491 (6) 5-0 200 (4) 1171 (4) 809 (6) 5-0 0-93 (6) H(03') 94(4) 738 (4...-5,-y + 1-0,2-0-5 2-770 (4) 2-959 (4) 3-085 (4) 2-797 (4) 2-741 (4) 2-780(4) 2-707 (4) 2-850(4) 2-836 (4) 3-03 (2) 2-06 (5) 2-36 (5) 2-23 (5) 1-89 (5) 1-93 (4) 1-72 (5) 1-88 (6) 1-96 (5) 2-17(5) 169 (5) 124 (4) 160 (6) 162 (5) 165...

  11. Nitric-phosphoric acid treatment of TRU wastes

    SciTech Connect (OSTI)

    Smith, J.R.; Pierce, R.A.; Sturcken, E.F.

    1993-09-30T23:59:59.000Z

    A general process is being developed for the treatment of solid TRU and hazardous organic waste. Experimental data indicates that 100 lb/hr of aliphatic organic (plastics) and 1,000 lb/hr of non-aliphatic organic compounds can be quantitatively oxidized in a 1,000 gallon reaction vessel. The process uses dilute nitric acid in a concentrated phosphoric acid media as the main oxidant for the organic compounds. Phosphoric acid allows oxidation at temperatures up to 200{degrees}C and is relatively non-corrosive on 304-L stainless steel, especially at room temperature. Many organic materials have been completely oxidized to CO{sub 2}, CO, and inorganic acids in a 0.1M HNO{sub 3}/14.8M H{sub 3}PO{sub 4} solution. Addition of 0.001M Pd{sup 2+} reduces the CO to near 1% of the released carbon gases. To accomplish complete oxidation the solution temperature must be maintained above 130--150{degrees}C. Organic materials quantitatively destroyed include neoprene, cellulose, EDTA, TBP, tartaric acid, and nitromethane. The oxidation is usually complete in a few hours for soluble organic materials. The oxidation rate for non-aliphatic organic solids is moderately fast and surface area dependent. Polyethylene is quantitatively oxidized in 1.0M HNO{sub 3}/13.8M H{sub 3}PO{sub 4} solution while contained in pressure vessels heated with microwave energy. This is probably due to the high concentrations of NO{sub 2}{center_dot} obtained in the reaction environment.

  12. Development of an integrated, in-situ remediation technology. Draft topical report for task No. 9. Part II. Entitled: TCE degradation using non-biological methods, September 26, 1994--May 25, 1996

    SciTech Connect (OSTI)

    Orth, R.G.; McKenzie, D.E.

    1997-04-01T23:59:59.000Z

    Contamination in low permeability soils poses a significant technical challenge to in-situ remediation efforts. Poor accessibility to the contaminants and difficulty in delivery of treatment reagents have rendered existing in-situ treatments such as bioremediation, vapor extraction, pump and treat rather ineffective when applied to low permeability soils present at many contaminated sites. The technology is an integrated in-situ treatment in which established geotechnical methods are used to install degradation zones directly in the contaminated soil and electro-osmosis is utilized to move the contaminants back and forth through those zones until the treatment is completed. The use of zero valence iron for reductive dechlorination of aliphatic chlorinated hydrocarbons is currently under investigation by a number of research groups as a potential method of in-situ treatment of contaminated ground water. The reaction appears to involve the transfer of electrons to chloro-aliphatic compounds by the oxidation of zero valence iron to ferrous iron (Fe{sup +2}). Our studies have indicated that this reaction is consistent with those of corrosion, and as such, can be influenced or increased by the presence of small amounts of metals (5% by weight) such as copper, tin, silver, gold and palladium coated on the iron surface. Incomplete coverage of the iron surface with a more electropositive metal results in an open galvanic cell, which increases the oxidation of iron and facilitates and increases the concurrent reduction of trichloroethylene and other chlorinated aliphatic compounds to the corresponding alkenes and alkanes. Our results show that plating more electropositive metals onto certain iron surfaces results in approximately a factor of ten increase in the dechlorination rate of small organochlorine compounds such as TCE.

  13. Anodic polymerization of vinyl ethylene carbonate in Li-Ion battery electrolyte

    SciTech Connect (OSTI)

    Chen, Guoying; Zhuang, Guorong V.; Richardson, Thomas J.; Gao, Liu; Ross Jr., Philip N.

    2005-02-28T23:59:59.000Z

    A study of the anodic oxidation of vinyl ethylene carbonate (VEC) was conducted with post-mortem analysis of reaction products by ATR-FTIR and gel permeation chromatography (GPC). The half-wave potential (E1/2) for oxidation of VEC is ca. 3.6 V producing a resistive film on the electrode surface. GPC analysis of the film on a gold electrode produced by anodization of a commercial Li-ion battery electrolyte containing 2 percent VEC at 4.1 V showed the presence of a high molecular weight polymer. IR analysis indicated polycarbonate with alkyl carbonate rings linked by aliphatic methylene and methyl branches.

  14. Selective sorbents for purification of hydrocarbons

    DOE Patents [OSTI]

    Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hernandez-Maldonado, Arturo J.

    2006-05-30T23:59:59.000Z

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  15. Selective sorbents for purification of hydrocartons

    DOE Patents [OSTI]

    Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hermandez-Maldonado, Arturo J.

    2006-12-12T23:59:59.000Z

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal ion that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  16. Selective Sorbents For Purification Of Hydrocarbons

    DOE Patents [OSTI]

    Yang, Ralph T. (Ann Arbor, MI); Yang, Frances H. (Ann Arbor, MI); Takahashi, Akira (Yoko-Machi, JP); Hernandez-Maldonado, Arturo J. (Ann Arbor, MI)

    2006-04-18T23:59:59.000Z

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal ion that is adapted to form p-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by p-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  17. Selective sorbents for purification of hydrocarbons

    DOE Patents [OSTI]

    Yang, Ralph T.; Hernandez-Maldonado, Arturo J.; Yang, Frances H.; Takahashi, Akira

    2006-08-22T23:59:59.000Z

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  18. Atomic Structures of Graphene, Benzene and Methane with Bond Lengths as Sums of the Single, Double and Resonance Bond Radii of Carbon

    E-Print Network [OSTI]

    Raji Heyrovska

    2008-04-25T23:59:59.000Z

    Two dimensional layers of graphene are currently drawing a great attention in fundamental and applied nanoscience. Graphene consists of interconnected hexagons of carbon atoms as in graphite. This article presents for the first time the structures of graphene at the atomic level and shows how it differs from that of benzene, due to the difference in the double bond and resonance bond based radii of carbon. The carbon atom of an aliphatic compound such as methane has a longer covalent single bond radius as in diamond. All the atomic structures presented here have been drawn to scale.

  19. Volatile organic acids and microbial processes in the Yegua formation, east-central Texas

    E-Print Network [OSTI]

    Routh, J.; Grossman, E. L.; Ulrich, G. A.; Suflita, J. M.

    2000-01-01T23:59:59.000Z

    ?171. Carothers, W.W., Kharaka, Y.K., 1978. Aliphatic acid anions in oil-field waters?implications for origin of natural gas. Bull. Am. Assoc. Petrol. Geol. 62, 2441?2453. Cedarstrom, D.J., 1946. Genesis of groundwaters in the coastal plain of Virginia. Econ. Geol.... Petrol. Geol., 37, pp. 127?149. Takijima, Y., 1964. Studies on organic acids in paddy field soils with reference to their inhibitory eC128ects on the growth of rice plants Part 1. Growth inhibitory action of organic acids and adsorption and decomposition...

  20. Kinetic data base for combustion modeling

    SciTech Connect (OSTI)

    Tsang, W.; Herron, J.T. [National Institute of Standards and Technology, Gaithersburg, MD (United States)

    1993-12-01T23:59:59.000Z

    The aim of this work is to develop a set of evaluated rate constants for use in the simulation of hydrocarbon combustion. The approach has been to begin with the small molecules and then introduce larger species with the various structural elements that can be found in all hydrocarbon fuels and decomposition products. Currently, the data base contains most of the species present in combustion systems with up to four carbon atoms. Thus, practically all the structural grouping found in aliphatic compounds have now been captured. The direction of future work is the addition of aromatic compounds to the data base.

  1. The application of soft X-ray microscopy to the in-situ analysis of sporopollenin/sporinite in a rank variable suite of organic rich sediments

    SciTech Connect (OSTI)

    Cody, G.D.; Botto, R.E. [Argonne National Lab., IL (United States). Chemistry Div.; Ade, H. [North Carolina State Univ., Raleigh, NC (United States). Dept. of Physics; Wirick, S. [State Univ. of New York, Stony Brook, NY (United States). Dept. of Physics

    1997-07-01T23:59:59.000Z

    Soft X-ray imaging and carbon near edge absorption fine structure spectroscopy (C-NEXAFS) has been used for the in-situ analysis of sporinite in a rank variable suite of organic rich sediments extending from recent up to high volatile A bituminous coal. The acquisition of chemically based images (contrast based on the 1s - 1{pi}* transition of unsaturated carbon), revealed a homogeneous chemical structure in the spore exine. C-NEXAFS microanalysis indicates chemical structural evolution in sporopollenin/sporinite with increases in maturation. The most significant change in the C-NEXAFS spectrum is an increase in unsaturated carbon, presumably aromatic, with rank. The rate of aromatization in sporinite exceeds that of the surrounding vitrinite. Increases in the concentration of unsaturated carbon are compensated by losses of aliphatic and hydroxylated aliphatic carbon components. Carboxyl groups are present in low and variable concentrations. Absorption due to carboxyl persists in the most mature specimen in this series, a high volatile A rank coal. The reactions which drive sporopollenin chemical structural evolution during diagenesis presumably involve dehydration, Diels-Alder cyclo-addition, and dehydrogenation reactions which ultimately lead to a progressively aromatized bio/geopolymer.

  2. Liquid fuels production from biomass. Final report, for period ending June 30, 1980

    SciTech Connect (OSTI)

    Levy, P. F.; Sanderson, J. E.; Ashare, E.; Wise, D. L.; Molyneaux, M. S.

    1980-01-01T23:59:59.000Z

    The current program to convert biomass into liquid hydrocarbon fuels is an extension of a previous program to ferment marine algae to acetic acid. In that study it was found that marine algae could be converted to higher aliphatic organic acids and that these acids could be readily removed from the fermentation broth by membrane or liquid-liquid extraction. It was then proposed to convert these higher organic acids via Kolbe electrolysis to aliphatic hydrocarbons, which may be used as a diesel fuel. The specific goals for the current program are: (1) establish conditions under which substrates other than marine algae may be converted in good yield to organic acids, here the primary task is methane suppression; (2) modify the current 300-liter fixed packed bed batch fermenter to operate in a continuous mode; (3) change from membrane extraction of organic acids to liquid-liquid extraction; (4) optimize the energy balance of the electrolytic oxidation process, the primary task is to reduce the working potential required for the electrolysis while maintaining an adequate current density; (5) scale the entire process up to match the output of the 300 liter fermenter; and (6) design pilot plant and commercial size plant (1000 tons/day) processes for converting biomass to liquid hydrocarbon fuels and perform an economic analysis for the 1000 ton/day design.

  3. Liquid fuels production from biomass. Final report

    SciTech Connect (OSTI)

    Levy, P. F.; Sanderson, J. E.; Ashare, E.; Wise, D. L.; Molyneaux, M. S.

    1980-06-30T23:59:59.000Z

    The current program to convert biomass into liquid hydrocarbon fuels is an extension of a previous program to ferment marine algae to acetic acid. In that study it was found that marine algae could be converted to higher aliphatic organic acids and that these acids could be readily removed from the fermentation broth by membrane or liquid-liquid extraction. It was then proposed to convert these higher organic acids via Kolbe electrolysis to aliphatic hydrocarbons, which may be used as a diesel fuel. The specific goals for the current porgram are: (1) establish conditions under which substrates other than marine algae may be converted in good yield to organic acids, here the primary task is methane suppression; (2) modify the current 300-liter fixed packed bed batch fermenter to operate in a continuous mode; (3) change from membrane extraction of organic acids to liquid-liquid extraction; (4) optimize the energy balance of the electrolytic oxidation process, the primary task is to reduce the working potential required for the electrolysis while maintaining an adequate current density; (5) scale the entire process up to match the output of the 300 liter fermenter; and (6) design pilot plant and commercial size plant (1000 tons/day) processes for converting biomass to liquid hydrocarbon fuels and perform an economic analysis for the 1000 ton/day design.

  4. Zinc ferrite nanoparticle as a magnetic catalyst: Synthesis and dye degradation

    SciTech Connect (OSTI)

    Mahmoodi, Niyaz Mohammad, E-mail: mahmoodi@icrc.ac.ir

    2013-10-15T23:59:59.000Z

    Graphical abstract: Photocatalytic degradation of Reactive Red 198 and Reactive Red 120 by the synthesized zinc ferrite nanoparticle. - Highlights: • Magnetic zinc ferrite nanoparticle was synthesized and characterized. • Photocatalytic dye degradation by magnetic nanoparticle was studied. • Formate, acetate and oxalate were detected as dominant dye degradation aliphatic intermediates. • Nitrate and sulfate ions were detected as mineralization products of dyes. • Zinc ferrite nanoparticle was an effective magnetic photocatalyst to degrade dyes. - Abstract: In this paper, magnetic zinc ferrite (ZnFe{sub 2}O{sub 4}) nanoparticle was synthesized and its photocatalytic dye degradation ability from colored wastewater was studied. Reactive Red 198 (RR198) and Reactive Red 120 (RR120) were used as model dyes. The characteristics of ZnFe{sub 2}O{sub 4} were investigated using Fourier transform infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM). Photocatalytic dye degradation by ZnFe{sub 2}O{sub 4} was studied by UV–vis spectrophotometer and ion chromatography (IC). The effects of ZnFe{sub 2}O{sub 4} dosage, initial dye concentration and salt on dye degradation were evaluated. Formate, acetate and oxalate anions were detected as dominant aliphatic intermediate. Inorganic anions (nitrate and sulfate anions) were detected as dye mineralization products. The results indicated that ZnFe{sub 2}O{sub 4} could be used as a magnetic photocatalyst to degrade dyes from colored wastewater.

  5. Synthesis of nickel–zinc ferrite magnetic nanoparticle and dye degradation using photocatalytic ozonation

    SciTech Connect (OSTI)

    Mahmoodi, Niyaz Mohammad, E-mail: mahmoodi@icrc.ac.ir [Department of Environmental Research, Institute for Color Science and Technology, Tehran (Iran, Islamic Republic of); Bashiri, Marziyeh; Moeen, Shirin Jebeli [Department of Environmental Research, Institute for Color Science and Technology, Tehran (Iran, Islamic Republic of)] [Department of Environmental Research, Institute for Color Science and Technology, Tehran (Iran, Islamic Republic of)

    2012-12-15T23:59:59.000Z

    Graphical abstract: Display Omitted Highlights: ? Nickel–zinc ferrite magnetic nanoparticle (NZFMN) was synthesized and characterized. ? Dye degradation by photocatalytic ozonation using NZFMN was studied. ? Formate, acetate and oxalate were detected as dominant dye degradation aliphatic intermediates. ? Nitrate, sulfate and chloride ions were detected as mineralization products of dyes. ? NZFMN was an effective magnetic nanocatalyst to degrade dyes. -- Abstract: In this paper, nickel–zinc ferrite magnetic nanoparticle (NZFMN) was synthesized and its dye degradation ability using photocatalytic ozonation was investigated. The NZFMN was characterized by X-ray diffraction (XRD), scanning electron microscopic (SEM), Fourier transforms infrared (FTIR) and alternative gradient force magnetometer (AGFM). Reactive Red 198 (RR198) and Direct Green 6 (DG6) were used as dye models. UV–vis and ion chromatography (IC) analyses were employed to study dye degradation. The effects of operational parameters on decolorization such as NZFMN dosage, dye concentration, salt and pH were studied. RR198 and DG6 were completely decolorized (100%) by photocatalytic ozonation using NZFMN. Formate, acetate and oxalate anions were detected as dominant aliphatic intermediates. Nitrate, sulfate and chloride ions were detected as mineralization products of dyes. Results showed that the photocatalytic ozonation using NZFMN was a very effective method for dye degradation.

  6. First-Principles Studies of Photoinduced Charge Transfer in Noncovalently Functionalized Carbon Nanotubes

    E-Print Network [OSTI]

    Chu, Iek-Heng; Cheng, Hai-Ping

    2013-01-01T23:59:59.000Z

    We have studied the energetics, electronic structure, optical excitation, and electron relaxation of dinitromethane molecules (CH$_{2}$N$_{2}$O$_{4}$) adsorbed on semiconducting carbon nanotubes (CNTs) of chiral index (n,0) (n=7, 10, 13, 16, 19). Using first-principles density functional theory (DFT) with generalized gradient approximations and van der Waals corrections, we have calculated adsorption energies of dinitropentylpyrene, in which the dinitromethane is linked to the pyrene via an aliphatic chain, on a CNT. A 75.26 kJ/mol binding energy has been found, which explains why such aliphatic chain-pyrene units can be and have been used in experiments to bind functional molecules to CNTs. The calculated electronic structures show that the dinitromethane introduces a localized state inside the band gap of CNT systems of n=10, 13, 16 and 19; such a state can trap an electron when the CNT is photoexcited. We have therefore investigated the dynamics of intra-band relaxations using the reduced density matrix fo...

  7. Liquid-liquid equilibria for mixtures of an alkane + an aromatic hydrocarbon + 1,4-dicyanobutane at 298.15 K

    SciTech Connect (OSTI)

    Letcher, T.M.; Naicker, P.K.

    2000-02-01T23:59:59.000Z

    The separation of pure aromatic and aliphatic compounds from their mixtures is an important goal in chemical operations (e.g., Fischer-Tropsch synthesis) that produce both types of compounds. In this work the authors have used 1,4-dicyanobutane (DCB) as a potential solvent for this separation. Liquid-liquid equilibrium results for mixtures of an alkane + an aromatic hydrocarbon + 1,4-dicyanobutane at 298.15 K are reported, where the alkane is hexane or nonane or dodecane or hexadecane and the aromatic hydrocarbon is benzene or methylbenzene or 1,2-dimethylbenzene, or 1,3-dimethylbenzene, or 1,4-dimethylbenzene or 1,3,5-trimethylbenzene or ethylbenzene. The results show that there is a small increase in the two-phase region as the chain length of the alkane is increased. The type of aromatic hydrocarbon present in the mixture has a noticeable effect on the slopes of the tie lines. There is also an increase in the area of the two phase-region with increasing substitution of methyl groups on the benzene ring. NRTL and UNIQUAC models were correlated to the data. The results show that 1,4-dicyanobutane may be used as a solvent for the separation of aromatic and aliphatic hydrocarbons.

  8. Liquid fuels production from biomass. Progress report No. 10, October 1-December 31, 1979

    SciTech Connect (OSTI)

    Sanderson, J.E.; Levy, P.F.; Wise, D.L.; Nabor, M.R.; Molyneaux, M.S.; Hughes, C.A.

    1980-02-01T23:59:59.000Z

    It was found that marine algae could be converted to higher aliphatic organic acids and that these acids could be readily removed from the fermentation broth by membrane or liquid-liquid extraction. It was then proposed to convert these higher organic acids via Kolbe Electrolysis to aliphatic hydrocarbons, which may be used as a diesel fuel. A coenzyme M analogue, 2-bromoethanesulfonic acid has been shown to be an effective suppressor of methane in nonsterile anaerobic fermentation of cellulosic substrates. Preliminary experiments have also been completed utilizing corn meal in which 2-bromoethanesulfonic acid and carbon monoxide were both found to be effective methane suppressors. An analysis of the energy outputs and requirements for the production of liquid hydrocarbon fuel from corn has been performed. As a means of expanding the number of potential substrates, pretreatment schemes are being investigated. A tapered auger device has been designed and built which has been demonstrated on the bench to be effective for adding substrate and removing residue in a continuous manner from a fixed packed bed fermenter. A solvent extractor system using kerosene as the nonaqueous phase has been constructed and is currently in operation in series with the 300 liter fixed packed bed fermenter. Although additional work is required to optimize the electrolysis process, the electrolytic oxidation of organic acids produced in the 300 liter fixed packed bed fermenter is operating with a favorable energy balance of 6/1 based on the applied potential.

