Palladium Catalyzed Coupling Reactions: Mechanism of Reductive Elimination. Progress Report, October 1, 1979-September 30, 1980. [Ethane Elimination] (open access)

Palladium Catalyzed Coupling Reactions: Mechanism of Reductive Elimination. Progress Report, October 1, 1979-September 30, 1980. [Ethane Elimination]

The 1,1-reductive elimination of ethane from three cis-bis(phosphine)-dimethylpalladium complexes, L/sub 2/Pd(CH/sub 3/)/sub 2/ (L = PPh/sub 3/, PPh/sub 2/,CH/sub 3/ and L/sub 2/ = Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/), and three trans analogs (L = PPh/sub 3/, PPh/sub 2/CH/sub 3/ and L/sub 2/ = 2,11-bis(diphenylphosphinomethyl)benzo(c)phenanthrene (TRANSPHOS)) was carried out. The three cis complexes underwent reductive elimination in the presence of coordinating solvents (DMSO, DMF, and THF). The trans complexes which could isomerize to cis (L = PPh/sub 3/, PPh/sub 2/CH/sub 3/) did so in polar solvents and then underwent reductive elimination. TRANSPHOS dimethylpalladium would not undergo reductive elimination of ethane. The eliminations from the cis isomers were intramolecular and displayed first order kinetics. Although TRANSPHOS dimethylpalladium(II) would not undergo a 1,1-reductive elimination of ethane, the addition of CD/sub 3/I to a DMSO solution of this complex at 25/sup 0/C rapidly produced CD/sub 3/-CH/sub 3/, implicating a transient palladium(IV) intermediate. E- and Z-bromostyrylbis(diphenylmethylphosphine)palladium(0) react with methyl lithium in THF at ambient temperature to give the E- and Z- propenylbenzenes, respectively. At -78/sup 0/C, the intermediate E- and Z-styrylmethylbis(diphenylmethylphosphine)palladium(II) complexes (9a,b) can be isolated. On raising the temperature of solutions of 9a,b in THF, E- and Z-propenylbenzenes are produced. The reductive elimination …
Date: September 1, 1980
Creator: Stille, J. K.
System: The UNT Digital Library
Mean and Peak Wind Load Reduction on Heliostats (open access)

Mean and Peak Wind Load Reduction on Heliostats

This report presents the results of wind-tunnel tests supported through the Solar Energy Research Institute (SERI) by the Office of Solar Thermal Technology of the US Department of Energy as part of the SERI research effort on innovative concentrators. As gravity loads on drive mechanisms are reduced through stretched-membrane technology, the wind-load contribution of the required drive capacity increases in percentage. Reduction of wind loads can provide economy in support structure and heliostat drive. Wind-tunnel tests have been directed at finding methods to reduce wind loads on heliostats. The tests investigated both mean and peak forces, and moments. A significant increase in ability to predict heliostat wind loads and their reduction within a heliostat field was achieved. In addition, a preliminary review of wind loads on parabolic dish collectors was conducted, resulting in a recommended research program for these type collectors. 42 refs., 38 figs., 1 tab.
Date: September 1, 1987
Creator: Peterka, J. A.; Tan, L.; Bienkiewcz, B. & Cermak, J. E.
System: The UNT Digital Library
Palladium Catalyzed Coupling Reactions: Mechanism of Reductive Elimination. Progress Report, June 1, 1978-September 30, 1979 (open access)

Palladium Catalyzed Coupling Reactions: Mechanism of Reductive Elimination. Progress Report, June 1, 1978-September 30, 1979

The coupling reaction of benzyl halides and organolithium, organotin, or Grignard Reagents is catalyzed by palladium. The sequence of events in the catalytic cycle is oxidative addition of the benzyl halide to palladium(0), methathesis by the organometallic reagent to give a benzyl methyl palladium(II) complex, oxidative addition of the benzyl halide to give a palladium(IV) complex, and reductive elimination of benzyl and methyl to give ethylbenzene. The reductive elimination from palladium bearing an optically active ..cap alpha..-deuteriobenzyl group takes place with retention of configuration at carbon, and is therefore concerted or nearly concerted. Since rho is positive in the catalytic reaction with substituted aryl halides, an oxidative addition, probably during the Pd(II) to Pd(IV) reaction, is the slow step in the catalytic cycle. The intermediate diorganopalladium species can be isolated when the two groups attached to palladium are both methyl or methyl and either cis or trans-..beta..-styryl. The decomposition of these species can be followed by NMR. In the case of methylstyrylpalladium(II) complexes, the reductive elimination gives propenyl benzene with stereospecific retention of double bond geometry. Cis-dimethylbis(diphenylmethylphosphine)palladium(II) does not undergo isomerization to the more stable trans isomer in an inert solvent, and is stable toward reductive elimination up to 50/sup …
Date: September 1, 1979
Creator: Stille, J. K.
System: The UNT Digital Library
Environmental Assessment of Remedial Action at the Slick Rock Uranium Mill Tailings Sites, Slick Rock, Colorado. Revision 1 (open access)