  9. Crosslinked Polyamide

    DOE Patents [OSTI]

    Huang, Zhi H. (East Lansing, MI); McDonald, William F. (Utica, OH); Wright, Stacy C. (Lansing, MI); Taylor, Andrew C. (Ann Arbor, MI)

    2002-06-04T23:59:59.000Z

    A crosslinked polyamide material and a process for preparing the crosslinked polyamide material are disclosed. The crosslinked polyamide material comprises a crosslinked chemical combination of (1) a polyamide of the formula: ##STR1## wherein n is between about 50 and 10,000, wherein each R is between 1 and 50 carbon atoms alone and is optionally substituted with heteroatoms, oxygen, nitrogen, sulfur, or phosphorus and combinations thereof, wherein multiple of the R are in vertically aligned spaced relationship along a backbone forming the polyamide, and wherein two or more of the R contain an amino group; and (2) a crosslinking agent containing at least two functional groups capable of reacting with the amino groups of the polyamide. In one embodiment of the invention, the crosslinking agent is an aliphatic or aromatic isocyanate compound having 2 or more --N.dbd.C.dbd.O groups. In another embodiment of the invention, the crosslinking agent is an aliphatic aldehyde or aromatic aldehyde compound having 2 or more --CHO groups. In still another embodiment of the invention, the crosslinking agent is selected from a phosphine having the general formula (A).sub.2 P(B) and mixtures thereof, wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or aryl. In yet another embodiment of the invention, the crosslinking agent is selected from the group consisting of epoxy resins having more than one epoxide group per molecule.

  10. Far- and mid-infrared spectroscopy of complex organic matter of astrochemical interest: coal, heavy petroleum fractions, and asphaltenes

    E-Print Network [OSTI]

    Cataldo, F; Manchado, A

    2012-01-01T23:59:59.000Z

    The coexistence of a large variety of molecular species (i.e., aromatic, cycloaliphatic and aliphatic) in several astrophysical environments suggests that unidentified IR emission (UIE) occurs from small solid particles containing a mix of aromatic and aliphatic structures (e.g., coal, petroleum, etc.), renewing the astronomical interest on this type of materials. A series of heavy petroleum fractions namely DAE, RAE, BQ-1, and asphaltenes derived from BQ-1 were used together with anthracite coal and bitumen as model compounds in matching the band pattern of the emission features of proto-planetary nebulae (PPNe). All the model materials were examined in the mid-infrared (2.5-16.7 um) and for the first time in the far-infrared (16.7-200 um), and the IR bands were compared with the UIE from PPNe. The best match of the PPNe band pattern is offered by the BQ-1 heavy aromatic oil fraction and by its asphaltenes fraction. Particularly interesting is the ability of BQ-1 to match the band pattern of the aromatic-ali...

  11. Soil organic matter factions of no-tilled and tilled soils and their reactivity with herbicides

    SciTech Connect (OSTI)

    Stearman, G.K.

    1987-01-01T23:59:59.000Z

    Properties of soil humic fractions were determined on surface and 7.5-15.0 cm soil samples of continuously (7-year) no-tilled and tilled cotton, corn, and soybean plots in West Tennessee. Soil humic and fulvic acid were extracted by standard methods and the humic acid was characterized by /sup 13/C-NMR spectroscopy, titration of total acidity and carboxyl groups, and infrared and elemental analysis. Humic acid composition differed by depth and crop. Small differences were observed between tillage systems. Humic acid aliphatic and aromatic carbons ranged from 48 to 65% and 25 to 40% of total peak area, respectively. The humic acids extracted from soils with larger amounts of carbon had larger aliphatic to aromatic ratios, indicating less decomposed organic matter. Carboxyl groups of the humic acids ranged from 9 to 13% and samples from tilled soil had slightly greater amounts of carboxyl and aromatic groups. Carboxyl group determinations by /sup 13/C-NMR, compared more closely with total acidity determinations by titration than with carboxyl determinations by titration. All infrared spectra were similar. Elemental composition of humic acid averaged C, 52.7%, 5.6%; N, 4.8%, and 36.9%.

  12. Characterization of the surface properties of Illinois basin coals. Final technical report, September 1, 1991--August 31, 1992

    SciTech Connect (OSTI)

    Demir, I.; Harvey, R.D.; Lizzio, A.A. [Illinois State Geological Survey, Champaign, IL (United States)

    1992-12-31T23:59:59.000Z

    Surface area and pore volume distributions, surface charge, and surface chemical structure of the eight coals in the Illinois Basin Coal Sample Program (IBCSP) were determined. The IBC-101 coal has the lowest total and micropore (3.5-20.0 {Angstrom}) surface areas. The IBC-103 coal has the lowest mesopore (20-500 {Angstrom}) surface area. The mesopore surface areas of IBC-101, IBC-102, and IBC-107 coals are higher than the other four coals. Pore volume in pores <1800 {Angstrom} in diameter varies almost five-fold with IBC-103 coal having the lowest value. These differences may affect the reactivity of these coals during cleaning, conversion, and combustion processes. Surface charge and isoelectric points vary among the samples. The isoelectric point, where processes such as agglomeration and dewatering is most efficient, shifted to higher pH values for some of the samples upon exposure to air oxidation at room temperature. Diffuse reflectance infrared spectroscopy (DRIS) data indicate that the surfaces of the IBCSP coals contain aromatic hydrocarbon components, aliphatic hydrocarbons, and an aldehyde group. Ball-mill grinding reduced the organic hydroxyls and thus enriched relative concentrations of nonpolar aliphatic functional groups in the samples. The room temperature air oxidation did not cause any significant change on the surface chemical structure of the coals.

  13. Exploring the Genome and Proteome of Desulfitobacterium hafniense DCB2 for its Protein Complexes Involved in Metal Reduction and Dechlorination

    SciTech Connect (OSTI)

    Kim, Sang-Hoon, Christina Harzman, John K. Davis, Rachel Hutcheson, Joan B. Broderick, Terence L. Marsh, James M. Tiedje.

    2012-09-27T23:59:59.000Z

    Desulfitobacteria are of interest to DOE mission because of their ability to reduce many electron acceptors including Fe(III), U(VI), Cr(VI), As(V), Mn(IV), Se(VI), NO3- and well as CO2, sulfite, fumarate and humates, their ability to colonize more stressful environments because they form spores, fix nitrogen and they have the more protective Gram positive cell walls. Furthermore at least some of them reductively dechlorinate aromatic and aliphatic pollutants. Importantly, most of the metals and the organochlorine reductions are coupled to ATP production and support growth providing for the organism's natural selection at DOE's contaminant sites. This work was undertaken to gain insight into the genetic and metabolic pathways involved in dissimilatory metal reduction and reductive dechlorination, (ii) to discern the commonalities among these electron-accepting processes, (iii) to identify multi-protein complexes catalyzing these functions and (iv) to elucidate the coordination in expression of these pathways and processes.

  14. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOE Patents [OSTI]

    Sen, A.; Jiang, Z.

    1996-05-28T23:59:59.000Z

    The compound, [Pd(Me-DUPHOS)(MeCN){sub 2}](BF{sub 4}){sub 2}, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic {alpha}-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone).

  15. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOE Patents [OSTI]

    Sen, Ayusman (State College, PA); Jiang, Zhaozhong (State College, PA)

    1996-01-01T23:59:59.000Z

    The compound, [Pd(Me-DUPHOS)(MeCN).sub.2 ](BF.sub.4).sub.2, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic .alpha.-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone)

  16. On the origin of the 11.3 micron unidentified infrared emission feature

    E-Print Network [OSTI]

    Sadjadi, SeyedAbdolreza; Kwok, Sun

    2015-01-01T23:59:59.000Z

    The 11.3 $\\mu$m emission feature is a prominent member of the family of unidentified infrared emission (UIE) bands and is frequently attributed to out-of-plane bending modes of polycyclic aromatic hydrocarbon (PAH) molecules. We have performed quantum mechanical calculations of 60 neutral PAH molecules and found that it is difficult to reconcile the observed astronomical feature with any or a mix of these PAH molecules. We have further analyzed the fitting of spectra of several astronomical objects by the NASA PAH database program and found that reasonable fittings to the observed spectra are only possible by including significant contributions from oxygen and/or magnesium containing molecules in the mix. A mixed of pure PAH molecules, even including units of different sizes, geometry and charged states, is unable to fit the astronomical spectra. Preliminary theoretical results on the vibrational spectra of simple molecules with mixed aromatic/aliphatic structures show that these structures have consistent bu...

  17. Reactor and method for hydrocracking carbonaceous material

    DOE Patents [OSTI]

    Duncan, Dennis A. (Downers Grove, IL); Beeson, Justin L. (Clarendon Hills, IL); Oberle, R. Donald (Hammond, IN); Dirksen, Henry A. (Harvey, IL)

    1980-01-01T23:59:59.000Z

    Solid, carbonaceous material is cracked in the presence of hydrogen or other reducing gas to provide aliphatic and aromatic hydrocarbons of lower molecular weight for gaseous and liquid fuels. The carbonaceous material, such as coal, is entrained as finely divided particles in a flow of reducing gas and preheated to near the decomposition temperature of the high molecular weight polymers. Within the reactor, small quantities of oxygen containing gas are injected at a plurality of discrete points to burn corresponding amounts of the hydrogen or other fuel and elevate the mixture to high temperatures sufficient to decompose the high molecular weight, carbonaceous solids. Turbulent mixing at each injection point rapidly quenches the material to a more moderate bulk temperature. Additional quenching after the final injection point can be performed by direct contact with quench gas or oil. The reactions are carried out in the presence of a hydrogen-containing reducing gas at moderate to high pressure which stabilizes the products.

  18. Method and apparatus for synthesizing hydrocarbons

    DOE Patents [OSTI]

    Colmenares, C.A.; Somorjai, G.A.; Maj, J.J.

    1985-04-16T23:59:59.000Z

    A method and apparatus for synthesizing a mixture of aliphatic alcohols having five carbons or less is disclosed. An equal molar ratio of CO and H/sub 2/ gases is caused to pass through a ThO/sub 2/ catalyst having a surface area of about 80 to 125 m/sup 2//g. The catalyst further optionally includes Na ions present as substitutional cations in an amount of about 5 to 10 atom %. At a temperature of about 570 to 630/sup 0/K, and at pressures of about 20 to 50 atm, methanol and isobutanol are the predominant products and are produced in amounts of about 90 wt % of the total hydrocarbon mixture. 6 figs.

  19. Biotreatment techniques get chemical help

    SciTech Connect (OSTI)

    Elizardo, K. (Solvay Interox, Houston, TX (United States))

    1993-11-01T23:59:59.000Z

    Biological treatment methods for contaminated soils and groundwater, including landfarming, pump-and-treat bioreactors and in situ bioremediation, are using hydrogen peroxide (H[sub 2]O[sub 2]) as an oxidant to reduce cleanup time and save money. Some examples of how the chemical is being used include the following: recent studies indicate peroxygen compounds, such as calcium peroxide, can be used to chemically aerate soils in landfarming applications. Pump-and-treat bioreactor systems for treating halogenated aliphatics can use an H[sub 2]O[sub 2] solution to deliver oxygen to oxygen-deficient systems. The solution has proven effective for improving bioreactor efficiency during limited oxygen solubility; in situ peroxidation can be used to partially oxidize soil contaminants to reduce their toxicity and enhance their biodegradability in the unsaturated zone prior to in situ bioremediation.

  20. Water soluble laser dyes

    DOE Patents [OSTI]

    Hammond, Peter R. (Livermore, CA); Feeman, James F. (Wyomissing, PA); Field, George F. (Santa Ana, CA)

    1998-01-01T23:59:59.000Z

    Novel water soluble dyes of the formula I are provided ##STR1## wherein R.sup.1 and R.sup.4 are alkyl of 1 to 4 carbon atoms or hydrogen; or R.sup.1 -R.sup.2 or R.sup.2 -R.sup.4 form part of aliphatic heterocyclic rings; R.sup.2 is hydrogen or joined with R.sup.1 or R.sup.4 as described above; R.sup.3 is --(CH.sub.2).sub.m --SO.sub.3.sup.-, where m is 1 to 6; X is N, CH or ##STR2## where Y is 2 --SO.sub.3.sup.- ; Z is 3, 4, 5 or 6 --SO.sub.3.sup.-. The novel dyes are particularly useful as the active media in water solution dye lasers.

  1. Bending elasticity of a curved amphiphilic film decorated anchored copolymers: a small angle neutron scattering study

    E-Print Network [OSTI]

    Jacqueline Appell; Christian Ligoure; Gregoire Porte

    2004-06-30T23:59:59.000Z

    Microemulsion droplets (oil in water stabilized by a surfactant film) are progressively decorated with increasing amounts of poly ethylene- oxide (PEO) chains anchored in the film by the short aliphatic chain grafted at one end of the PEO chain . The evolution of the bending elasticity of the surfactant film with increasing decoration is deduced from the evolution in size and polydispersity of the droplets as reflected by small angle neutron scattering. The optimum curvature radius decreases while the bending rigidity modulus remains practically constant. The experimental results compare well with the predictions of a model developed for the bending properties of a curved film decorated by non-adsorbing polymer chains, which takes into account, the finite curvature of the film and the free diffusion of the chains on the film.

  2. Reduction of Aromatic Hydrocarbons by Zero-Valent Iron and Palladium Catalyst

    SciTech Connect (OSTI)

    Kim, Young-Hun; Shin, Won Sik; Ko, Seok-Oh; Kim, Myung-Chul

    2004-03-31T23:59:59.000Z

    Permeable reactive barrier (PRB) is an alternative technology for soil and groundwater remediation. Zero valent iron, which is the most popular PRB material, is only applicable to halogenated aliphatic organics and some heavy metals. The objective of this study was to investigate reductive dechlorination of halogenated compounds and reduction of non-halogenated aromatic hydrocarbons using zero valent metals (ZVMs) and catalysts as reactive materials for PRBs. A group of small aromatic hydrocarbons such as monochlorophenols, phenol and benzene were readily reduced with palladium catalyst and zero valent iron. Poly-aromatic hydrocarbons (PAHs) were also tested with the catalysts and zero valent metal combinations. The aromatic rings were reduced and partly reduced PAHs were found as the daughter compounds. The current study demonstrates reduction of aromatic compounds by ZVMs and modified catalysts and implicates that PRB is applicable not only for halogenated organic compounds but nonhalogenated aromatic compounds such as PAHs.

  3. An Assessment of the Stability and the Potential for In-Situ Synthesis of Regulated Organic Compounds in High Level Radioactive Waste Stored at Hanford, Richland, Washington

    SciTech Connect (OSTI)

    Wiemers, K.D.; Babad, H.; Hallen, R.T.; Jackson, L.P.; Lerchen, M.E.

    1999-01-04T23:59:59.000Z

    The stability assessment examined 269 non-detected regulated compounds, first seeking literature references of the stability of the compounds, then evaluating each compound based upon the presence of functional groups using professional judgment. Compounds that could potentially survive for significant periods in the tanks (>1 year) were designated as stable. Most of the functional groups associated with the regulated organic compounds were considered unstable under tank waste conditions. The general exceptions with respect to functional group stability are some simple substituted aromatic and polycyclic aromatic compounds that resist oxidation and the multiple substituted aliphatic and aromatic halides that hydrolyze or dehydrohalogenate slowly under tank waste conditions. One-hundred and eighty-one (181) regulated, organic compounds were determined as likely unstable in the tank waste environment.

  4. Evaluation of the atmospheric deposition of toxic contaminants to Puget Sound

    SciTech Connect (OSTI)

    Not Available

    1991-08-01T23:59:59.000Z

    A growing recognition of the potential for transfer of pollutants from air to water prompted the study of the contribution of airborne toxic contaminants to water quality problems in Puget Sound. The study objectives were: (1) to develop a better understanding of the relative contribution of atmospheric deposition to toxic contaminants in Commencement Bay and (2) to develop efficient and cost-effective tools which could be used for assessing the question in other Puget Sound reaches and embayments. Commencement Bay was selected to represent a 'worst case' test area in Puget Sound because it is heavily industrialized, having a complex mix of air pollution sources and high concentrations of chemicals in the bay sediments. The study design included sampling and analysis for metals, polycyclic aromatic hydrocarbons, PCBs, aliphatic hydrocarbons, and nutrients. Several mathematical models were created or modified for the study.

  5. Separation of sulfur and trace elements from high-viscosity petroleums and tar sands

    SciTech Connect (OSTI)

    Nadirov, N.K.; Bychkova, L.V.; Rudenko, N.V.; Dzhakupova, A.N.; Sarsembaeva, B.K.

    1992-07-10T23:59:59.000Z

    Characteristic features of high-viscosity petroleums and tar sands of western Kazakhstan are a great chemical nonuniformity, a diverse combination of proportions of aromatic and heteroatomic structures, and a wide variation in trace-element composition. They contain, moreover, large quantities of aliphatic ethers and esters, sulfo acids, cyclic hydrocarbons, and other valuable components that may be used in the chemical, petrochemical, and other industries. The authors study employed acetylacetone or propanol for organic solvent extraction of a sulfurous concentrate, magnifying the selective separation of organosulfur compounds with the use of ultrasonic phase stratification. Oxidation of organosulfur compounds to sulfoxides, sulfones, and sulfo acids was accomplished with ionizing radiation from Co{sup 60}. 17 refs., 2 tabs.

  6. N,N'-DICYCLOHEXYL-N"-ISOTRIDECYLGUANIDINE AS SUPPRESSOR FOR THE NEXT GENERATION CAUSTIC SIDE SOLVENT EXTRACTION (NG-CSSX) PROCESS

    SciTech Connect (OSTI)

    Duncan, Nathan C [ORNL; Roach, Benjamin D [ORNL; Williams, Neil J [ORNL; Bonnesen, Peter V [ORNL; Rajbanshi, Arbin [ORNL; Moyer, Bruce A [ORNL

    2012-01-01T23:59:59.000Z

    ABSTRACT The purity, concentration, and source of the N,N'-dicyclohexyl-N"-isotridecylguanidine (DCiTG) suppressor (guanidine) used in the NG-CSSX process were found to influence solvent performance. As the starting isotridecanol used in the preparation of DCiTG is comprised of a mixture of branched-chain aliphatic alcohols, varying in composition with manufacturer, the resulting DCiTG itself is a mixture. Thus, it is necessary to address how the solvent performance will be affected by the different preparations of the DCiTG solvent component. In this study, four preparations of DCiTG from three sources were analyzed and evaluated for purity and performance, both in the absence and presence of an anionic surfactant impurity.

  7. Water soluble laser dyes

    DOE Patents [OSTI]

    Hammond, P.R.; Feeman, J.F.; Field, G.F.

    1998-08-11T23:59:59.000Z

    Novel water soluble dyes of the formula 1 are provided by the formula described in the paper wherein R{sup 1} and R{sup 4} are alkyl of 1 to 4 carbon atoms or hydrogen; or R{sup 1}--R{sup 2} or R{sup 2}--R{sup 4} form part of aliphatic heterocyclic rings; R{sup 2} is hydrogen or joined with R{sup 1} or R{sup 4} as described above; R{sup 3} is --(CH{sub 2}){sub m}--SO{sub 3}{sup {minus}}, where m is 1 to 6; X is N, CH or formula 2 given in paper where Y is 2 --SO{sub 3}{sup {minus}} ; Z is 3, 4, 5 or 6 --SO{sub 3}{sup {minus}}. The novel dyes are particularly useful as the active media in water solution dye lasers.

  8. {gamma} Irradiation-induced degradation of organochlorinated pollutants in fatty esters and in Cod

    SciTech Connect (OSTI)

    Lepine, F.L.; Brochu, F.; Milot, S. [Institut Armand-Frappier, Quebec (Canada)] [and others

    1995-02-01T23:59:59.000Z

    The {gamma} irradiation-induced degradation of 2,2-bis(4-chlorophenyl)-1,1,1-trichloroethane (DDT), 2,2-bis(4-chlorophenyl)-1,1-dichloroethane (DDD), and 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (DDE) dissolved in methyl myristate and methyl oleate was studied. DDT and DDE produced DDD and 2,2-bis(4-chlorophenyl)chloroethylene (DDMU) respectively, in agreement with a previous study performed with aliphatic solvents. The degradation of these two former compounds was larger in methyl myristate than in methyl oleate and addition products between methyl myristate and the organochlorines were found. While DDD, DDE, and many PCB congeners in a cod sample were not measurably degraded at 15 KGy, DDT underwent 30% degradation. 9 refs., 1 fig., 2 tabs.

  9. Structural features of Athabasca bitumen related to upgrading performance

    SciTech Connect (OSTI)

    Strausz, O.P.; Lown, E.M. (Dept. of Chemistry, Univ. of Alberta, Edmonton, Alberta T6G 2G2 (CA))

    1991-01-01T23:59:59.000Z

    Using a combination of instrumental and chemical methods, many new classes of compounds appearing as homologous series have been detected in Athabasca oil sand bitumen and in the chemical and thermal degradative products of asphaltene and the heavy ends of maltene. In general, the volatile portion of the maltene is rich in cyclic terpenoid structures and devoid in aliphatic compounds or normal alkane-derived cyclic molecules while the asphaltene fraction and heavy ends of maltene are abundant in normal alkyl-substituted aromatics, thianes, thiolanes, thiophenes, benzo- and dibenzothiophenes. This paper reports that Ru(VIII)-catalyzed oxidation permitted the quantitative estimation of the n-alkyl groups attached to aromatic carbons and of n-alkyl bridges between two aromatic units and their concentration distribution according to chain length. It also showed the presence of a large naphthenic core containing cyclic sulfides, which, during oxidation, were converted to their sulfones.

  10. Identification of organic compounds contained in the bitumen of Chattanooga oil shale

    SciTech Connect (OSTI)

    Mc Gowan, C.W.; Greenwell, B.E.; Markuszewski, R.; Richard, J.J.; Sepaniak, M.J.

    1986-09-01T23:59:59.000Z

    The bitumen of Chattanooga Oil Shale has been extracted with benzene. The benzene-soluble material was separated into acid base and neutral fractions with ion exchange chromatography. This separation scheme has been used extensively to separate the organic material in Green River Oil Shale. The acid fraction was esterified with BF/sub 3//MeOH. A large portion of the acid fraction was not esterified and this material was considered to be phenolic. The bases were separated into two fractions using alumina. The esters, the two base fractions and the total neutral fraction were analyzed using gas chromatography coupled to mass spectrometry. Two series constituting the methyl esters of normal and isoprenoid acids were identified. Several homologous series were indicated in the base fraction. The major components in the neutral fractions were two series constituting normal and isoprenoid alkanes. The analysis scheme apparently does a good job of separating and identifying aliphatic materials.

  11. Solute retention in column liquid chromatography. X. Determination of solute infinite-dilution activity coefficients in methanol, water, and their mixtures, by combined gas-liquid and liquid-liquid chromatography

    SciTech Connect (OSTI)

    Djerki, R.A.; Laub, R.J.

    1988-01-01T23:59:59.000Z

    The Raoult's-law activity coefficients of 3- to 7-carbon aliphatic aldehyde, ketone, ester, and alcohol solutes at infinite dilution in methanol, water, and mixtures of the two and in polydimethysiloxane, all at 293-308 K, have been determined for the first time by appropriate combination of GLC and LLC retention data. The latter data are reported in terms of mole factions, while the former are given in concentration units of molality. However, interpretation of the data is difficult because of the multiplicity of the retention mechanisms. Nevertheless, the combined GLC/LLC technique, which had been applied previously only to pure solvents, is said to offer a number of advantages over static techniques for the determination of solute infinite-dilution activity coefficients with volatile solvents, especially with mixtures of solvents.

  12. Nonhazardous solvent composition and method for cleaning metal surfaces

    DOE Patents [OSTI]

    Googin, J.M.; Simandl, R.F.; Thompson, L.M.

    1993-05-04T23:59:59.000Z

    A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140 F and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140 F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

  13. Nonhazardous solvent composition and method for cleaning metal surfaces

    DOE Patents [OSTI]

    Googin, John M. (Oak Ridge, TN); Simandl, Ronald F. (Farragut, TN); Thompson, Lisa M. (Knoxville, TN)

    1993-01-01T23:59:59.000Z

    A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140.degree. F. and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140.degree. F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

  14. Protein Vivisection Reveals Elusive Intermediates in Folding

    SciTech Connect (OSTI)

    Zheng, Zhongzhou; Sosnick, Tobin R. (UC)

    2010-05-25T23:59:59.000Z

    Although most folding intermediates escape detection, their characterization is crucial to the elucidation of folding mechanisms. Here, we outline a powerful strategy to populate partially unfolded intermediates: A buried aliphatic residue is substituted with a charged residue (e.g., Leu {yields} Glu{sup -}) to destabilize and unfold a specific region of the protein. We applied this strategy to ubiquitin, reversibly trapping a folding intermediate in which the {beta}5-strand is unfolded. The intermediate refolds to a native-like structure upon charge neutralization under mildly acidic conditions. Characterization of the trapped intermediate using NMR and hydrogen exchange methods identifies a second folding intermediate and reveals the order and free energies of the two major folding events on the native side of the rate-limiting step. This general strategy may be combined with other methods and have broad applications in the study of protein folding and other reactions that require trapping of high-energy states.

  15. Metagenomics, metatranscriptomics and single cell genomics reveal functional response of active Oceanospirillales to Gulf oil spill

    SciTech Connect (OSTI)

    Mason, Olivia U.; Hazen, Terry C.; Borglin, Sharon; Chain, Patrick S. G.; Dubinsky, Eric A.; Fortney, Julian L.; Han, James; Holman, Hoi-Ying N.; Hultman, Jenni; Lamendella, Regina; Mackelprang, Rachel; Malfatti, Stephanie; Tom, Lauren M.; Tringe, Susannah G.; Woyke, Tanja; Zhou, Jizhong; Rubin, Edward M.; Jansson, Janet K.

    2012-06-12T23:59:59.000Z

    The Deepwater Horizon oil spill in the Gulf of Mexico resulted in a deep-sea hydrocarbon plume that caused a shift in the indigenous microbial community composition with unknown ecological consequences. Early in the spill history, a bloom of uncultured, thus uncharacterized, members of the Oceanospirillales was previously detected, but their role in oil disposition was unknown. Here our aim was to determine the functional role of the Oceanospirillales and other active members of the indigenous microbial community using deep sequencing of community DNA and RNA, as well as single-cell genomics. Shotgun metagenomic and metatranscriptomic sequencing revealed that genes for motility, chemotaxis and aliphatic hydrocarbon degradation were significantly enriched and expressed in the hydrocarbon plume samples compared with uncontaminated seawater collected from plume depth. In contrast, although genes coding for degradation of more recalcitrant compounds, such as benzene, toluene, ethylbenzene, total xylenes and polycyclic aromatic hydrocarbons, were identified in the metagenomes, they were expressed at low levels, or not at all based on analysis of the metatranscriptomes. Isolation and sequencing of two Oceanospirillales single cells revealed that both cells possessed genes coding for n-alkane and cycloalkane degradation. Specifically, the near-complete pathway for cyclohexane oxidation in the Oceanospirillales single cells was elucidated and supported by both metagenome and metatranscriptome data. The draft genome also included genes for chemotaxis, motility and nutrient acquisition strategies that were also identified in the metagenomes and metatranscriptomes. These data point towards a rapid response of members of the Oceanospirillales to aliphatic hydrocarbons in the deep sea.

  16. Alkaline-Side Extraction of Cesium from Savannah River Tank Waste Using a Calixarene-Crown Ether Extractant

    SciTech Connect (OSTI)

    Bonnesen, P.V.; Delmau, L.H.; Haverlock, T.J.; Moyer, B.A.

    1998-12-01T23:59:59.000Z

    Results are presented supporting the viability of the alkaline-side CSEX process as a potential replacement for the In-Tank Precipitation process for removal of cesium from aqueous high-level waste (HLW) at the Savannah River Site (SRS). Under funding from the USDOE Efficient Separations and Crosscutting program, a flowsheet was suggested in early June of 1998, and in the following four months, this flowsheet underwent extensive testing, both in batch tests at ORNL and ANL and in two centrifugal-contactor tests at ANL. To carry out these tests, the initial ESP funding was augmented by direct funds from Westinghouse Savannah River Corporation. The flowsheet employed a solvent containing a calixarene-crown hybrid compound called BoBCalixC6 that was invented at ORNL and can now be obtained commercially for government use from IBC Advanced Technologies. This special extractant is so powerful and selective that it can be used at only 0.01 M, compensating for its expense, but a modifier is required for use in an aliphatic diluent, primarily to increase the cesium distribution ratio D{sub Cs} in extraction. The modifier selected is a relatively economical fluorinated alcohol called Cs3, invented at ORNL and so far available. only from ORNL. For the flowsheet, the modifier is used at 0.2 M in the branched aliphatic kerosene Isopar{reg_sign} L. Testing at ORNL and ANL involved simulants of the SRS HLW. After extraction of the Cs from the waste simulant, the solvent is scrubbed with 0.05 M HNO{sub 3} and stripped with a solution comprised of 0.0005 M HNO{sub 3} and 0.0001 M CsNO{sub 3}. The selection of these conditions is justified in this report, both on the basis of experimental data and underlying theory.

  17. Systematic modulation and enhancement of CO{sub 2} : N{sub 2} selectivity and water stability in an isoreticular series of bio-MOF-11 analogues

    SciTech Connect (OSTI)

    Li, Tao; Chen, De-Li; Sullivan, Jeanne E.; Kozlowski, Mark T.; Johnson, J. Karl; Rosi, Nathaniel L.

    2013-02-01T23:59:59.000Z

    An isoreticular series of cobalt-adeninate bio-MOFs (bio-MOFs 11-14) is reported. The pores of bio-MOFs 11-14 are decorated with acetate, propionate, butyrate, and valerate, respectively. The nitrogen (N{sub 2}) and carbon dioxide (CO{sub 2}) adsorption properties of these materials are studied and compared. The isosteric heats of adsorption for CO{sub 2} are calculated, and the CO{sub 2}:N{sub 2} selectivities for each material are 10 determined. As the lengths of the aliphatic chains decorating the pores in bio-MOFs 11-14 increase, the BET surface areas decrease from 1148 m{sup 2}/g to 17 m{sup 2}/g while the CO{sub 2}:N{sub 2} selectivities predicted from ideal adsorbed solution theory at 1 bar and 273 K for a 10:90 CO{sub 2}:N{sub 2} mixture range from 73:1 for bio-MOF-11 to 123:1 for bio-MOF-12 and finally to 107:1 for bio-MOF-13. At 298 K, the selectivities are 43:1 for bio-MOF-11, 52:1 for bio-MOF-12, and 40:1 for bio-MOF-13. Additionally, it is shown that 15 bio-MOF-14 exhibits a unique molecular sieving property that allows it to adsorb CO{sub 2} but not N{sub 2} at 273 and 298 K. Finally, the water stability of bio-MOFs 11-14 increases with increasing aliphatic chain length. Bio-MOF-14 exhibits no loss of crystallinity or porosity after soaking in water for one month.

  18. Investigation of test methods, material properties, and processes for solar cell encapsulants. Eighteenth quarterly progress report, August 12-November 12, 1980

    SciTech Connect (OSTI)

    Willis, P. B.; Baum, B.; Davis, M.

    1980-12-01T23:59:59.000Z

    The goal of this program is to identify, evaluate, and recommend encapsulant materials and processes for the production of cost-effective, long-life solar cell modules. A survey was made of elastomers for use as gaskets for the photovoltaic module. Of the wide variety of materials examined EPDM offered the optimum combination of low compression set and low cost. The preference for EPDM is borne out by its long history of use as an automobile gasket. The commercial availability of materials that would be useful for sealants between the edge of the module and the gasket was investigated. Butyl sealants have the best combination of physical properties, low cost and a well-documented history of performance. A preferred composition has not yet been identified. One laminating type pottant ethylene/methyl acrylate copolymer (EMA), and two casting polymers, polybutyl acrylate and polyurethane, have been under investigation this past quarter. An EMA formulation has been developed which is easily extrudable and cures to a high gel content. So far only one commercial US source (Quinn) of aliphatic polyurethane has been located. Work is continuing to improve reaction rate as well as to eliminate source(s) of bubble formation during module fabrication. Considerable effort was spent in developing an improved polybutyl acrylate casting formulation providing high gel. Many viable curing systems are now available: however, the best formulation considering physical properties, freedom from bubbles as well as cure time utilizes Lupersol II (aliphatic peroxide) initiator. This initiator gives the desired gel after 20 minute cure at 45/sup 0/C or 12 minute cure at 55/sup 0/C.

  19. Fluoroalkyl and Alkyl Chains Have Similar Hydrophobicities in Binding to the “Hydrophobic Wall” of Carbonic Anhydrase

    SciTech Connect (OSTI)

    J Mecinovic; P Snyder; K Mirica; S Bai; E Mack; R Kwant; D Moustakas; A Heroux; G Whitesides

    2011-12-31T23:59:59.000Z

    The hydrophobic effect, the free-energetically favorable association of nonpolar solutes in water, makes a dominant contribution to binding of many systems of ligands and proteins. The objective of this study was to examine the hydrophobic effect in biomolecular recognition using two chemically different but structurally similar hydrophobic groups, aliphatic hydrocarbons and aliphatic fluorocarbons, and to determine whether the hydrophobicity of the two groups could be distinguished by thermodynamic and biostructural analysis. This paper uses isothermal titration calorimetry (ITC) to examine the thermodynamics of binding of benzenesulfonamides substituted in the para position with alkyl and fluoroalkyl chains (H{sub 2}NSO{sub 2}C{sub 6}H{sub 4}-CONHCH{sub 2}(CX{sub 2}){sub n}CX{sub 3}, n = 0-4, X = H, F) to human carbonic anhydrase II (HCA II). Both alkyl and fluoroalkyl substituents contribute favorably to the enthalpy and the entropy of binding; these contributions increase as the length of chain of the hydrophobic substituent increases. Crystallography of the protein-ligand complexes indicates that the benzenesulfonamide groups of all ligands examined bind with similar geometry, that the tail groups associate with the hydrophobic wall of HCA II (which is made up of the side chains of residues Phe131, Val135, Pro202, and Leu204), and that the structure of the protein is indistinguishable for all but one of the complexes (the longest member of the fluoroalkyl series). Analysis of the thermodynamics of binding as a function of structure is compatible with the hypothesis that hydrophobic binding of both alkyl and fluoroalkyl chains to hydrophobic surface of carbonic anhydrase is due primarily to the release of nonoptimally hydrogen-bonded water molecules that hydrate the binding cavity (including the hydrophobic wall) of HCA II and to the release of water molecules that surround the hydrophobic chain of the ligands. This study defines the balance of enthalpic and entropic contributions to the hydrophobic effect in this representative system of protein and ligand: hydrophobic interactions, here, seem to comprise approximately equal contributions from enthalpy (plausibly from strengthening networks of hydrogen bonds among molecules of water) and entropy (from release of water from configurationally restricted positions).

  20. Interfacial activity of phosphonated-polyethylene glycol functionalized cerium oxide nanoparticles

    E-Print Network [OSTI]

    L. Qi; J. Fresnais; P. Muller; O. Theodoly; J. -F. Berret; J. -P. Chapel

    2013-05-04T23:59:59.000Z

    In a recent publication, we have highlighted the potential of phosphonic acid terminated PEG oligomers to functionalize strong UV absorption cerium oxide nanoparticles[1], which yield suspensions that are stable in aqueous or organic solvents and are redispersible in different solvent after freeze-drying. In the present work, we highlight the interfacial activity of the functional ceria nanoparticles and their potential to modify hydrophobic surfaces. We first investigated Phosphonated-PEG amphiphilic oligomers behavior as strong surface active species forming irreversibly adsorbed layers. We then show that the oligomers interfacial properties translate to the functional nanoparticles. In particular, the addition of a small fraction of phosphonated-PEG oligomers with an extra C16 aliphatic chain (stickers) into the formulation enabled the tuning of i) the nanoparticles adsorption at the air/water, polystyrene/water, oil/water interfaces and ii) the particle/particle interaction in aqueous solutions. We also found that dense and closely packed two dimensional monolayers of nanoceria can be formed by spontaneous adsorption or surface compression using a Langmuir trough. A hexagonal organization controlled by reversible and repulsive repulsion has been characterized by GISAXS. Mono- or multilayers can also be stably formed or transferred on solid surfaces. Our results are key features in the field of polymer surface modification, solid stabilized emulsions (Pickering) or supracolloidal assemblies.

  1. Influence of Carbon Sources and Electron Shuttles on Ferric Iron Reduction by Cellulomonas sp. Strain ES6

    SciTech Connect (OSTI)

    Dr Robin Gerlach; Erin K. Field; Sridhar Viamajala; Brent M. Peyton; William A. Apel; Al B. Cunningham

    2011-09-01T23:59:59.000Z

    Microbially reduced iron minerals can reductively transform a variety of contaminants including heavy metals, radionuclides, chlorinated aliphatics, and nitroaromatics. A number of Cellulomonas spp. strains, including strain ES6, isolated from aquifer samples obtained at the U.S. Department of Energy's Hanford site in Washington, have been shown to be capable of reducing Cr(VI), TNT, natural organic matter, and soluble ferric iron [Fe(III)]. This research investigated the ability of Cellulomonas sp. strain ES6 to reduce solid phase and dissolved Fe(III) utilizing different carbon sources and various electron shuttling compounds. Results suggest that Fe(III) reduction by and growth of strain ES6 was dependent upon the type of electron donor, the form of iron present, and the presence of synthetic or natural organic matter, such as anthraquinone-2,6-disulfonate (AQDS) or humic substances. This research suggests that Cellulomonas sp. strain ES6 could play a significant role in metal reduction in the Hanford subsurface and that the choice of carbon source and organic matter addition can allow for independent control of growth and iron reduction activity.

  2. Separation and structure elucidation of coal molecule fragments. Final report, February 1, 1976-August 31, 1979

    SciTech Connect (OSTI)

    Schultz, R V; Jorgenson, J W; Maskarinec, M P; Kump, R L; Marli, F; Novotny, M; Todd, L J

    1980-01-01T23:59:59.000Z

    Separation and identification of the polynuclear aromatic and aliphatic fractions of solvent-refined coal and its recycle oil were performed using a combination of solvent partition and chromatographic fractionation procedures with glass-capillary gas chromatography/mass spectrometry. Chromatographic profiles were generated for each fraction and some semiquantitative data were also obtained. In total, 146 polynuclear aromatic components of SRC were tentatively identified by their molecular weights, as indicated by the mass spectra of the gas chromatography peaks. In addition, wherever possible, specific isomers have been indicated, based on comparison of spectral characteristics and retention data. Separation and identification of nitrogen-containing aromatics of the recycle oil of SRC was accomplished with a combination solvent partition and capillary gas chromatography with deactivated glass columns. High-precision retention measurements of known pyridine and quinoline derivatives are reported, utilizing parent aza-arenes as retention standards. Both precisely measured retention data and mass spectral information combined lead to positive identification of some compounds in SRC samples. A total of 48 two-membered or three-membered aza-arenes have been tentatively identified in the recycle oil.