Environmental Assessment of Remedial Action at the Slick Rock Uranium Mill Tailings Sites, Slick Rock, Colorado. Revision 1

The Uranium Mill Tailings Radiation Control Act of 1978 (42 USC {section}7901 et seq.), hereafter referred to as the UMTRCA, authorized the US Department of Energy (DOE) to clean up two uranium mill tailings processing sites near Slick Rock, Colorado, in San Miquel County. Contaminated materials cover an estimated 63 acres of the Union Carbide (UC) processing site and 15 ac of the North Continent (NC) processing site. The sites are within 1 mile of each other and are adjacent to the Dolores River. The sites contain concrete foundations of mill buildings, tailings piles, and areas contaminated by windblown and waterborne radioactive tailings materials. The total estimated volume of contaminated materials is approximately 621,300 cubic yards (yd{sup 3}). In addition to the contamination in the two processing site areas, four VPs were found to contain contamination. As a result of the tailings being exposed to the environment, contamination associated with the UC and NC sites has leached into shallow ground water. Surface water has not been affected. The closest residence is approximately 0.3 air mi from either site. The proposed action is to remediate the UC and NC sites by removing all contaminated materials within the designing site boundaries or …
Date: September 1, 1994
Creator: unknown
System: The UNT Digital Library
Chemically Assisted in Situ Recovery of Oil Shale. [Quarterly] Report, April 1, 1993--June 30, 1993 (open access)

Chemically Assisted in Situ Recovery of Oil Shale. [Quarterly] Report, April 1, 1993--June 30, 1993

The objective of this work is to investigate, in the laboratory, the parameters associated with a chemically assisted in situ recovery procedure, using hydrogen chloride (HCI), carbon dioxide (CO{sub 2}), and steam (H{sub 2}0), to obtain data useful to develop a process more economic than existing processes and to report all findings. The technical progress of the project is reported. The project status is that the progress is being made towards being able to run meaningful experiments.
Date: September 1, 1993
Creator: Ramirez, W. F.
System: The UNT Digital Library
Direct Methane Conversion to Methanol. Quarterly Project Status Report, January 1, 1994--March 31, 1994 (open access)

Direct Methane Conversion to Methanol. Quarterly Project Status Report, January 1, 1994--March 31, 1994

We proposed to demonstrate the effectiveness of a catalytic membrane reactor (a ceramic membrane combined with a catalyst) to solely produce methanol by partial oxidation of methane. Methanol is used as a chemical feedstock, gasoline additive, and turbine fuel. Methane partial oxidation using a catalytic membrane reactor has been determined as one of the promising approaches for methanol synthesis from methane. In the original proposal the membrane was used to selectively remove methanol from the reaction zone before carbon oxides form, thus increasing the methanol yield. Methanol synthesis and separation in one step would also make methane more valuable for producing chemicals and fuels. The cooling tube inserted inside the membrane reactor has created a low temperature zone that rapidly quenches the product stream. Both ceramic and metal membranes were tested in this study and similar results were obtained. This membrane reactor system has proved effective for increasing methanol selectivity during CH{sub 4} oxidation. We are currently using this non-isothermal non-permselective membrane reactor, and evaluating modifications to further improve performance. Metal membrane was used to avoid the membrane breakage problem. A series of experiments were carried out in order to optimize the operation of the process. A methanol yield of …
Date: September 1, 1994
Creator: Noble, R. D. & Falconer, J. L.
System: The UNT Digital Library
Evaluation of Aftermarket Fuel Delivery Systems for Natural Gas and Lpg Vehicles (open access)