  3. Effect of Ligands on Characteristics of (CdSe)13 Quantum Dot

    SciTech Connect (OSTI)

    Gao, Yang; Zhou, Bo; Kang, Seung-gu; Xin, Minsi; Yang, Ping; Dai, Xing; Wang, Zhigang; Zhou, Ruhong

    2014-01-01T23:59:59.000Z

    The widespread applications of quantum dots (QDs) have spurred an increasing interest in the study of their coating ligands, which can not only protect the electronic structures of the central QDs, but also control their permeability through biological membranes with both size and shape. In this work, we have used density functional theory (DFT) to investigate the electronic structures of (CdSe)13 passivated by OPMe2(CH2)nMe ligands with different lengths and various numbers of branches (Me=methyl group, n = 0, 1-3). Our results show that the absorption peak in the ultraviolet-visible (UV-vis) spectra displays a clear blue-shift, on the scale of ~100 nm, upon the binding of ligands. Once the total number of ligands bound with (CdSe)13 reached a saturated number (9 or 10), no more blue-shift occurred in the absorption peak in the UV-vis spectra. On the other hand, the aliphatic chain length of ligands has a negligible effect on the optical properties of the QD core. Analyses of the bonding characteristics confirm that optical transitions are dominantly governed by the central QD core rather than the organic passivation. Interestingly, the density of states (DOS) share similar characteristics as vibrational spectra, even though there is no coordination vibration mode between the ligands and the central QD. These findings might provide insights on the material design for the passivation of quantum dots for biomedical applications.

  4. Yellow phosphorus process to convert toxic chemicals to non-toxic products

    DOE Patents [OSTI]

    Chang, Shih-Ger (El Cerrito, CA)

    1994-01-01T23:59:59.000Z

    The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O.sub.3, PO, PO.sub.2, etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like.

  5. Predictors of plasticity in bituminous coals. Technical progress report No. 6

    SciTech Connect (OSTI)

    Lloyd, W.G.; Reasoner, J.W.; Hower, J.C.; Yates, L.P.; Bowling, C.C.; Davis, E.; Fitzpatrick, A.; Whitt, J.M.

    1983-03-01T23:59:59.000Z

    We have completed the pyrolysis/gas chromatographic analysis of all 40 coals in the present study, at two temperatures, 450/sup 0/ and 650/sup 0/C. We have also completed triplicate quantitative extraction analyses of all 40 coals, using tetrahydrofuran as the extractant solvent, and have completed a parallel set of extractions using N,N-dimethylformamide as the extractant solvent. In addition, we have completed analysis of over 100 additional isothermal Gieseler plastometer runs, and have made the first series of quantitative estimates of H(aromatic)/H(aliphatic) ratios from Fourier Transform Infrared Spectroscopy data. Exploratory work has begun on the petrographic characterization of the semi-coke residues from Gieseler plastometer runs, and also in characterizing THF extracts by thin layer chromatography and by column chromatography (quantitative group separations). Proximate, ultimate and petrographic characterization of the 40 coals has been completed previously. We are now prepared to start a study, using freshly re-sampled coals, of the effects of varying pressure upon the several parameters of fluidity.

  6. Analysis of volatile contaminants in US Navy fleet soda lime. Technical report, August 1992-May 1995

    SciTech Connect (OSTI)

    Lillo, R.S.; Ruby, R.; Gummin, D.D.; Porter, W.R.; Caldwell, J.M.

    1995-06-01T23:59:59.000Z

    Contamination was suspected of U.S. Navy Fleet soda lime (High Performance Sodasorb(R)) when an ammonia-like odor was reported during its use in August 1992. This material contained indicator dye and was used for carbon dioxide absorption during diving. This incident had a major impact on the U.S Navy diving program when the Navy temporarily banned use of Sodasorb(R) and authorized Sofnolime(R) as an interim replacement. The Naval Medical Research Institute was immediately assigned to investigate. Testing involved sampling from the headspace (gas space) inside closed buckets and from an apparatus simulating conditions during operational diving. Volatile organic compounds were analyzed by gas chromatography and mass spectrometry; ammonia and amines were measured by infrared spectroscopy. Significant amounts of ammonia (up to 30 ppm), ethyl and diethyl amines (up to several ppm), and various aliphatic hydrocarbons (up to 60 ppm) were detected during testing of both Sodasorb(R) and Sofnolime(R). Contaminants were slowly removed by gas flow and did not return. The source(s) of the ammonia and amines are unknown, although they may result from the breakdown of the indicator dye. Hydrocarbon contamination appeared to result from the materials of which the bucket is constructed. Based on these findings, the U.S. Navy is expected to phase in non-indicating soda lime that will be required to meet defined contaminant limits.

  7. Process for the extended use of strip acid employed in the reclamation of battery acid fluid from expanded lead-acid batteries

    SciTech Connect (OSTI)

    Spitz, R.A.; Bricker, M.

    1991-04-23T23:59:59.000Z

    This patent describes a method for recycling contaminated sulfuric acid from lead acid batteries to reclaimed sulfuric acid for reuse in the batteries by removing contaminating iron impurities. It includes diluting the contaminated sulfuric acid to a concentration between 150 and 230 grams per liter; filtering the sulfuric acid through a first filter means to remove solid impurities; oxidizing the sulfuric acid to assure that the iron contaminants are substantially in a ferric form; removing the iron contaminants from the sulfuric acid through liquid-liquid extracting using an extraction agent comprising mixture of a mono- or di-alkyl phosphoric acid and a metal chelation collector selected from the group consisting of a 8- hydroxyquinoline substituted in the No. 7 position with a long chain aliphatic hydrocarbon radical and an oil-soluble 2-hydroxy benzophenoneoxime, a modifier which maintains solubility of the phosphoric acid and the metal chelation collector and enhances phase disengagement, and a water immiscible carrier, the molar ratio of the 8-hydroxyquinoline and the phosphoric acid being between 1:1::1:4, respectively; wherein the ratio of extraction agent to water immiscible carrier is greater than 10:90; the extraction performed at a volumetric ratio between 4:1::1:4, and repeated until the contaminating iron impurities are substantially reduced.

  8. BIOTIGER, A NATURAL MICROBIAL PRODUCT FOR ENHANCED HYDROCARBON RECOVERY FROM OIL SANDS.

    SciTech Connect (OSTI)

    Brigmon, R; Topher Berry, T; Whitney Jones, W; Charles Milliken, C

    2008-05-27T23:59:59.000Z

    BioTiger{trademark} is a unique microbial consortia that resulted from over 8 years of extensive microbiology screening and characterization of samples collected from a century-old Polish waste lagoon. BioTiger{trademark} shows rapid and complete degradation of aliphatic and aromatic hydrocarbons, produces novel surfactants, is tolerant of both chemical and metal toxicity and shows good activity at temperature and pH extremes. Although originally developed and used by the U.S. Department of Energy for bioremediation of oil-contaminated soils, recent efforts have proven that BioTiger{trademark} can also be used to increase hydrocarbon recovery from oil sands. This enhanced ex situ oil recovery process utilizes BioTiger{trademark} to optimize bitumen separation. A floatation test protocol with oil sands from Ft. McMurray, Canada was used for the BioTiger{trademark} evaluation. A comparison of hot water extraction/floatation test of the oil sands performed with BioTiger{trademark} demonstrated a 50% improvement in separation as measured by gravimetric analysis in 4 h and a five-fold increase at 25 hr. Since BioTiger{trademark} performs well at high temperatures and process engineering can enhance and sustain metabolic activity, it can be applied to enhance recovery of hydrocarbons from oil sands or other complex recalcitrant matrices.

  9. Improved resolution of hydrocarbon structures and constitutional isomers in complex mixtures using Gas Chromatography-Vacuum Ultraviolet-Mass Spectrometry (GC-VUV-MS)

    SciTech Connect (OSTI)

    Aerosol Dynamics Inc; Aerodyne Research, Inc.,; Tofwerk AG, Thun; Isaacman, Gabriel; Wilson, Kevin R.; Chan, Arthur W. H.; Worton, David R.; Kimmel, Joel R.; Nah, Theodora; Hohaus, Thorsten; Gonin, Marc; Kroll, Jesse H.; Worsnop, Doug R.; Goldstein, Allen H.

    2011-09-13T23:59:59.000Z

    Understanding the composition of complex hydrocarbon mixtures is important for environmental studies in a variety of fields, but many prevalent compounds cannot be confidently identified using traditional gas chromatography-mass spectrometry (GC-MS) techniques. This work uses vacuum-ultraviolet (VUV) ionization to elucidate the structures of a traditionally"unresolved complex mixture" by separating components by GC retention time, tR, and mass-to-charge ratio, m/Q, which are used to determine carbon number, NC, and the number of rings and double bonds, NDBE. Constitutional isomers are resolved based on tR, enabling the most complete quantitative analysis to date of structural isomers in an environmentally-relevant hydrocarbon mixture. Unknown compounds are classified in this work by carbon number, degree of saturation, presence of rings, and degree of branching, providing structural constraints. The capabilities of this analysis are explored using diesel fuel, in which constitutional isomer distribution patterns are shown to be reproducible between carbon numbers and follow predictable rules. Nearly half of the aliphatic hydrocarbon mass is shown to be branched, suggesting branching is more important in diesel fuel than previously shown. The classification of unknown hydrocarbons and the resolution of constitutional isomers significantly improves resolution capabilities for any complex hydrocarbon mixture.

  10. Chlorine isotope investigation of natural attenuation of trichloroethene in an aerobic aquifer

    SciTech Connect (OSTI)

    Sturchio, N.C.; Heraty, L.J.; Huang, L.; Holt, B.D.; Abrajano, T.A. Jr. [Argonne National Lab., IL (United States)] [Argonne National Lab., IL (United States); Clausen, J.L. [Lockheed-Martin Energy Services, Inc., Kevil, KY (United States)] [Lockheed-Martin Energy Services, Inc., Kevil, KY (United States)

    1998-10-15T23:59:59.000Z

    Natural attenuation of chlorinated aliphatic hydrocarbons (CAHs) can be an important mechanism for groundwater remediation. It is difficult to determine the effectiveness of natural CAH attenuation from chemical analyses of groundwater samples because mixing, dispersion, and secondary reactions can mask the chemical evidence of attenuation. In this paper, the authors explore the application of stable chlorine isotope ratio measurements as a new tool for evaluating natural attenuation of CAHs. They report stable isotope ratios of chlorine in both trichloroethene (TCE) and inorganic chloride in groundwater from an aerobic aquifer beneath an extensively contaminated industrial site, the Paducah Gaseous Diffusion Plant in western Kentucky. Variations in the concentrations and chlorine isotope ratios of TCE and chloride in the groundwater are consistent with those expected from natural attenuation. These data support a model in which partial TCE degradation occurred in relatively impermeable, clay-rich sediments above the aquifer, and little or no further degradation of TCE occurred within the aquifer. A record of changing conditions within the TCE source area can be inferred from the spatial variation of chlorine isotope ratios for TCE and chloride within the plume.

  11. Mechanisms, Chemistry, and Kinetics of Anaerobic Biodegradation of cis-Dichloroethene and Vinyl Chloride

    SciTech Connect (OSTI)

    McCarty, P.L.; Spormann, A.M.

    2000-12-01T23:59:59.000Z

    Anaerobic biological processes can result in PCE and TCE destruction through conversion to cis-dichloroethene (cDCE) then to vinyl chloride (VC), and finally to ethene. Here, the chlorinated aliphatic hydrocarbons (CAHs) serve as electron acceptors in energy metabolism, requiring electron donors such as hydrogen from an external source. The purpose of this study was to learn more about the biochemistry of cDCE and VC conversion to ethene, to better understand the requirements for electron donors, and to determine factors affecting the rates of CAH degradation and organism growth. The biochemistry of reductive dehalogenation of VC was studied with an anaerobic mixed culture enriched on VC. In other studies on electron donor needs for dehalogenation of cDCE and VC, competition for hydrogen was found to occur between the dehalogenators and other microorganisms such as methanogens and homoacetogens in a benzoate-acclimated dehalogenating methanogenic mixed culture. Factors affecting the relative rates of destruction of the solvents and their intermediate products were evaluated. Studies using a mixed PCE-dehalogenating culture as well as the VC enrichment for biochemical studies suggested that the same species was involved in both cDCE and VC dechlorination, and that cDCE and VC competitively inhibited each other's dechlorination rate.

  12. Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry

    SciTech Connect (OSTI)

    Tao, Shikang; Lu, Xiaohui; Levac, Nicole A.; Bateman, Adam P.; Nguyen, Tran B.; Bones, David L.; Nizkorodov, Sergey; Laskin, Julia; Laskin, Alexander; Yang, Xin

    2014-08-21T23:59:59.000Z

    Aerosol samples collected in the urban areas of Shanghai and Los Angeles were analyzed by nanospray-desorption electrospray ionization mass spectrometry (nano-DESI MS) with high mass resolution (m/?m=100,000). Solvent mixtures of acetonitrile/water and acetonitrile/toluene were used to extract and ionize polar and non-polar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. Majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates in the two samples have distinctly different molecular characteristics. Specifically, organosulfates in the Los Angeles sample were dominated by isoprene- or monoterpene-derived products, while organosulfates of yet unknown origin in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degree of oxidation and unsaturation. The use of acetonitrile/toluene solvent facilitated identification of this type of organosulfates, suggesting they could be missed in previous studies relying on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the organosulfates detected in the Shanghai sample suggest that they may act as surfactants, and plausibly affect the surface tension and hygroscopicity of the atmospheric particulate matter. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in liquid phase could be the formation pathway of these special organosulfates. Long-chain alkanes from vehicle emissions might be their precursors.

  13. Inhalation developmental toxicology studies: Teratology study of acetone in mice and rats: Final report

    SciTech Connect (OSTI)

    Mast, T.J.; Evanoff, J.J.; Rommereim, R.L.; Stoney, K.H.; Weigel, R.J.; Westerberg, R.B.

    1988-11-01T23:59:59.000Z

    Acetone, an aliphatic ketone, is a ubiquitous industrial solvent and chemical intermediate; consequently, the opportunity for human exposure is high. The potential for acetone to cause developmental toxicity was assessed in Sprague-Dawley rats exposed to 0, 440, 2200, or 11000 ppm, and in Swiss (CD-1) mice exposed to 0, 440, 2200, and 6600 ppm acetone vapors, 6 h/day, 7 days/week. Each of the four treatment groups consisted of 10 virgin females (for comparison), and approx.32 positively mated rats or mice. Positively mated mice were exposed on days 6-17 of gestation (dg), and rats on 6-19 dg. The day of plug or sperm detection was designated as 0 dg. Body weights were obtained throughout the study period, and uterine and fetal body weights were obtained at sacrifice (rats, 20 dg; mice, 18 dg). Implants were enumerated and their status recorded. Live fetuses were sexed and examined for gross, visceral, skeletal, and soft-tissue craniofacial defects. 46 refs., 6 figs., 27 tabs.

  14. CHARACTERIZATION AND EVALUATION OF CAUSTIC WASH TANK AND SOLVENT HOLD TANK SAMPLES FROM MCU FROM AUGUST TO SEPTEMBER 2011

    SciTech Connect (OSTI)

    Fondeur, F.; Fink, S.

    2012-08-01T23:59:59.000Z

    During processing of Salt Batches 3 and 4 in the Modular Caustic-Side Solvent Extraction Unit (MCU), the decontamination efficiency for cesium declined from historical values and from expectations based on laboratory testing. This report documents efforts to analyze samples of solvent and process solutions from MCU in an attempt to understand the cause of the reduced performance and to recommend mitigations. CWT Solutions from MCU from the time period of variable decontamination factor (DF) performance which covers from April 2011 to September 2011 (during processing of Salt Batch 4) were examined for impurities using chromatography and spectroscopy. The results indicate that impurities were found to be of two types: aromatic containing impurities most likely from Modifier degradation and aliphatic type impurities most likely from Isopar{reg_sign} L and tri-n-octylamine (TOA) degradation. Caustic washing the Solvent Hold Tank (SHT) solution with 1M NaOH improved its extraction ability as determined from {sup 22}Na uptake tests. Evidence from this work showed that pH variance in the aqueous solutions within the range of 1M nitric acid to 1.91M NaOH that contacted the solvent samples does not influence the analytical determination of the TOA concentration by GC-MS.

  15. Design, construction, operation, and evaluation of solar systems for industrial process-heat applications in the intermediate-temperature range (212/sup 0/F to 550/sup 0/F). Environmental assessment

    SciTech Connect (OSTI)

    none,

    1982-01-01T23:59:59.000Z

    The environmental impacts are assessed for a proposed 50,000 square foot field of single axis tracking, concentrating solar collectors along the Ohio River in southern Ohio. The facility is planned to produce process steam for use in the production of polystyrene. Absorbed solar energy would heat an aliphatic hydrocarbon synthetic heat transfer fluid to a maximum temperature of 500/sup 0/F. The existing environment is briefly described, particularly regarding air quality. The potential environmental impacts of the solar process heat system on the air, water, soil, endangered species and archaeological and historical resources are examined, including risks due to flood and glare and a comparison of alternatives. Also included are a Consent Judgment relating to two coal-fired boilers in violation of EPA regulations, property data of Gulf Synfluid 4CS (a candidate heat transfer fluid), piping and instrumentation diagrams and schematics, site grade and drainage plan, geological survey map, subsurface soil investigation, Ohio endangered species list, Ohio Archaeological Counsel certification list, and a study of heat transfer fluids and their properties. (LEW)

  16. Oxidative derivatization and solubilization of coal. Final report. Period: October 1, 1986 - April 30, 1988

    SciTech Connect (OSTI)

    Schulz, J.G.; Porowski, E.N.; Straub, A.M.

    1988-05-01T23:59:59.000Z

    We investigated the solubilization of coal by oxidative means to produce motor fuels. Nitric acid was used in the first of two approaches taken to cleave aliphatic linkages in coal and reduce the size of its macrostructure. Mild conditions, with temperatures up to a maximum of 75 C, and nitric acid concentrations below 20% by weight, characterize this process. The solid product, obtained in high yields, is soluble in polar organic solvents. Lower alcohols, methanol in particular, are of interest as carrier solvents in diesel fuel applications. Coals investigated were New York State peat, Wyodak subbituminous coal, North Dakota lignite, and Illinois No. 6 bituminous coal. The lower tank coals were easily converted and appear well suited to the process, while the bituminous Illinois No. 6 and Pitt Seam coals were unreactive. We concentrated our efforts on Wyodak coal and North Dakota lignite. Reaction conditions with regards to temperature, acid concentration, and time were optimized to obtain high product selectivity at maximum conversion. A continuous process scheme was developed for single pass coal conversions of about 50% to methanol-soluble product.

  17. Low-temperature pyrolysis of coal to produce diesel-fuel blends

    SciTech Connect (OSTI)

    Shafer, T.B.; Jett, O.J.; Wu, J.S.

    1982-10-01T23:59:59.000Z

    Low-temperature (623 to 773/sup 0/K) coal pyrolysis was investigated in a bench-scale retort. Factorially designed experiments were conducted to determine the effects of temperature, coal-particle size, and nitrogen flow rate on the yield of liquid products. Yield of condensable organic products relative to the proximate coal volatile matter increased by 3.1 and 6.4 wt % after increasing nitrogen purge flow rate from 0.465 to 1.68 L/min and retort temperature from 623 to 723/sup 0/K, respectively. The liquid product may be suitable for blending with diesel fuel. The viscosity and density of coal liquids produced at 723/sup 0/K were compared with those of diesel fuel. The coal liquids had a higher carbon-to-hydrogen ratio and a lower aliphatic-to-aromatic ratio than premium quality No. 2 diesel fuel. It was recommended that liquids from coal pyrolysis be blended with diesel fuel to determine stability of the mixture and performance of the blend in internal combustion engines.

  18. Experimental and modeling investigation of aromatic and polycyclic aromatic hydrocarbon formation in a premixed ethylene flame

    SciTech Connect (OSTI)

    Castaldi, M.J.; Marinov, N.M.; Melius, C.F. [and others

    1996-02-01T23:59:59.000Z

    Experimental and detailed chemical kinetic modeling has been performed to investigate aromatic and polyaromatic hydrocarbon formation pathways in a rich, sooting, ethylene-oxygen-argon premixed flame. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.5 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph/mass spectrometer (GC/MS) technique. Measurements were made in the flame and post-flame zone for a number of low molecular weight species, aliphatics, aromatics and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-aromatic fused rings. The modeling results show the key reaction sequences leading to aromatic and polycyclic aromatic hydrocarbon growth involve the combination of resonantly stabilized radicals. In particular, propargyl and 1-methylallenyl combination reactions lead to benzene and methyl substituted benzene formation, while polycyclic aromatics are formed from cyclopentadienyl radicals and fused rings that have a shared C{sub 5} side structure. Naphthalene production through the reaction step of cyclopentadienyl self-combination and phenanthrene formation from indenyl and cyclopentadienyl combination were shown to be important in the flame modeling study. The removal of phenyl by O{sub 2} leading to cyclopentadienyl formation is expected to play a pivotal role in the PAH or soot precursor growth process under fuel-rich oxidation conditions.

  19. Monsoon-driven vertical fluxes of organic pollutants in the western Arabian Sea

    SciTech Connect (OSTI)

    Dachs, J.; Bayona, J.M.; Ittekkot, V.; Albaiges, J.

    1999-11-15T23:59:59.000Z

    A time series of sinking particles from the western Arabian Sea was analyzed for aliphatic and polycyclic aromatic hydrocarbons, polychlorinated biphenyls, 4,4{prime}-DDT and 4,4{prime}-DDE, to assess the role of monsoons on their vertical flux in the Indian Ocean. Concurrently, molecular markers such as sterols and linear and branched alkanes were analyzed enabling the characterization of the biogenic sources and biogeochemical processes occurring during the sampling period. Hierarchical cluster analysis (HCA) of the data set of concentrations and fluxes of these compounds confirmed a seasonal variability driven by the SW and NE monsoons. Moreover, the influence of different air masses is evidenced by the occurrence of higher concentrations of DDT, PCBs, and pyrolytic PAHs during the NE monsoon and of fossil hydrocarbons during the SW monsoon. Total annual fluxes to the deep Arabian Sea represent an important removal contribution of persistent organic pollutants, thus not being available for the global distillation process (volatilization and atmospheric transport from low or mid latitudes to cold areas). Therefore, monsoons may play a significant role on the global cycle of organic pollutants.

  20. Identification and origin of Delta sup 8(14) 5. alpha. - and. Delta. sup 14 5. alpha. -sterenes and related hydrocarbons in an immature bitumen from the Monterey Formation, California

    SciTech Connect (OSTI)

    Peakman, T.M. (Forschungszentrum Juelich GmbH (Germany)); Leeuw, J.W. de; Rijpstra, W.I.C. (Delft Univ. of Technology (Netherlands))

    1992-03-01T23:59:59.000Z

    The aliphatic hydrocarbon fraction of an immature Monterey bitumen contains a high relative abundance of C{sub 27}-C{sub 29} {Delta}{sup 4}, {Delta}{sup 5}, {Delta}{sup 8(14)} 5{alpha}- and {Delta}{sup 14} 5{alpha}-sterenes, each having a very similar carbon number distribution. This is the first report of abundant {Delta}{sup 8(14)} 5{alpha}- and {Delta}{sup 14} 5{alpha}-sterenes in an immature sediment. The {Delta}{sup 4} and {Delta}{sup 5} sterenes appear to originate directly from {Delta}{sup 5} sterols. For the Delta{sup 8(14)} 5{alpha}-sterenes the authors propose an origin from {Delta}{sup 7} 5{alpha}-sterols which may be derived from a microbial transformation of {Delta}{sup 5} sterols. The presence of 5{alpha}- and 5{beta}-steranes in an unusual ratio of ca. 55:45 suggests the formation of a high abundance of 5{beta}-stanols via the known microbial reduction pathway of {Delta}{sup 5} sterols.

  1. Pollution Prevention Wipe Application Study

    SciTech Connect (OSTI)

    Lopez, E.P.; Modderman, W.E.; Montoya, M.G.

    1999-02-10T23:59:59.000Z

    As part of a pollution prevention program, a study was conducted at Sandia National Laboratories and at the Amarillo, ''Pantex Plant'' to identify a suitable replacement solvent(s) for cleaning hardware during routine maintenance operations. Current cleaning is performed using solvents (e.g. acetone, toluene, MEK, alcohols) that are classified as Resource Conservation and Recovery Act (RCW) materials. The Environmental Protection Agency (EPA) has assigned four characteristics as the criteria for determining whether a material is identified as hazardous under RCRA: Ignitability, Corrosivity, Reactivity and Toxicity. Within the DOE and DoD sector, these solvents are used with hand wipes to clean surfaces prior to O-ring replacement, to remove decals for new labeling, to clean painted surfaces prior to reconditioning, and for other general maintenance purposes. In some cases, low level radioactive contamination during cleaning necessitates that the RCIL4 solvent-containing wipes be classified as mixed waste. To avoid using RCRA materials, cleaning candidates were sought that had a flashpoint greater than 140 F, a pH between 2.5 and 12.5, and did not fail the reactivity and toxicity criteria. Three brominated cleaners, two hydrofluoroether azeotropes and two aliphatic hydrocarbon cleaner formulations were studied as potential replacements. Cleaning efficacy, materials compatibility, corrosion and accelerated aging studies were conducted and used to screen potential candidates. Hypersolve NPB (an n-propyl bromide based formulation) consistently ranked high in removing typical contaminants for weapons applications.

  2. Role of minerals in the thermal alteration of organic matter. IV. Generation of n-alkanes, acyclic isoprenoids, and alkenes in laboratory experiments

    SciTech Connect (OSTI)

    Huizinga, B.J.; Tannenbaum, E.; Kaplan, I.R.

    1987-05-01T23:59:59.000Z

    A series of pyrolysis experiments, utilizing two different immature oil-prone kerogens mixed with common sedimentary minerals (calcite, illite, or Na-montmorillonite), was conducted to study the effects of minerals on the generation of n-alkanes, acyclic isoprenoids, and alkenes during laboratory-simulated catagenesis of kerogen. The influence of clay minerals on the aliphatic hydrocarbons is critically dependent on the water concentration during laboratory thermal maturation. Under extremely low contents of water, C/sub 12+/-range n-alkanes and acyclic isoprenoids are mostly destroyed by montmorillonite but undergo only a minor alteration with illite. Both clay minerals significantly reduce alkene formation during dry pyrolysis. Under hydrous conditions (mineral/water = 2:1), the effects of the clay minerals are substantially reduced. In addition, the dry-pyrolysis experiments show that illite and montmorillonite preferentially retain large amounts of the polar constituents of bitumen, but not n-alkanes of acyclic isoprenoids. Therefore, bitumen fractionation according to polarity differences occurs in the presence of these clay minerals. By this process, n-alkanes, and acyclic isoprenoids are concentrated in the bitumen fraction that is not strongly adsorbed on the clay matrices. In contrast, calcite has no significant influence on the thermal evolution of the hydrocarbons. In addition, calcite is incapable of retaining bitumen. Therefore, the fractionation of n-alkanes or acyclic isoprenoids relative to the polar constituents of bitumen is insignificant in the presence of calcite.

  3. The Molecular Structure of a Phosphatidylserine Bilayer Determined by Scattering and Molecular Dynamics Simulations

    SciTech Connect (OSTI)

    Pan, Jianjun [University of South Florida, Tampa (USF)] [University of South Florida, Tampa (USF); Cheng, Xiaolin [ORNL] [ORNL; Monticelli, Luca [Institut National de la Santé et de la Recherche Médicale (INSERM) and INTS, France] [Institut National de la Santé et de la Recherche Médicale (INSERM) and INTS, France; Heberle, Frederick A [ORNL] [ORNL; Kucerka, Norbert [Atomic Energy of Canada Limited (AECL), Canadian Neutron Beam Centre (CNBC) and Comenius University,] [Atomic Energy of Canada Limited (AECL), Canadian Neutron Beam Centre (CNBC) and Comenius University,; Tieleman, D. Peter [University of Calgary, ALberta, Canada] [University of Calgary, ALberta, Canada; Katsaras, John [ORNL] [ORNL

    2014-01-01T23:59:59.000Z

    Phosphatidylserine (PS) lipids play essential roles in biological processes, including enzyme activation and apoptosis. We report on the molecular structure and atomic scale interactions of a fluid bilayer composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylserine (POPS). A scattering density profile model, aided by molecular dynamics (MD) simulations, was developed to jointly refine different contrast small-angle neutron and X-ray scattering data, which yielded a lipid area of 62.7 A2 at 25 C. MD simulations with POPS lipid area constrained at different values were also performed using all-atom and aliphatic united-atom models. The optimal simulated bilayer was obtained using a model-free comparison approach. Examination of the simulated bilayer, which agrees best with the experimental scattering data, reveals a preferential interaction between Na+ ions and the terminal serine and phosphate moieties. Long-range inter-lipid interactions were identified, primarily between the positively charged ammonium, and the negatively charged carboxylic and phosphate oxygens. The area compressibility modulus KA of the POPS bilayer was derived by quantifying lipid area as a function of surface tension from area-constrained MD simulations. It was found that POPS bilayers possess a much larger KA than that of neutral phosphatidylcholine lipid bilayers. We propose that the unique molecular features of POPS bilayers may play an important role in certain physiological functions.

  4. Metal catalyzed synthesis of hyperbranched ethylene and/or .alpha.-olefin polymers

    DOE Patents [OSTI]

    Sen, Ayusman (State College, PA); Kim, Jang Sub (State College, PA); Pawlow, James H. (Gainesville, FL); Murtuza, Shahid (State College, PA); Kacker, Smita (Annandale, NJ); Wojcinski, III, Louis M. (State College, PA)

    2001-01-01T23:59:59.000Z

    Oily hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin, and a method for their synthesis, are disclosed. The polymers have non-regular microstructures and are characterized by a ratio ({character pullout})of methyl hydrogens centered around 0.85 ppm on the 1H-NMR spectra of the polymers relative to total aliphatic hydrogens of from about 0.40 to about 0.65 for polymers derived from ethylene or butene, and a ratio ({character pullout})of from greater than 0.50 to about 0.65 for polymers derived from propylene. A method for grafting hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin onto aromatic rings in organic molecules and polymers, and the resulting grafted materials, are also disclosed. The hyperbranched polymers and grafted materials are useful, for example, as lubricants and lubricant additives.

  5. Regioselective thermolysis of 1,4-diphenylbutane enhanced by restricted radical mobility

    SciTech Connect (OSTI)

    Britt, P.F.; Buchanan, A.C. III; Biggs, C.A. (Oak Ridge National Lab., TN (USA))

    1989-01-01T23:59:59.000Z

    Thermal decomposition of coal has been postulated to involve the formation of free radicals by processes such as the homolysis of aliphatic or ether-containing bridges which connect polycyclic aromatic units into a macromolecular structure. Understanding the thermal reactivity of coal is important in the study of pyrolysis, liquefaction, and coking. Mechanistic insights into the chemical reactivity of coal at the molecular level can be gained from the study of model compounds which represent structural features in coal. However, radicals generated in a cross-linked macromolecular material such as coal may experience restricted mobility when the radical center remains bound to the residual molecular structure. To model the effects of restricted radical mobility on thermally induced decomposition reactions, thermolyses of model compounds covalently attached to an inert support have been studied. Thermolysis of surface-immobilized 1,2-diphenylethane showed a substantially altered free radical reaction pathway compared with the corresponding liquid phase behavior, while thermolysis of surface-immobilized 1,3-diphenylpropane ({approximately}DPP) showed unexpected regioselectivity resulting from conformational restrictions on hydrogen transfer reactions as the surface coverage of {approximately}DPP decreased. In order to further explore the regionselectivity of hydrogen transfer induced by restricted diffusion, the thermolysis of surface-immobilized 1,4-diphenylbutane ({approximately}DPB) is being examined.

  6. Thermolysis of surface-attached 1,3-diphenylpropane: impact of surface immobilization on thermal reaction mechanisms

    SciTech Connect (OSTI)

    Buchanan, A.C. III; Biggs, C.A.

    1988-01-01T23:59:59.000Z

    Attempts to understand the thermal chemistry of coal at the molecular level are severely complicated by its inherent properties: a diverse array of structural units (e.g., aromatic, hydroaromatic, and heterocyclic aromatic clusters connected by short aliphatic and ether links) and functional groups (e.g., phenolic hydroxyls, carboxyls, and basic nitrogens) in a cross-linked macromolecular framework with no repeating units. One simplifying experimental approach has been the study of individual model compounds that highlight structural features in coal. We are studying the thermolysis of model compounds that are immobilized by covalent attachment to an inert surface. Previous studies of surface-immobilized bibenzyl (1,2-diphenylethane) showed that immobilization can profoundly alter free-radical reaction pathways compared with the corresponding fluid phase behavior. In particular, free-radical chain pathways became dominant decay routes leading to rearrangement, cyclization, and hydrogenolysis of the bibenzyl groups. In this paper we describe preliminary results on the effects of surface immobilization on the thermolysis of 1,3-diphenylpropane, whose fluid phase behavior has been extensively investigated.

  7. Role of solid-state interactions in the acid-catalyzed thermolysis of surface-attached diphenylalkanes

    SciTech Connect (OSTI)

    Buchanan, A.C. III; Britt, P.F.; Biggs, C.A.

    1991-01-01T23:59:59.000Z

    The cross-linked, network structure of coal may impose constraints on conventional reaction mechanisms as a consequence of restricted mass transport. We have examined this phenomenon for thermal reactions through the study of model compounds that are covalently anchored to an inert silica surface (1). We have now initiated studies that employ these immobilized model compounds as solid-state probes in modeling fundamental aspects of catalyzed, heterogeneous reactions of coal. There have been numerous recent reports on the development of unsupported, highly dispersed catalysts for improving the conversion and product selectivity in coal liquefaction (2,3) and hydropyrolysis (4). A potential advantage of such dispersed catalysts is the improved contact between the coal, solvent vehicle if present, hydrogen gas, and the catalyst surface, particularly when catalysts with very small particle sizes can be generated. In this paper, we report initial results from a model system that begins to address the mechanistic question of if, in the early stages of coal dissolution, significant activation of solid coal particles by solid catalyst can occur. For this study, surface-immobilized 1,3-diphenylpropane ({approx}DPP) has been employed as a model for related trimethylene (and longer) aliphatic linking groups between aromatic clusters in coal, and its reactivity in the presence of a dispersed aluminosilicate at 310--375{degree}C has been investigated. 8 refs., 2 figs.

  8. Thermolysis of surface-attached 1,3-diphenylpropane: Impact of surface immobilization on thermal reaction mechanisms

    SciTech Connect (OSTI)

    Buchanan, A.C. III; Biggs, C.A.

    1987-01-01T23:59:59.000Z

    Attempts to understand the thermal chemistry of coal at the molecular level are severely complicated by its inherent properties: a diverse array of structural units (e.g., aromatic, hydroaromatic, and heterocyclic aromatic clusters connected by short aliphatic and ether links) and functional groups (e.g., phenolic hydroxyls, carboxyls, and basic nitrogens) in a cross-linked macromolecular framework with no repeating units. One simplifying experimental approach has been the study of individual model compounds that highlight structural features in coal. A complicating feature in the interpretive extrapolation of model compound behavior to coal is the possible modifications in free-radical reactivity patterns resulting from restricted translational mobility in the coal where breaking one bond in the macromolecular structure will result in radical centers that are still attached to the residual framework. We are modeling this phenomenon by studying the thermolysis of model compounds that are immobilized by covalent attachment to an inert surface. Previous studies of surface-immobilized bibenzyl (1,2-diphenylethane) showed that immobilization can profoundly alter free-radical reaction pathways compared with the corresponding fluid phase behavior. In particular, free-radical chain pathways became dominant decay routes leading to rearrangement, cyclization, and hydrogenolysis of the bibenzyl groups. In this paper we describe preliminary results on the effects of surface immobilization on the thermolysis of 1,3-diphenylpropane, whose fluid phase behavior has been extensively investigated. 9 refs., 1 fig.

  9. Yellow phosphorus process to convert toxic chemicals to non-toxic products

    DOE Patents [OSTI]

    Chang, S.G.

    1994-07-26T23:59:59.000Z

    The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O[sub 3], PO, PO[sub 2], etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like. 20 figs.

  10. Molecular and crystal structures of p-heptyloxyphenyl p-hexyloxybenzoate and p-butyloxyphenyl p-heptyloxybenzoate: Mesophase design

    SciTech Connect (OSTI)

    Kuz'mina, L. G., E-mail: kuzmina@igic.ras.ru; Gunina, M. A.; Churakov, A. V. [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation)] [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation); Pestov, S. M. [Lomonosov University of Fine Chemical Technology (Russian Federation)] [Lomonosov University of Fine Chemical Technology (Russian Federation)

    2013-03-15T23:59:59.000Z

    Two aromatic esters with the formulas C{sub 6}H{sub 13}-O-C{sub 6}H{sub 4}-C(O)O-C{sub 6}H{sub 4}-O-C{sub 7}H{sub 15} (1) and C{sub 7}H{sub 15}-O-C{sub 6}H{sub 4}-C(O)O-C{sub 6}H{sub 4}-O-C{sub 4}H{sub 9} (2) belonging to nematic liquid-crystal compounds were studied by X-ray diffraction. Compound 1 crystallizes in two modifications: monoclinic (1-m) and triclinic (1-tr). The crystal packing of 1 and 2 is built from alternating loosely packed aliphatic regions and closely packed aromatic regions. In crystal structures 1-m and 2, the aromatic regions are linked into chains by hydrogen bonds with the participation of the carbonyl oxygen atom of the ester group and the C-H fragment of the benzene ring, but these hydrogen bonds in 1-m are much weaker than in 2. In 1-m there are {pi}-stacking interactions between the molecules, resulting in the formation of centrosymmetric dimers with an interplanar distance of 3.45 A. In 1-tr, the aromatic fragments form a herringbone packing motif favorable for a two-dimensional network of directional C-H...{pi}-system interactions.

  11. Process for hydrocracking carbonaceous material in liquid carrier

    DOE Patents [OSTI]

    Duncan, Dennis A. (Downers Grove, IL)

    1980-01-01T23:59:59.000Z

    Solid carbonaceous material is hydrocracked to provide aliphatic and aromatic hydrocarbons for use as gaseous and liquid fuels or chemical feed stock. Particulate carbonaceous material such as coal in slurry with recycled product oil is preheated in liquid state to a temperature of 600.degree.-1200.degree. F. in the presence of hydrogen gas. The product oil acts as a sorbing agent for the agglomerating bitumins to minimize caking within the process. In the hydrocracking reactor, the slurry of oil and carbonaceous particles is heated within a tubular passageway to vaporize the oil and form a gas-solid mixture which is further heated to a hydropyrolysis temperature in excess of 1200.degree. F. The gas-solid mixture is quenched by contact with additional oil to condense normally liquid hydrocarbons for separation from the gases. A fraction of the hydrocarbon liquid product is recycled for quenching and slurrying with the carbonaceous feed. Hydrogen is recovered from the gas for recycle and additional hydrogen is produced by gasification of residual char.