Evaluation of Aftermarket Fuel Delivery Systems for Natural Gas and Lpg Vehicles

This study was designed to evaluate the effectiveness of aftermarket fuel delivery systems for vehicles fueled by compressed natural gas (CNG) and liquefied petroleum gas (LPG). Most of the CNG and LPG vehicles studied were converted to the alternative fuel after purchase. There are wide variations in the quality of the conversion hardware and the installation. This leads to questions about the overall quality of the converted vehicles, in terms of emissions, safety, and performance. There is a considerable body of emissions data for converted light-duty vehicles, and a smaller amount for medium- and heavy-duty vehicles. However, very few of these data involve real world conditions, and there is growing concern about in-use emissions. This report also attempts to assess factors that could allow in-use emissions to vary from the ``best-case`` results normally reported. The study also addresses issues of fuel supply, fuel composition, performance, safety, and warranty waivers. The report is based on an extensive literature and product survey and on the author`s experience with fuel delivery systems for light-duty vehicles.
Date: September 1, 1992
Creator: Willson, B.
System: The UNT Digital Library
Records of Selected Wells and Springs in the Rulison Project Area, Garfield and Mesa Counties, Colorado. (open access)

Records of Selected Wells and Springs in the Rulison Project Area, Garfield and Mesa Counties, Colorado.

None
Date: September 1969
Creator: Hurr, R. T.; Wilson, W. W.; Welder, F. A. & Emerson, R.L.
System: The UNT Digital Library
Advanced NMR approaches in the characterization of coal. Final technical report, September 1, 1990--August 31, 1993 (open access)

Advanced NMR approaches in the characterization of coal. Final technical report, September 1, 1990--August 31, 1993

This project addressed two main goals and one much smaller one. The main goals were (1) to improve the significance, reliability and information content in high-resolution NMR (nuclear magnetic resonance) characterization of coal samples and (2) to develop chemically informative NMR imaging techniques for coal. The minor goal was to explore advanced features of dynamic nuclear polarization (DNP) as a technique for coal characterization; this included the development of two DNP probes and the examination of DNP characteristics of various carbonaceous samples, including coals. {sup 13}C NMR advances for coal depended on large-sample MAS devices, employing either cross-polarization (CP) or direct polarization (DP) approaches. CP and DP spin dynamics and their relationships to quantitation and spin counting were elucidated. {sup 1}H NMR studies, based on CRAMPS, dipolar dephasing and saturation with perdeuteropyridine, led to a {sup 1}H NMR-based elucidation of chemical functionality in coal. {sup 1}H and {sup 13}C NMR imaging techniques, based on magic-angle spinning and rotating magnetic field gradients, were developed for introducing chemical shift information (hence, chemical detail) into the spatial imaging of coal. The TREV multiple-pulse sequence was found to be useful in the {sup 1}H CRAMPS imaging of samples like coal.
Date: September 30, 1993
Creator: Maciel, G. E.
System: The UNT Digital Library
Evaluation of Aftermarket Fuel Delivery Systems for Natural Gas and Lpg Vehicles (open access)

Evaluation of Aftermarket Fuel Delivery Systems for Natural Gas and Lpg Vehicles

This study was designed to evaluate the effectiveness of aftermarket fuel delivery systems for vehicles fueled by compressed natural gas (CNG) and liquefied petroleum gas (LPG). Most of the CNG and LPG vehicles studied were converted to the alternative fuel after purchase. There are wide variations in the quality of the conversion hardware and the installation. This leads to questions about the overall quality of the converted vehicles, in terms of emissions, safety, and performance. There is a considerable body of emissions data for converted light-duty vehicles, and a smaller amount for medium- and heavy-duty vehicles. However, very few of these data involve real world conditions, and there is growing concern about in-use emissions. This report also attempts to assess factors that could allow in-use emissions to vary from the best-case'' results normally reported. The study also addresses issues of fuel supply, fuel composition, performance, safety, and warranty waivers. The report is based on an extensive literature and product survey and on the author's experience with fuel delivery systems for light-duty vehicles.
Date: September 1, 1992
Creator: Willson, B. (Colorado State Univ., Fort Collins, CO (United States))
System: The UNT Digital Library
Alfred A. Arraj U.S. Courthouse; Denver, Colorado: A Model of Sustainability (open access)

Alfred A. Arraj U.S. Courthouse; Denver, Colorado: A Model of Sustainability

This brochure describes the sustainability of the Alfred A. Arraj United States Courthouse in Denver, Colorado.
Date: September 1, 2005
Creator: unknown
System: The UNT Digital Library
Solar is Saving Energy for the Alfred A. Arraj U.S. Courthouse: Achieving Results with Renewable Energy in the Federal Government Case Study (open access)

Solar is Saving Energy for the Alfred A. Arraj U.S. Courthouse: Achieving Results with Renewable Energy in the Federal Government Case Study

Solar is Saving Energy for the Alfred A. Arraj U.S. Courthouse is a case study that describes how building-integrated photovoltaic systems can be incorporated into the federal sector, and also how they can provide opportunities to meet federal renewable energy goals.
Date: September 1, 2005
Creator: unknown
System: The UNT Digital Library