  12. Electron localization in liquid acetonitrile.

    SciTech Connect (OSTI)

    Shkrob, I. A.; Sauer, M. C.; Chemistry

    2002-10-03T23:59:59.000Z

    Time-resolved one- and two-pulse laser dc photoconductivity has been used to observe two kinds of reducing species, anion-1 and anion-2, in liquid acetonitrile. At 25 C, the standard enthalpy of conversion from anion-1 to anion-2 is -44.3 {+-} 3.6 kJ/mol and the conversion time is 3 ns. The high-temperature form, anion-1, absorbs in the IR and migrates >3.3 times faster than any other ion in acetonitrile. This rapid migration has a low activation energy of 3.2 kJ/mol (vs 7.6 kJ/mol for other ions). Anion-1 rapidly transfers the electron to acceptors with high electron affinity, with rate constant up to 10{sup 11} M{sup -1} s{sup -1}. The low-temperature form, anion-2, absorbs in the visible and exhibits normal mobility and electron-transfer rates, ca. 1.5 x 10{sup 10} M{sup -1} s{sup -1}. It reacts, by proton transfer, with two hydrogen-bonded molecules of water and/or aliphatic alcohols. Laser photoexcitation of these two solvent anions in their respective absorption bands leads to the formation of CH{sub 3} and CN{sup -}. We present arguments indicating that anion-2 is a dimer radical anion of acetonitrile, whereas anion-1 is a multimer radical anion that may be regarded as a 'solvated electron'.

  13. Non-Ideal Behavior in Solvent Extraction

    SciTech Connect (OSTI)

    Peter Zalupski

    2011-09-01T23:59:59.000Z

    This report presents a summary of the work performed to meet FCR&D level 3 milestone M31SW050801, 'Complete the year-end report summarizing FY11 experimental and modeling activities.' This work was carried out under the auspices of the Non-Ideality in Solvent Extraction Systems FCR&D work package. The report summarizes our initial considerations of potential influences that non-ideal chemistry may impose on computational prediction of outcomes in solvent extraction systems. The report is packaged into three separate test cases where a robustness of the prediction by SXFIT program is under scrutiny. The computational exercises presented here emphasize the importance of accurate representation of both an aqueous and organic mixtures when modeling liquid-liquid distribution systems. Case No.1 demonstrates that non-ideal behavior of HDEHP in aliphatic diluents, such as n-dodecane, interferes with the computation. Cases No.2 and No.3 focus on the chemical complexity of aqueous electrolyte mixtures. Both exercises stress the need for an improved thermodynamic model of an aqueous environment present in the europium distribution experiments. Our efforts for year 2 of this project will focus on the improvements of aqueous and non-aqueous solution models using fundamental physical properties of mixtures acquired experimentally in our laboratories.

  14. The Role of a Dipeptide Outer-Coordination Sphere on H2 -Production Catalysts: Influence on Catalytic Rates and Electron Transfer

    SciTech Connect (OSTI)

    Reback, Matthew L.; Ginovska-Pangovska, Bojana; Ho, Ming-Hsun; Jain, Avijita; Squier, Thomas C.; Raugei, Simone; Roberts, John A.; Shaw, Wendy J.

    2013-02-04T23:59:59.000Z

    The outer-coordination sphere of enzymes acts to fine-tune the active site reactivity and control catalytic rates, suggesting that incorporation of analogous structural elements into molecular catalysts may be necessary to achieve rates comparable to those observed in enzyme systems at low overpotentials. In this work, we evaluate the effect of an amino acid and dipeptide outer-coordination sphere on [Ni(PPh2NPh-R2)2]2+ hydrogen production catalysts. A series of 12 new complexes containing non-natural amino acids or dipeptides were prepared to test the effects of positioning, size, polarity and aromaticity on catalytic activity. The non-natural amino acid was either 3-(meta- or para-aminophenyl)propionic acid terminated as an acid, an ester or an amide. Dipeptides consisted of one of the non-natural amino acids coupled to one of four amino acid esters: alanine, serine, phenylalanine or tyrosine. All of the catalysts are active for hydrogen production, with rates averaging ~1000 s-1, 40% faster than the unmodified catalyst. Structure and polarity of the aliphatic or aromatic side chains of the C-terminal peptide do not strongly influence rates. However, the presence of an amide bond increases rates, suggesting a role for the amide in assisting catalysis. Overpotentials were lower with substituents at the N-phenyl meta position. This is consistent with slower electron transfer in the less compact, para-substituted complexes, as shown in digital simulations of catalyst cyclic voltammograms and computational modeling of the complexes. Combining the current results with insights from previous results, we propose a mechanism for the role of the amino acid and dipeptide based outer-coordination sphere in molecular hydrogen production catalysts.

  15. Pyrolysis of waste tyres: A review

    SciTech Connect (OSTI)

    Williams, Paul T., E-mail: p.t.williams@leeds.ac.uk

    2013-08-15T23:59:59.000Z

    Graphical abstract: - Highlights: • Pyrolysis of waste tyres produces oil, gas and char, and recovered steel. • Batch, screw kiln, rotary kiln, vacuum and fluidised-bed are main reactor types. • Product yields are influenced by reactor type, temperature and heating rate. • Pyrolysis oils are complex and can be used as chemical feedstock or fuel. • Research into higher value products from the tyre pyrolysis process is reviewed. - Abstract: Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H{sub 2}, C{sub 1}–C{sub 4} hydrocarbons, CO{sub 2}, CO and H{sub 2}S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.

  16. Fission product solvent extraction

    SciTech Connect (OSTI)

    Moyer, B.A.; Bonnesen, P.V.; Sachleben, R.A. [and others

    1998-02-01T23:59:59.000Z

    Two main objectives concerning removal of fission products from high-level tank wastes will be accomplished in this project. The first objective entails the development of an acid-side Cs solvent-extraction (SX) process applicable to remediation of the sodium-bearing waste (SBW) and dissolved calcine waste (DCW) at INEEL. The second objective is to develop alkaline-side SX processes for the combined removal of Tc, Cs, and possibly Sr and for individual separation of Tc (alone or together with Sr) and Cs. These alkaline-side processes apply to tank wastes stored at Hanford, Savannah River, and Oak Ridge. This work exploits the useful properties of crown ethers and calixarenes and has shown that such compounds may be economically adapted to practical processing conditions. Potential benefits for both acid- and alkaline-side processing include order-of-magnitude concentration factors, high rejection of bulk sodium and potassium salts, and stripping with dilute (typically 10 mM) nitric acid. These benefits minimize the subsequent burden on the very expensive vitrification and storage of the high-activity waste. In the case of the SRTALK process for Tc extraction as pertechnetate anion from alkaline waste, such benefits have now been proven at the scale of a 12-stage flowsheet tested in 2-cm centrifugal contactors with a Hanford supernatant waste simulant. SRTALK employs a crown ether in a TBP-modified aliphatic kerosene diluent, is economically competitive with other applicable separation processes being considered, and has been successfully tested in batch extraction of actual Hanford double-shell slurry feed (DSSF).

  17. Carbon-Type Analysis and Comparison of Original and Reblended FACE Diesel Fuels (FACE 2, FACE 4, and FACE 7)

    SciTech Connect (OSTI)

    Bays, J. Timothy; King, David L.; O'Hagan, Molly J.

    2012-10-01T23:59:59.000Z

    This report summarizes the carbon-type analysis from 1H and 13C{1H} nuclear magnetic resonance spectroscopy (NMR) of Fuels for Advanced Combustion Engines (FACE) diesel blends, FD-2B, FD 4B, and FD-7B, and makes comparison of the new blends with the original FACE diesel blends, FD 2A, FD 4A, and FD-7A, respectively. Generally, FD-2A and FD-2B are more similar than the A and B blends of FD-4 and FD-7. The aromatic carbon content is roughly equivalent, although the new FACE blends have decreased monoaromatic content and increased di- and tri-cycloaromatic content, as well as a higher overall aromatic content, than the original FACE blends. The aromatic components of the new FACE blends generally have a higher alkyl substitution with longer alkyl substituents. The naphthenic and paraffinic contents remained relatively consistent. Based on aliphatic methyl and methylene carbon ratios, cetane numbers for FD-2A and -2B, and FD-7A and -7B are predicted to be consistent, while the cetane number for FD-4B is predicted to be higher than FD-4A. Overall, the new FACE fuel blends are fairly consistent with the original FACE fuel blends, but there are observable differences. In addition to providing important comparative compositional information on reformulated FACE diesel blends, this report also provides important information about the capabilities of the team at Pacific Northwest National Laboratory in the use of NMR spectroscopy for the detailed characterization and comparison of fuels and fuel blends.

  18. New organically templated photoluminescence iodocuprates(I)

    SciTech Connect (OSTI)

    Hou Qin [College of Chemistry and Material Science, Shandong Agricultural University, Taian, Shandong 271018 (China); Zhao Jinjing [College of Chemistry, Jilin University, Changchun 130023 (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023 (China); Zhao Tianqi [College of Chemistry, Jilin University, Changchun 130023 (China); Jin Juan [College of Chemistry, Jilin University, Changchun 130023 (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023 (China); Yu Jiehui, E-mail: jiehuiyu@yahoo.com.cn [College of Chemistry, Jilin University, Changchun 130023 (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023 (China); Xu Jiqing, E-mail: xjq@mail.jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130023 (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023 (China)

    2011-07-15T23:59:59.000Z

    Two types of organic cyclic aliphatic diamine molecules piperazine (pip) and 1,3-bis(4-piperidyl)propane (bpp) were used, respectively, to react with an inorganic mixture of CuI and KI in the acidic CH{sub 3}OH solutions under the solvothermal conditions, generating finally three new organically templated iodocuprates as 2-D layered [(Hpip)Cu{sub 3}I{sub 4}] 1, 1-D chained [tmpip][Cu{sub 2}I{sub 4}] 2 (tmpip=N,N,N',N'-tetramethylpiperazinium) and dinuclear [H{sub 2}bpp]{sub 2}[Cu{sub 2}I{sub 5}] I.2H{sub 2}O 3. Note that the templating agent tmpip{sup 2+} in compound 2 originated from the in situ N-alkylation reaction between the pip molecule and the methanol solvent. The photoluminescence analysis indicates that the title compounds emit the different lights: yellow for 1, blue for 2 and yellow-green for 3, respectively. - Graphical abstract: The solvothermal self-assemblies of CuI, KI and pip/bpp in acidic CH{sub 3}OH solutions created three iodocuprates 2-D layered [(Hpip)Cu{sub 3}I{sub 4}] 1, 1-D chained [tmpip][Cu{sub 2}I{sub 4}] 2 and dinuclear [H{sub 2}bpp]{sub 2}[Cu{sub 2}I{sub 5}] I.2H{sub 2}O 3. Highlights: > A new layered iodocuprate(I) with 20-membered rings was hydrothermally prepared. > A simple approach to prepare the new organic templating agent was reported. > Photoluminescence analysis indicates the emission for iodocuprate(I) is associated with the Cu...Cu interactions.

  19. Hydrocarbon-bearing fluid inclusions in fluorite associated with the Windy Knoll bitumen deposit, UK

    SciTech Connect (OSTI)

    Moser, M.R. (Imperial College, London (United Kingdom) University College, London (United Kingdom)); Rankin, A.H. (Imperial College, London (United Kingdom)); Milledge, H.J. (University College, London (United Kingdom))

    1992-01-01T23:59:59.000Z

    Hydrocarbon-bearing fluid inclusions in fluorite, associated with an outcropping bitumen deposit at Windy Knoll, Derbyshire, have been analyzed in situ using a combination of microthermometry, Fourier transform infrared (FTIR) microspectrometry, and ultraviolet (UV) microscopy. The inclusions in these samples can be considered as a series with two end members: aqueous inclusions containing a low-density vapor phase and inclusions containing liquid oil' with no detectable aqueous phase. The majority of the inclusions are mixed types containing both aqueous and liquid hydrocarbon phases. Although microthermometry distinguishes at least two different aqueous fluids with varying homogenization temperatures and salinities, the oil fraction is cogenetic and trapped together with just one fluid, a low-salinity, low-calcium brine with an average homogenization temperature of 134C. The majority of the liquid hydrocarbon-bearing inclusions fluoresce bright blue under UV illumination with peaks around 475 nm, characteristic of paraffinic oils. The FTIR spectra of these inclusions are dominated by peaks assigned to aliphatic C-H bonding. However, inclusions have also been found which display a fluorescence typical of the red-shift associated with less mature oils. The FTIR spectra display peaks assigned to C{double bond}O, C-O, and O-CH{sub 2} bonding. This study presents new data on the in-situ analysis of hydrocarbon-bearing fluid inclusion from this important area of natural petroleum seepage and ore mineralization. The results suggest a direct link between the fluid inclusion populations, the outcropping bitumens, and fluorite deposition.

  20. Solid state 13C NMR analysis of shales and coals from Laramide Basins. Final report, March 1, 1995--March 31, 1996

    SciTech Connect (OSTI)

    Miknis, F.P.; Jiao, Z.S.; Zhao, Hanqing; Surdam, R.C.

    1998-12-31T23:59:59.000Z

    This Western Research Institute (WRI) jointly sponsored research (JSR) project augmented and complemented research conducted by the University of Wyoming Institute For Energy Research for the Gas Research Institute. The project, {open_quotes}A New Innovative Exploitation Strategy for Gas Accumulations Within Pressure Compartments,{close_quotes} was a continuation of a project funded by the GRI Pressure Compartmentalization Program that began in 1990. That project, {open_quotes}Analysis of Pressure Chambers and Seals in the Powder River Basin, Wyoming and Montana,{close_quotes} characterized a new class of hydrocarbon traps, the discovery of which can provide an impetus to revitalize the domestic petroleum industry. In support of the UW Institute For Energy Research`s program on pressure compartmentalization, solid-state {sup 13}C NMR measurements were made on sets of shales and coals from different Laramide basins in North America. NMR measurements were made on samples taken from different formations and depths of burial in the Alberta, Bighorn, Denver, San Juan, Washakie, and Wind River basins. The carbon aromaticity determined by NMR was shown to increase with depth of burial and increased maturation. In general, the NMR data were in agreement with other maturational indicators, such as vitrinite reflectance, illite/smectite ratio, and production indices. NMR measurements were also obtained on residues from hydrous pyrolysis experiments on Almond and Lance Formation coals from the Washakie Basin. These data were used in conjunction with mass and elemental balance data to obtain information about the extent of carbon aromatization that occurs during artificial maturation. The data indicated that 41 and 50% of the original aliphatic carbon in the Almond and Lance coals, respectively, aromatized during hydrous pyrolysis.

  1. Influence of pressure on coal pyrolysis and char gasification

    SciTech Connect (OSTI)

    Haiping Yang; Hanping Chen; Fudong Ju; Rong Yan; Shihong Zhang [Huazhong University of Science and Technology, Wuhan (China). State Key Laboratory of Coal Combustion

    2007-12-15T23:59:59.000Z

    Coal char structure varied greatly with pyrolysis pressure, which has a significant influence on the gasification reactivity. In this study, the influence of pressure on the behavior of coal pyrolysis and physicochemical structure and gasification characteristics of the resultant coal char was investigated using a pressurized thermogravimetric analyzer combined with an ambient thermogravimetric analyzer. First, the pyrolysis of Shenfu (SF) bituminous coal was performed in a pressurized thermogravimetric analyzer (TGA) at different pressures (0.1, 0.8, 1.5, 3, and 5 MPa). The volatile mainly evolved out at 400-800{sup o}C. The gas products are mainly CO{sub 2}, CO, CH{sub 4}, and light aliphatics with some water. It was observed that the pyrolysis of coal was shifted to lower temperature (50{sup o}C) with pressure increasing from ambient to 5 MPa, and the devolatilization rate of coal pyrolysis was decreased and the coal char yield was increased slightly. The structure of solid coal char was analyzed using FTIR, ASAP2020, and CNHS. In the solid char, the main organic functional groups are mainly CO, C-C (alkane), C-H ar, C-O-C, and C=C ar. The carbon content was increased while H content decreased. Finally, the gasification of the solid char was preformed at ambient pressure with CO{sub 2} as gasify agent. The gasification process of coal char can be divided into postpyrolysis and char gasification. Higher pressure accelerated the initial stage of char gasification, and higher gasification reactivity was observed for char derived at 5 MPa. 23 refs., 8 figs., 5 tabs.

  2. Behavior of sulfur and chlorine in coal during combustion and boiler corrosion. [Quarterly] technical report, March 1, 1992--May 31, 1992

    SciTech Connect (OSTI)

    Chou, C.L.; Hackley, K.C.; Donnals, G.L.; Cao, J.; Ruch, R.R. [Illinois State Geological Survey, Champaign, IL (United States); Pan, W.P.; Shao, D. [Western Kentucky Univ., Bowling Green, KY (United States)

    1992-10-01T23:59:59.000Z

    Four replicate experiments of pyrolysis with quadrupole gas analyzer and ion selective electrode were conducted to monitor the release of chlorine and sulfur from a high-chlorine Illinois coal IBC-109 (0.42% chlorine on dry basis). The chlorine in coal is released solely as HCl, and the HCl release profile shows a broad peak between 250{degree}C and 600{degree}C with a maximum at 445{degree}C. In contrast, the sulfur release profile shows three peaks; the sulfur released around 370{degree}C may be derived from a labile (possibly aliphatic) component of organic sulfur, the main peak at 475{degree}C corresponds to the release of the main component (thiophenic) of organic sulfur, and the third peak at 600{degree} results from the decomposition of pyrite. Sulfur dioxide (SO{sub 2}) is the major sulfur species under an oxidizing condition in the combustion gas; additional gaseous sulfur species (COS and H{sub 2}S) are observed when the atmosphere is changed to a reducing condition. Sodium and chlorine contents in char residues determined by neutron activation analysis showed that 98% of chlorine in coal was volatilized during pyrolysis to 800{degree}C, and all the sodium is retained in the chars. The thermogravimetry-Fourier transform infrared (FTIR) spectroscopy experiments were carried out to characterize gaseous species during pyrolysis of four Illinois coals (IBC-103, -105, -106, and -109). Gas evolution profiles of sulfur (H{sub 2}S, S0{sub 2}, and COS), chlorine (HCl), and nitrogen (NH{sub 3} and HCN) species were determined. Similar release profiles of HCl and NH{sub 3} supported an interpretation that chlorine and nitrogen are closely associated in coal. COS may be formed by reaction of CO with H{sub 2}S in the gas phase.

  3. PCB extraction from ORNL tank WC-14 using a unique solvent

    SciTech Connect (OSTI)

    Bloom, G.A.; Lucero, A.J.; Koran, L.J.; Turner, E.N.

    1995-09-01T23:59:59.000Z

    This report summarizes the development work of the Engineering Development Section of the Chemical Technology Division at Oak Ridge National Laboratory (ORNL) for an organic extraction method for removing polychlorinated biphenyls (PCBs) from tank WC-14. Tank WC-14 is part of the ORNL liquid low-level radioactive tank waste system and does not meet new secondary containment and leak detection regulations. These regulations require the tank to be taken out of service, and remediated before tank removal. To remediate the tank, the PCBs must be removed; the tank contents can then be transferred to the Melton Valley Storage Tanks before final disposal. The solvent being used for the PCB extraction experiments is triethylamine, an aliphatic amine that is soluble in water below 60{degrees}F but insoluble in water above 90{degrees}F. This property will allow the extraction to be carried out under fully miscible conditions within the tank; then, after tank conditions have been changed, the solvent will not be miscible with water and phase separation will occur. Phase separation between sludge, water, and solvent will allow solvent (loaded with PCBs) to be removed from the tank for disposal. After removing the PCBs from the sludge and removing the sludge from the tank, administrative control of the tank can be transferred to ORNL`s Environmental Restoration Program, where priorities will be set for tank removal. Experiments with WC-14 sludge show that greater than 90% extraction efficiencies can be achieved with one extraction stage and that PCB concentration in the sludge can be reduced to below 2 ppm in three extractions. It is anticipated that three extractions will be necessary to reduce the PCB concentration to below 2 ppm during field applications. The experiments conducted with tank WC-14 sludge transferred less than 0.03% of the original alpha contamination and less than 0.002% of the original beta contamination.

  4. Solvent extraction of thorium(IV), uranium(VI), and europium(III) with lipophilic alkyl-substituted pyridinium salts. Final report for subcontract 9-XZ2-1123E-1, June 1, 1992--December 1, 1995

    SciTech Connect (OSTI)

    Ensor, D.D.

    1997-01-01T23:59:59.000Z

    In the treatment of high level nuclear wastes, aromatic pyridinium salts which are radiation-resistant are desired for the extraction of actinides and lanthanides. The solvent extraction of Th{sup +4}, UO{sub 2}{sup +2}, and Eu{sup +3} by three aromatic extractants, 3,5-didodecylpyridinium nitrate (35PY), 2,6-didodecylpyridinium nitrate (26PY), and 1-methyl-3,5-didodecyl-pyridinium iodide (1M35PY) has been studied in nitric acid media. The general order of extractability of the three extractants in toluene was 1M35PY>> 26PY > 35PY. The overall extraction efficiency of the metal ions was Th{sup +4} >UO{sub 2}{sup +2} > Eu{sup +3}. The extraction of HNO{sub 3}, which was competitive with the extraction of metal ions, was quantitatively investigated by NaOH titration and UV spectrometry. The loading capacity suggested that the extracted species in the organic phase for thorium was (R{sub 4}N{sup +}){sub 2}Th(NO{sub 3}{sup -}){sub 6}, where R{sub 4}N{sup +} denotes 1M35PY. A comparison of 1M35PY to the well-characterized extractant, Aliquat-336, an aliphatic ammonium salt was made. At the same extractant concentration, 1M35PY extracted thorium more efficiently than Aliquat-336 at high acidity. Thorium could be readily stripped with dilute nitric acid from 1M35PY. After irradiation of 0.1M 1M35PY with {sup 60}Co at 40R/min for 48 hours, no change in the extraction efficiency of thorium was observed.

  5. Hydrocarbon biomarkers, thermal maturity, and depositional setting of tasmanite oil shales from Tasmania, Australia

    SciTech Connect (OSTI)

    Revill, A.T.; Volkman, J.K.; O'Leary, T. (CSIRO Division of Oceanography, Tasmania (Australia)); Summons, R.E.; Boreham, C.J. (Australian Geological Survey Organisation, Canberra (Australia)); Banks, M.R.; Denwer, K. (Univ. of Tasmania (Australia))

    1994-09-01T23:59:59.000Z

    This study represents the first geological and organic geochemical investigation of samples of tasmanite oil shale representing different thermal maturities from three separate locations in Tasmania, Australia. The most abundant aliphatic hydrocarbon in the immature oil shale from Latrobe is a C[sub 19] tricyclic alkane, whereas in the more mature samples from Oonah and Douglas River low molecular weight n-alkanes dominate the extractable hydrocarbon distribution. The aromatic hydrocarbons are predominantly derivatives of tricyclic compounds, with 1,2,8-trimethylphenanthrene increasing in relative abundance with increasing maturity. Geological and geochemical evidence suggests that the sediments were deposited in a marine environment of high latitude with associated cold waters and seasonal sea-ice. It is proposed that the organism contributing the bulk of the kerogen, Tasmanites, occupied an environmental niche similar to that of modern sea-ice diatoms and that bloom conditions coupled with physical isolation from atmospheric CO[sub 2] led to the distinctive [open quotes]isotopically heavy[close quotes] [delta][sup 13]C values for the kerogen. [delta][sup 13]C data from modern sea-ice diatoms supports this hypothesis. Isotopic analysis of n-alkanes in the bitumen suggests a multiple source from bacteria and algae. On the other hand, the n-alkanes generated from closed-system pyrolysis of the kerogen are mainly derived from the preserved Tasmanites biopolymer algaenan. The tricyclic compounds (mean -8[per thousand]) both in the bitumen and pyrolysate, have a common precursor. They are consistently enriched in [sup 13]C compared with the kerogen and probably have a different source from the n-alkanes. The identification of a location where the maturity of the tasmanite oil shale approaches the [open quotes]oil window[close quotes] raises the possibility that it may be a viable petroleum source rock.

  6. Evolution of Substrate Specificity within a Diverse Family of [beta/alpha]-Barrel-fold Basic Amino Acid Decarboxylases X-ray Structure Determination of Enzymes with Specificity for L-Arginine and Carboxynorspermidine

    SciTech Connect (OSTI)

    Deng, Xiaoyi; Lee, Jeongmi; Michael, Anthony J.; Tomchick, Diana R.; Goldsmith, Elizabeth J.; Phillips, Margaret A. (Sungkyunkwan); (UTSMC)

    2010-08-26T23:59:59.000Z

    Pyridoxal 5{prime}-phosphate (PLP)-dependent basic amino acid decarboxylases from the {beta}/{alpha}-barrel-fold class (group IV) exist in most organisms and catalyze the decarboxylation of diverse substrates, essential for polyamine and lysine biosynthesis. Herein we describe the first x-ray structure determination of bacterial biosynthetic arginine decarboxylase (ADC) and carboxynorspermidine decarboxylase (CANSDC) to 2.3- and 2.0-{angstrom} resolution, solved as product complexes with agmatine and norspermidine. Despite low overall sequence identity, the monomeric and dimeric structures are similar to other enzymes in the family, with the active sites formed between the {beta}/{alpha}-barrel domain of one subunit and the {beta}-barrel of the other. ADC contains both a unique interdomain insertion (4-helical bundle) and a C-terminal extension (3-helical bundle) and it packs as a tetramer in the asymmetric unit with the insertions forming part of the dimer and tetramer interfaces. Analytical ultracentrifugation studies confirmed that the ADC solution structure is a tetramer. Specificity for different basic amino acids appears to arise primarily from changes in the position of, and amino acid replacements in, a helix in the {beta}-barrel domain we refer to as the 'specificity helix.' Additionally, in CANSDC a key acidic residue that interacts with the distal amino group of other substrates is replaced by Leu{sup 314}, which interacts with the aliphatic portion of norspermidine. Neither product, agmatine in ADC nor norspermidine in CANSDC, form a Schiff base to pyridoxal 5{prime}-phosphate, suggesting that the product complexes may promote product release by slowing the back reaction. These studies provide insight into the structural basis for the evolution of novel function within a common structural-fold.

  7. Manganese Porphyrins Catalyze Selective C-H Bond Halogenations

    SciTech Connect (OSTI)

    Liu, Wei; Groves, John T

    2010-01-01T23:59:59.000Z

    We report a manganese porphyrin mediated aliphatic C?H bond chlorination using sodium hypochlorite as the chlorine source. In the presence of catalytic amounts of phase transfer catalyst and manganese porphyrin Mn(TPP)Cl 1, reaction of sodium hypochlorite with different unactivated alkanes afforded alkyl chlorides as the major products with only trace amounts of oxygenation products. Substrates with strong C?H bonds, such as neopentane (BDE =?100 kcal/mol) can be also chlorinated with moderate yield. Chlorination of a diagnostic substrate, norcarane, afforded rearranged products indicating a long-lived carbon radical intermediate. Moreover, regioselective chlorination was achieved by using a hindered catalyst, Mn(TMP)Cl, 2. Chlorination of trans-decalin with 2 provided 95% selectivity for methylene-chlorinated products as well as a preference for the C2 position. This novel chlorination system was also applied to complex substrates. With 5?-cholestane as the substrate, we observed chlorination only at the C2 and C3 positions in a net 55% yield, corresponding to the least sterically hindered methylene positions in the A-ring. Similarly, chlorination of sclareolide afforded the equatorial C2 chloride in a 42% isolated yield. Regarding the mechanism, reaction of sodium hypochlorite with the Mn{sup III} porphyrin is expected to afford a reactive Mn{sup V}?O complex that abstracts a hydrogen atom from the substrate, resulting in a free alkyl radical and a Mn{sup IV}—OH complex. We suggest that this carbon radical then reacts with a Mn{sup IV}—OCl species, providing the alkyl chloride and regenerating the reactive Mn{sup V}?O complex. The regioselectivity and the preference for CH{sub 2} groups can be attributed to nonbonded interactions between the alkyl groups on the substrates and the aryl groups of the manganese porphyrin. The results are indicative of a bent [Mn{sup v}?O---H---C] geometry due to the C—H approach to the Mn{sup v}?O (d??p?)* frontier orbital.

  8. Hydrotreating Pyrolytic Lignin to Produce a Refinery Feedstock (Poster)

    SciTech Connect (OSTI)

    French, R. J.

    2013-09-01T23:59:59.000Z

    Fast pyrolysis of biomass followed by water separation to produce pyrolytic lignin and hydrotreating of the lignin could be used to produce a stable volatile low-oxygen intermediate liquid. Such a liquid could be converted into a finished motor-fuel in a refinery, taking advantage of the existing infrastructure and economies of scale of refineries. Hydrotreating just the lignin would consume less hydrogen while preserving about half of the energy of the original oil. The aqueous by-products could be reformed to produce the needed hydrogen and would contain much of the unwanted acids and unstable oxygenates. To assess such intermediate liquids, several pyrolytic lignins were prepared by mixing pyrolysis oil with water at 1:1 and 3:1 ratios. The carboxylic acidity in the pyrolytic lignin was reduced to 24 and 10 mg-KOH/g-lignin compared to 81 in the whole oil. These lignins were hydrotreated using Ni-Mo(S)/alumina, Pt/char, or Pd/C(activated) in a semi-batch 1 L stirred autoclave. The oil was stabilized under hydrogen at 150-280 degrees C, then water and light organics were removed by partial depressurization. Hydrodeoxygenation was then performed at 340-400 degrees C. Total pressure was controlled at 70 or 170 bar with hydrogen gas. Organic liquid yields of 39-56% were obtained. For many experiments the organic oxygen content was <7%, acidity was < 7 mg-KOH/g-oil, the volatility was greater than or equal to 94% and, on a carbon basis, the total yield of organic products miscible in hydrocarbons at a 1:10 ratio was over 50%. These properties are probably acceptable to a refinery.The residual liquids left in the reactor at the end of the experiment comprised 60-85% of the organic-phase product while the rest was condensate. 13C-NMR of the residual liquids showed that they were 50-80% aliphatic. 13C-NMR coupled with GC-MS identified phenolic compounds as the main oxygenates in most residual liquids.

  9. Source Signatures of Fine Particulate Matter from Petroleum Refining and Fuel Use

    SciTech Connect (OSTI)

    Gerald P. Huffman; Frank E. Huggins; Naresh Shah; Robert Huggins

    1999-12-31T23:59:59.000Z

    Combustion experiments were carried out on four different residual fuel oils in a 732 kW boiler. Particulate matter (PM) emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 microns in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the <2.5 micron fraction (PM{sub 2.5}) in fact consists of carbonaceous cenospheres and vesicular particles that range up to 10 microns in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As Kedges, and at the Pb L-edge. Deconvolution of the x-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM{sub 2.5} samples than in the >2.5 micron samples (PM{sub 2.5+}). Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agree fairly well with that of NiSO4, while most of the V spectra closely resemble that of vanadyl sulfate (VO{center_dot}SO{sub 4}{center_dot}xH{sub 2}O). The other metals investigated (Fe, Cu, Zn, and Pb) were also present predominantly as sulfates. Arsenic is present as an arsenate (As{sup +5}). X-ray diffraction patterns of the PM{sub 2.5} fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the LOI ranging from 64 to 87 % for the PM{sub 2.5} fraction and from 88 to 97% for the PM{sub 2.5+} fraction. {sup 13}C nuclear magnetic resonance (NMR) analysis indicates that the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.

  10. FY-2011 Status Report for Thermodynamics and Kinetics of Advanced Separations Systems

    SciTech Connect (OSTI)

    Leigh R. Martin; Peter R. Zalupski; Travis S. Grimes

    2011-09-01T23:59:59.000Z

    This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR&D) program during FY 2011 at the INL. On the thermodynamic front, investigations of liquid-liquid distribution of lanthanides at TALSPEAK-related conditions continued in FY11. It has been determined that a classical ion-exchanging phase transfer mechanism, where three HDEHP dimers solvate the metal ion in the organic phase, dominates metal extraction for systems that contain up to 0.1 M free lactate in solution. The correct graphical interpretation of the observed data in those regions relied on incorporating corrections for non-ideal behavior of HDEHP dimer in aliphatic diluents as well as sodium extraction equilibria. When aqueous conditions enter the complex regions of high lactate concentrations, slope analysis is no longer possible. When normalized metal distribution ratios were studied along the increasing concentration of free lactate, a slope of -1 was apparent. Such dependency either indicates aqueous complexing competition from lactate, or, a more likely scenario, a participation of lactate in the extracted metal complex. This finding agrees with our initial assessment of postulated changes in the extraction mechanism as a source of the lactate-mediated loss of extraction efficiency. The observed shape in the lanthanide distribution curve in our studies of TALSPEAK systems was the same for solutions containing no lactate or 2.3 M lactate. As such we may conclude that the mechanism of phase transfer is not altered dramatically and remains similarly sensitive to effective charge density of the metal ion. In addition to these thermodynamics studies, this report also summarizes the first calorimetric determination of heat of extraction of 248Cm in a bi-phasic system. The heat of extraction measured by isothermal titration calorimetry is compared to that determined using van't Hoff calculations. Further investigations on the kinetics of extraction in TALSPEAK with macro quantities of lanthanides present in the initial aqueous phase composition have been performed. These results have been summarized and compared to previous work performed for FCR&D. In addition, the effects of HDEHP concentration in the organic phase on europium extraction have been studied.

  11. Mechanistic, Mutational, and Structural Evaluation of a Taxus Phenylalanine Aminomutase

    SciTech Connect (OSTI)

    Feng, Lei; Wanninayake, Udayanga; Strom, Susan; Geiger, James; Walker, Kevin D. (MSU)

    2014-10-02T23:59:59.000Z

    The structure of a phenylalanine aminomutase (TcPAM) from Taxus canadensis has been determined at 2.4 {angstrom} resolution. The active site of the TcPAM contains the signature 4-methylidene-1H-imidazol-5(4H)-one prosthesis, observed in all catalysts of the class I lyase-like family. This catalyst isomerizes (S)-{alpha}-phenylalanine to the (R)-{beta}-isomer by exchange of the NH{sub 2}/H pair. The stereochemistry of the TcPAM reaction product is opposite of the (S)-{beta}-tyrosine made by the mechanistically related tyrosine aminomutase (SgTAM) from Streptomyces globisporus. Since TcPAM and SgTAM share similar tertiary- and quaternary-structures and have several highly conserved aliphatic residues positioned analogously in their active sites for substrate recognition, the divergent product stereochemistries of these catalysts likely cannot be explained by differences in active site architecture. The active site of the TcPAM structure also is in complex with (E)-cinnamate; the latter functions as both a substrate and an intermediate. To account for the distinct (3R)-{beta}-amino acid stereochemistry catalyzed by TcPAM, the cinnamate skeleton must rotate the C{sub 1}-C{sub {alpha}} and C{sub ipso}-C{sub {beta}} bonds 180{sup o} in the active site prior to exchange and rebinding of the NH{sub 2}/H pair to the cinnamate, an event that is not required for the corresponding acrylate intermediate in the SgTAM reaction. Moreover, the aromatic ring of the intermediate makes only one direct hydrophobic interaction with Leu-104. A L104A mutant of TcPAM demonstrated an 1.5-fold increase in k{sub cat} and a decrease in K{sub M} values for sterically demanding 3'-methyl-{alpha}-phenylalanine and styryl-{alpha}-alanine substrates, compared to the kinetic parameters for TcPAM. These parameters did not change significantly for the mutant with 4'-methyl-{alpha}-phenylalanine compared to those for TcPAM.

  12. Electron localization in solid acetonitrile.

    SciTech Connect (OSTI)

    Shkrob, I. A.; Takeda, K.; Williams, F.; Chemistry; Univ. of Tennessee

    2002-10-03T23:59:59.000Z

    Electron localization in the bulk condensed phases of acetonitrile differs drastically from the corresponding processes that take place in water and aliphatic alcohols. In particular, electron capture following the ionization of liquid and solid acetonitrile yields well-defined radical anions in place of the largely structureless solvated and trapped electrons characteristic of irradiated solutions and rigid glasses. This is remarkable given the many similarities that exist not only between the intrinsic properties of these individual solvent molecules, such as polarity, but also in their cooperative capacity to function as solvents. Here, with the aid of detailed experimental and computational studies, we examine on a fundamental level what gives rise to such a sharp contrast in the behavior of these alkyl cyanides as compared to water and alcohols. EPR and optical spectra, and ab initio calculations on the radical anions are used together with diffraction data for the crystal structures to demonstrate that electron attachment to nitrile molecules in the crystalline state results in a significant bending of the linear CCN moiety. Moreover, in the formation of the dimer anions, which only takes place in certain crystalline phases, it is determined that the intermolecular bonding occurs between the cyanide carbons in an antiparallel arrangement. A staggered structure for the dimer anion in {alpha}-acetonitrile is then suggested, in which there is a nearly coplanar arrangement with the two bent CCN fragments. The resulting structure accounts for the observed EPR parameters, the position of the UV-vis absorption band, and the trends observed in the vibronic progressions for the four H/D isotopomers. The dimer radical anion in a-acetonitrile retains the same orientation and symmetry as that of the preexisting neutral {l_brace}CH{sub 3}CN{r_brace}{sub 2} pairs in this crystal despite the resulting changes in molecular geometry and in the translational coordinates for the cyanide carbons as the two acetonitrile molecules come together. We suggest that dimer anions of nitriles can form only in the phases where such 'antiparallel' pairs occur, including liquid systems; otherwise, the electron remains attached to a single molecule, as in {beta}-acetonitrile. Because electron capture by water or alcohol molecules in the condensed phase appears to require larger molecular clusters, the contrast between the behavior of these solvents and acetonitrile is attributable to the relative ease with which acetonitrile molecules in the crystal or solvent can undergo valence-electron attachment via their accessible low-lying {pi}* orbitals.

  13. SUBTASK 3.11 – PRODUCTION OF CBTL-BASED JET FUELS FROM BIOMASS-BASED FEEDSTOCKS AND MONTANA COAL

    SciTech Connect (OSTI)

    Sharma, Ramesh

    2014-06-01T23:59:59.000Z

    The Energy & Environmental Research Center (EERC), in partnership with the U.S. Department of Energy (DOE) and Accelergy Corporation, an advanced fuels developer with technologies exclusively licensed from Exxon Mobil, undertook Subtask 3.11 to use a recently installed bench-scale direct coal liquefaction (DCL) system capable of converting 45 pounds/hour of pulverized, dried coal to a liquid suitable for upgrading to fuels and/or chemicals. The process involves liquefaction of Rosebud mine coal (Montana coal) coupled with an upgrading scheme to produce a naphthenic fuel. The upgrading comprises catalytic hydrotreating and saturation to produce naphthenic fuel. A synthetic jet fuel was prepared by blending equal volumes of naphthenic fuel with similar aliphatic fuel derived from biomass and 11 volume % of aromatic hydrocarbons. The synthetic fuel was tested using standard ASTM International techniques to determine compliance with JP-8 fuel. The composite fuel thus produced not only meets but exceeds the military aviation fuel-screening criteria. A 500-milliliter synthetic jet fuel sample which met internal screening criteria was submitted to the Air Force Research Laboratory (AFRL) at Wright–Patterson Air Force Base, Dayton, Ohio, for evaluation. The sample was confirmed by AFRL to be in compliance with U.S. Air Force-prescribed alternative aviation fuel initial screening criteria. The results show that this fuel meets or exceeds the key specification parameters for JP-8, a petroleum-based jet fuel widely used by the U.S. military. JP-8 specifications include parameters such as freeze point, density, flash point, and others; all of which were met by the EERC fuel sample. The fuel also exceeds the thermal stability specification of JP-8 fuel as determined by the quartz crystalline microbalance (QCM) test also performed at an independent laboratory as well as AFRL. This means that the EERC fuel looks and acts identically to petroleum-derived jet fuel and can be used interchangeably without any special requirements and thus provides a pathway to energy security to the U.S. military and the entire nation. This subtask was funded through the EERC–DOE Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FC26- 08NT43291. Nonfederal funding was provided by Accelergy Corporation.

  14. Ion Exchange and Solvent Extraction: Supramolecular Aspects of Solvent Exchange Volume 21

    SciTech Connect (OSTI)

    Gloe, Karsten [Technischen Universität Dresden] [Technischen Universität Dresden; Tasker, Peter A [ORNL] [ORNL; Oshima, Tatsuya [University of Miyazaki] [University of Miyazaki; Watarai, Hitoshi [Institute for NanoScience Design at Osaka University] [Institute for NanoScience Design at Osaka University; Nilsson, Mikael [University of California, Irvine] [University of California, Irvine

    2013-01-01T23:59:59.000Z

    Preface The theme of supramolecular chemistry (SC), entailing the organization of multiple species through noncovalent interactions, has permeated virtually all aspects of chemical endeavor over the past several decades. Given that the observed behavior of discrete molecular species depends upon their weak interactions with one another and with matrix components, one would have to conclude that SC must indeed form part of the fabric of chemistry itself. A vast literature now serves to categorize SC phenomena within a body of consistent terminology. The word supramolecular itself appears in the titles of dozens of books, several journals, and a dedicated encyclopedia. Not surprisingly, the theme of SC also permeates the field of solvent extraction (SX), inspiring the framework for this volume of Ion Exchange and Solvent Extraction. It is attempted in the six chapters of this volume to identify both how supramolecular behavior occurs and is studied in the context of SX and how SC is influencing the current direction of SX. Researchers and practitioners have long dealt with supramolecular interactions in SX. Indeed, the use of polar extractant molecules in nonpolar media virtually assures that aggregative interactions will dominate the solution behavior of SX. Analytical chemists working in the 1930s to the 1950s with simple mono- and bidentate chelating ligands as extractants noted that extraction of metal ions obeyed complicated mass-action equilibria involving complex stoichiometries. As chemists and engineers developed processes for nuclear and hydrometallurgical applications in the 1950s and 1960s, the preference for aliphatic diluents only enhanced the complexity and supramolecular nature of extraction chemistry. Use of physical techniques such as light scattering and vapor-pressure measurements together with various spectroscopic methods revealed organic-phase aggregates from well-defined dimers to small aggregates containing a few extractant molecules to large inverse micelles swollen with water molecules. Extraction systems involving long-chain cations such as alkylammonium species or long-chain anions such as sulfonates or carboxylates proved especially prone to extensive aggregate formation. The related phenomenon of third-phase formation in SX systems, long misunderstood, is now yielding to spectroscopic and scattering techniques showing extensive long-range organization. Over the last 50 years, tools for studying the structure and thermodynamics of aggregation have grown increasingly sophisticated, leading to a rich and detailed understanding of what we can now recognize as SC phenomena in SX. In the 1970s and 1980s, the rapid growth of SC elicited a paradigm shift in SX. The influence of SC principles had two major effects on the course of SX research. First, it provided a framework for understanding the supramolecular behavior that was already well appreciated in the field of SX, though earlier without the SC terminology. Second, it provided the conceptual tools to control supramolecular behavior in SX, direct it for intended functionality, and to simplify it. Extraction by designed reagents has been steadily progressing ever since, with commercial applications emerging to successfully validate this approach. With the discovery of crown ethers in the late 1960s, the advancement of extractant design has fruitfully employed the concept of inclusion. While considerable initial progress occurred with such molecules, especially because of their affinity and selectivity for alkali and alkaline earth metals, other molecular platforms such as calixarenes have proven more versatile. Multidentate receptors for partial to full inclusion of cations, anions, ion pairs, as well as neutral species, have now become commonplace for selective extraction. This volume of Ion Exchange and Solvent Extraction examines how the principles of SC are being employed both in advancing the design of new highly selective SX systems and in understanding aggregation phenomena in SX systems. Chapter 1 discusses the nature and definition of SC

  15. Selective Extraction of Uranium from Liquid or Supercritical Carbon Dioxide

    SciTech Connect (OSTI)

    Farawila, Anne F.; O'Hara, Matthew J.; Wai, Chien M.; Taylor, Harry Z.; Liao, Yu-Jung

    2012-07-31T23:59:59.000Z

    Current liquid-liquid extraction processes used in recycling irradiated nuclear fuel rely on (1) strong nitric acid to dissolve uranium oxide fuel, and (2) the use of aliphatic hydrocarbons as a diluent in formulating the solvent used to extract uranium. The nitric acid dissolution process is not selective. It dissolves virtually the entire fuel meat which complicates the uranium extraction process. In addition, a solvent washing process is used to remove TBP degradation products, which adds complexity to the recycling plant and increases the overall plant footprint and cost. A liquid or supercritical carbon dioxide (l/sc -CO2) system was designed to mitigate these problems. Indeed, TBP nitric acid complexes are highly soluble in l/sc -CO2 and are capable of extracting uranium directly from UO2, UO3 and U3O8 powders. This eliminates the need for total acid dissolution of the irradiated fuel. Furthermore, since CO2 is easily recycled by evaporation at room temperature and pressure, it eliminates the complex solvent washing process. In this report, we demonstrate: (1) A reprocessing scheme starting with the selective extraction of uranium from solid uranium oxides into a TBP-HNO3 loaded Sc-CO2 phase, (2) Back extraction of uranium into an aqueous phase, and (3) Conversion of recovered purified uranium into uranium oxide. The purified uranium product from step 3 can be disposed of as low level waste, or mixed with enriched uranium for use in a reactor for another fuel cycle. After an introduction on the concept and properties of supercritical fluids, we first report the characterization of the different oxides used for this project. Our extraction system and our online monitoring capability using UV-Vis absorbance spectroscopy directly in sc-CO2 is then presented. Next, the uranium extraction efficiencies and kinetics is demonstrated for different oxides and under different physical and chemical conditions: l/sc -CO2 pressure and temperature, TBP/HNO3 complex used, reductant or complexant used for selectivity, and ionic liquids used as supportive media. To complete the extraction and recovery cycle, we then demonstrate uranium back extraction from the TBP loaded sc-CO2 phase into an aqueous phase and the characterization of the uranium complex formed at the end of this process. Another aspect of this project was to limit proliferation risks by either co-extracting uranium and plutonium, or by leaving plutonium behind by selectively extracting uranium. We report that the former is easily achieved, since plutonium is in the tetravalent or hexavalent oxidation state in the oxidizing environment created by the TBP-nitric acid complex, and is therefore co-extracted. The latter is more challenging, as a reductant or complexant to plutonium has to be used to selectively extract uranium. After undertaking experiments on different reducing or complexing systems (e.g., AcetoHydroxamic Acid (AHA), Fe(II), ascorbic acid), oxalic acid was chosen as it can complex tetravalent actinides (Pu, Np, Th) in the aqueous phase while allowing the extraction of hexavalent uranium in the sc-CO2 phase. Finally, we show results using an alternative media to commonly used aqueous phases: ionic liquids. We show the dissolution of uranium in ionic liquids and its extraction using sc-CO2 with and without the presence of AHA. The possible separation of trivalent actinides from uranium is also demonstrated in ionic liquids using neodymium as a surrogate and diglycolamides as the extractant.

  16. Mill Designed Bio bleaching Technologies

    SciTech Connect (OSTI)

    Institute of Paper Science Technology

    2004-01-30T23:59:59.000Z

    A key finding of this research program was that Laccase Mediator Systems (LMS) treatments on high-kappa kraft could be successfully accomplished providing substantial delignification (i.e., > 50%) without detrimental impact on viscosity and significantly improved yield properties. The efficiency of the LMS was evident since most of the lignin from the pulp was removed in less than one hour at 45 degrees C. Of the mediators investigated, violuric acid was the most effective vis-a-vis delignification. A comparative study between oxygen delignification and violuric acid revealed that under relatively mild conditions, a single or a double LMS{sub VA} treatment is comparable to a single or a double O stage. Of great notability was the retention of end viscosity of LMS{sub VA} treated pulps with respect to the end viscosity of oxygen treated pulps. These pulps could then be bleached to full brightness values employing conventional ECF bleaching technologies and the final pulp physical properties were equal and/or better than those bleached in a conventional ECF manner employing an aggressively O or OO stage initially. Spectral analyses of residual lignins isolated after LMS treated high-kappa kraft pulps revealed that similar to HBT, VA and NHA preferentially attack phenolic lignin moieties. In addition, a substantial decrease in aliphatic hydroxyl groups was also noted, suggesting side chain oxidation. In all cases, an increase in carboxylic acid was observed. Of notable importance was the different selectivity of NHA, VA and HBT towards lignin functional groups, despite the common N-OH moiety. C-5 condensed phenolic lignin groups were overall resistant to an LMS{sub NHA, HBT} treatments but to a lesser extent to an LMS{sub VA}. The inactiveness of these condensed lignin moieties was not observed when low-kappa kraft pulps were biobleached, suggesting that the LMS chemistry is influenced by the extent of delignification. We have also demonstrated that the current generation of laccase has a broad spectrum of operating parameters. Nonetheless, the development of future genetically engineered laccases with enhanced temperature, pH and redox potentials will dramatically improve the overall process. A second challenge for LMS bleaching technologies is the need to develop effective, catalytic mediators. From the literature we already know this is feasible since ABTS and some inorganic mediators are catalytic. Unfortunately, the mediators that exhibit catalytic properties do not exhibit significant delignification properties and this is a challenge for future research studies. Potential short-term mill application of laccase has been recently reported by Felby132 and Chandra133 as they have demonstrated that the physical properties of linerboard can be improved when exposed to laccase without a chemical mediator. In addition, xxx has shown that the addition of laccase to the whitewater of the paper machine has several benefits for the removal of colloidal materials. Finally, this research program has presented important features on the delignification chemistry of LMS{sub NHA} and LMS{sub VA} that, in the opinion of the author, are momentous contributions to the overall LMS chemistry/biochemistry knowledge base which will continue to have future benefits.

  17. Stable isotopic investigations of in-situ bioremediation of chlorinated organic solvents. 1998 annual progress report

    SciTech Connect (OSTI)

    Sturchio, N.C.

    1998-06-01T23:59:59.000Z

    'Contamination of soils and groundwaters with chlorinated aliphatic hydrocarbons (CAHs) is one of the most serious environmental problems in the DOE system and in the nation at large. These compounds are designated as priority pollutants by the US Environmental Protection Agency (EPA) and are known or suspected to be carcinogenic or mutagenic in humans. These compounds are readily transported by groundwater and are not reduced to acceptable concentrations for human consumption by most municipal water supply treatments; thus the compounds represent a significant hazard to a large portion of the human population. In situ bioremediation is an emerging technology that shows great promise for mitigation of CAH contamination at many sites. One of the most severe limitations of in-situ bioremediation is the difficulty of proving when it is working at a given site. The concentrations of CAHs and their degradation products in plumes may be difficult to relate to the efficiency of the remediation process because of dilution effects, but this problem is mitigated to a large extent by measuring isotope ratios. If there is a significant isotopic fractionation between CAHs and derivative chlorine-bearing products, then the fraction of CAH that is dechlorinated can be inferred from the {sup 37}Cl/{sup 35}Cl and {sup 13}C/{sup 12}C isotope ratios of the residual CAH. It is important to point out that there is currently no published information available on the magnitude of chlorine and carbon isotopic fractionation associated with biological degradation of CAHs. The authors plan to help eliminate this important gap in the knowledge with the work being performed here. This work is relevant to EMSP goals because it will provide a new and cost-effective means of evaluating and monitoring the effectiveness of in-situ bioremediation. It will employ newly developed techniques to characterize isotopic fractionation (of chlorine and carbon) associated with biotic and abiotic degradation of CAHs in laboratory microcosms. These techniques and the data acquired by using them in laboratory studies will form the fundamental basis for quantitative assessment of the mechanisms, rates, and efficiencies of various in-situ bioremediation schemes for CAHs. This report summarizes work as of 21 months into a 36-month project. First, the author has developed methods for precise measurement of stable carbon and chlorine isotope ratios of micromolar amounts of CAHs. He has also developed methods for quantitative extraction of CAHs from water and air. He has applied these methods in laboratory experiments, to investigate isotopic fractionation caused by microbial degradation and by abiotic processes such as evaporation and chemical reduction. He has also applied these methods to field investigations of contaminated groundwater aquifers at the Paducah Gaseous Diffusion Plant, Kentucky and at several manufacturing plants in the Chicago and Kansas City metropolitan areas. Results of much of this work have already been incorporated into four manuscripts that have been published, accepted for publication, or are in review.'

  18. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    SciTech Connect (OSTI)

    Guodong Du

    2004-12-19T23:59:59.000Z

    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl{sub 2} (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph){sub 2}C(Ph){sub 2}O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and {alpha}-hydroxy ketones to benzaldehyde and {alpha}-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono-, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation of {alpha}-ketols to {alpha}-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were designed and synthesized. Examination of iron(II) complexes showed that they were efficient catalysts for the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.

  19. IMPROVED ANTIFOAM AGENT STUDY END OF YEAR REPORT, EM PROJECT 3.2.3

    SciTech Connect (OSTI)

    Lambert, D.; Koopman, D.; Newell, J.

    2011-09-30T23:59:59.000Z

    Antifoam 747 is added to minimize foam produced by process gases and water vapor during chemical processing of sludge in the Defense Waste Processing Facility (DWPF). This allows DWPF to maximize acid addition and evaporation rates to minimize the cycle time in the Chemical Processing Cell (CPC). Improvements in DWPF melt rate due to the addition of bubblers in the melter have resulted in the need for further reductions in cycle time in the CPC. This can only be accomplished with an effective antifoam agent. DWPF production was suspended on March 22, 2011 as the result of a Flammable Gas New Information/(NI) Potential Inadequacy in the Safety Analysis (PISA). The issue was that the DWPF melter offgas flammability strategy did not take into account the H and C in the antifoam, potentially flammable components, in the melter feed. It was also determined the DWPF was using much more antifoam than anticipated due to a combination of longer processing in the CPC due to high Hg, longer processing due to Actinide Removal Process (ARP)/Modular Caustic Side Solvent Extraction Unit (MCU) additions, and adding more antifoam than recommended. The resolution to the PISA involved and assessment of the impact of the antifoam on melter flammability and the implementation of a strategy to control additions within acceptable levels. This led to the need to minimize the use of Antifoam 747 in processing beginning in May 2011. DWPF has had limited success in using Antifoam 747 in caustic processing. Since starting up the ARP facility, the ARP product (similar chemically to caustic sludge) is added to the Sludge Receipt and Adjustment Tank (SRAT) at boiling and evaporated to maintain a constant SRAT volume. Although there is very little offgas generated during caustic boiling, there is a large volume of water vapor produced which can lead to foaming. High additions and more frequent use of antifoam are used to mitigate the foaming during caustic boiling. The result of these three issues above is that DWPF had three antifoam needs in FY2011: (1) Determine the cause of the poor Antifoam 747 performance during caustic boiling; (2) Determine the decomposition products of Antifoam 747 during CPC processing; and (3) Improve the effectiveness of Antifoam 747, in order to minimize the amount used. Testing was completed by Illinois Institute of Technology (IIT) and Savannah River National Laboratory (SRNL) researchers to address these questions. The testing results reported were funded by both DWPF and DOE/EM 31. Both sets of results are reported in this document for completeness. The results of this research are summarized: (1) The cause for the poor Antifoam 747 performance during caustic boiling was the high hydrolysis rate, cleaving the antifoam molecule in two, leading to poor antifoam performance. In testing with pH solutions from 1 to 13, the antifoam degraded quickly at a pH < 4 and pH > 10. As the antifoam decomposed it lost its spreading ability (wetting agent performance), which is crucial to its antifoaming performance. During testing of a caustic sludge simulants, there was more foam in tests with added Antifoam 747 than in tests without added antifoam. (2) Analyses were completed to determine the composition of the two antifoam components and Antifoam 747. In addition, the decomposition products of Antifoam 747 were determined during CPC processing of sludge simulants. The main decomposition products were identified primarily as Long Chain Siloxanes, boiling point > 400 C. Total antifoam recovery was 33% by mass. In a subsequent study, various compounds potentially related to antifoam were found using semi-volatile organic analysis and volatile organic analysis on the hexane extractions and hexane rinses. These included siloxanes, trimethyl silanol, methoxy trimethyl silane, hexamethyl disiloxane, aliphatic hydrocarbons, dioctyl phthalate, and emulsifiers. Cumulatively, these species amounted to less than 3% of the antifoam mass. The majority of the antifoam was identified using carbon analysis of the SRAT product (40-80% by ma

  20. Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

    SciTech Connect (OSTI)

    Klobukowski, Erik

    2011-12-29T23:59:59.000Z

    This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and conditions, it was found that the oxidative dehydrogenation of dibenzylamine to Nbenzylidenebenzylamine, with N-methylmorpholine N-oxide (NMMO), was nearly quantitative (96%) within 24 h. However, the reaction with oxygen was much slower, with only a 52% yield of imine product over the same time period. Moreover, the rate of reaction was found to be influenced by the nature of the amine N-oxide. For example, the use of the weakly basic pyridine N-oxide (PyNO) led to an imine yield of only 6% after 24 h. A comparison of amine N-oxide and O2 was also examined in the oxidation of PhCH{sub 2}OH to PhCHO catalyzed by bulk gold. In this reaction, a 52% yield of the aldehyde was achieved when NMMO was used, while only a 7% product yield was afforded when O{sub 2} was the oxidant after 48 h. The bulk gold-catalyzed oxidative dehydrogenation of cyclic amines generates amidines, which upon treatment with Aerosil and water were found to undergo hydrolysis to produce lactams. Moreover, 5-, 6-, and 7-membered lactams could be prepared through a one-pot reaction of cyclic amines by treatment with oxygen, water, bulk gold, and Aerosil. This method is much more atom economical than industrial processes, does not require corrosive acids, and does not generate undesired byproducts. Additionally, the gold and Aerosil catalysts can be readily separated from the reaction mixture. The second project involved studying iron(III) tetraphenylporphyrin chloride, Fe(TPP)Cl, as a homogeneous catalyst for the generation of carbenes from diazo reagents and their reaction with heteroatom compounds. Fe(TPP)Cl, efficiently catalyzed the insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds of aliphatic and aromatic alcohols. Fe(TPP)Cl was also found to be an effective catalyst for tandem N-H and O-H insertion/cyclization reactions when 1,2-diamines and 1,2-alcoholamines were treated with diazo reagents. This approach provides a one-pot process for synthesizing piperazinones and morpholinones and related analogues such as quinoxalinones and benzoxazin-2-ones.