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.
Object Type: Report
System: The UNT Digital Library
Novel Concepts in Electrochemical Solar Cells. Third Quarterly Progress Report, November 15, 1979-January 15, 1980. [Molten Salt Electrolytes] (open access)

Novel Concepts in Electrochemical Solar Cells. Third Quarterly Progress Report, November 15, 1979-January 15, 1980. [Molten Salt Electrolytes]

Efforts have been primarily directed toward evaluation of the room temperature molten salt electrolyte in terms of its overall performance for photovoltaic cells. Mass transport processes may prove to be the rate-limiting factor for such electrolytes, unless the concentration of the photo-active redox component can be increased and the solvent viscosity reduced. Acid-base surface chemistry of n-GaAs as occurs in aqueous systems, has been found present and its consequences will be further explored. The selection and optimization of PEC electrolytes is a complex task and we believe that a systems approach would facilitate in identifying the basic electrolyte properties needed. A preliminary analysis reveals that although some of the criteria for an electrolyte are definable precisely, others do require empirical experimentation. It can be concluded that relatively few electrolytes in current use are adequate and it would appear that greater efforts to develop electrolytes would be advantageous. The various types of electrolytes that could be used for PEC's have been identified. Good quality MoSe/sub 2/ single crystals can be grown and short circuit currents greater than previously reported have been achieved in an I/sub 2//I/sup -//Pt cell. A novel technique to produce photo-active films by anodization is being investigated, initially …
Date: January 1, 1980
Creator: DuBow, J.; Job, R. & Krishnan, R.
Object Type: Report
System: The UNT Digital Library
Wind Load Reduction for Heliostats (open access)

Wind Load Reduction for 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 primarily the mean forces, moments, and the possibility of measuring fluctuating forces in anticipation of reducing those forces. A significant increase in ability to predict heliostat wind loads and their reduction within a heliostat field was achieved.
Date: May 1, 1986
Creator: Peterka, J. A.; Hosoya, N.; Bienkiewicz, B. & Cermak, J. E.
Object Type: Report
System: The UNT Digital Library
Influence of Geometry on Natural Convection in Buildings (open access)

Influence of Geometry on Natural Convection in Buildings

Strong free convection airflows occur within passive solar buildings resulting from elevated temperatures of surfaces irradiated by solar energy compared with the cooler surfaces not receiving radiation. The geometry of a building has a large influence on the directions and magnitudes of natural airflows, and thus heat transfer between zones. This investigation has utilized a variety of reduced-scale building configurations to study the effects of geometry on natural convection heat transfer. Similarity between the reduced-scale model and a full-scale passive solar building is achieved by having similar geometries and by replacing air with Freon-12 gas as the model's working fluid. Filling the model with Freon-12 gas results in similarity in Prandtl numbers and Rayleigh numbers based on temperature differences in the range from 10/sup 9/ to 10/sup 11/. Results from four geometries are described with an emphasis placed on the effects of heat loss on zone temperature stratification shifts.
Date: January 1, 1985
Creator: White, M. D.; Winn, C. B.; Jones, G. F. & Balcomb, J. D.
Object Type: Article
System: The UNT Digital Library
Rapid estimation of /sup 226/Ra in soil for the Grand Junction RASA/UMTRA project (open access)

Rapid estimation of /sup 226/Ra in soil for the Grand Junction RASA/UMTRA project

The Radiological Survey Activities (RASA) Group of the Health and Safety Research Division at Oak Ridge National Laboratory (ORNL) is an Inclusion Survey Contractor (ISC) for the Uranium Mill Tailings Remedial Action Program (UMTRAP). The purpose of the ISC is to survey designated sites potentially contaminated with radioactive material originating from the 24 inactive uranium mill sites and make recommendations as to whether the site should be included in or excluded from further consideration by UMTRAP. An important aspect of the program is a prompt and inexpensive estimation of Radium-226 (/sup 226/Ra) concentration in soil samples. A large sodium iodide (NaI) well crystal coupled to a multichannel analyzer is used to count soil samples. Count data are currently analyzed with an algorithm that utilizes three regions of interest (ROI). A lack of agreement was observed when samples were also analyzed with lithium-drifted germanium (GeLi) spectrometers. The average estimate of /sup 226/Ra obtained using the current algorithm was 19% greater than the GeLi determination. Some possible reasons for these differences were examined. In 8.5% of the samples, the relative concentration of Cesium-137 (/sup 137/Cs) was highly correlated to the extent of error. Using alternative analysis techniques, the error for /sup 226/Ra …
Date: January 1, 1986
Creator: Kark, J.B.; Borak, T.B.; Kearney, P.D. & Rood, A.S.
Object Type: Article
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.
Object Type: Report
System: The UNT Digital Library
Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes (open access)

Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes

We have obtained a neutron diffraction data set for Os{sub 2}(CO){sub 8}({mu}-C{sub 2}H{sub 4}). While the structure is still being solved, it is already clear that the hybridization at both of the ethylene carbons is sp{sup 3}. Our first interpretation of our liquid crystal NMR results had suggested a very acute H-C-H angle. We have also obtained {sup 13}C liquid crystal data for Os{sub 2}(CO){sub 8}({mu}-C{sub 2}H{sub 4}). Liquid crystal NMR ({sup 13}C as well as {sup 1}H) spectra have been obtained for Os(CO){sub 4}(C{sub 2}H{sub 4}) and its solution structure determined, in order to test our methodology on a molecule with a rigid structure. The normal modes of Os(CO){sub 4}({mu}-C{sub 2}H{sub 4}) and its deuterated and {sup 13}C-labelled isotopomers have been completely assigned. A partial vibrational analysis of Os{sub 2}(CO){sub 8}({mu}-propene), Os{sub 2}(CO){sub 8}(trans-2-butene), and Os{sub 2}(CO){sub 8}(1-butene) has been completed. We have prepared Os(CO){sub 4}({mu}-CH{sub 2}CH{sub 2}CH{sub 2}) and its 3,3-dideuterio analog. In the course of this work the reaction of Na{sub 2}Os(CO){sub 4} with a number of 1,3-propanediol derivatives has been examined. 1,3-Propanediol ditosylate afforded much better yields of the osmacycle than did either the ditriflate or diiodide. 2,2-Dideutero-1,3-propanediol ditosylate was used to prepare the deuterium-labelled osmacyclobutane.
Date: January 1, 1989
Creator: Norton, J.R.
Object Type: Report
System: The UNT Digital Library
Overburden Characterization and Post-Burn Study of the Hanna Iv, Underground Coal Gasification Site, Wyoming, and Comparison to Other Wyoming Ucg Sites (open access)

Overburden Characterization and Post-Burn Study of the Hanna Iv, Underground Coal Gasification Site, Wyoming, and Comparison to Other Wyoming Ucg Sites

Analysis of 21 post-burn cores taken from the Hanna IV UCG site allows 96 m (315 ft) of overburden to be subdivided into four local stratigraphic units. The 7.6 m (25 ft) thick Hanna No. 1 coal seam is overlain by a laterally discontinuous, 3.3 m (11 ft) thick shaley mudstone (Unit A') in part of the Hanna IV site. A more widespread, 30 m (90 ft) thick well-indurated sandstone (Unit A) overlies the A' unit. Unit A is the roof rock for both of the Hanna IV cavities. Overlying Unit A is a 33 m (108 ft) thick sequence of mudstone and claystone (Unit B), and the uppermost unit at the Hanna IV site (Unit C) is a coarse-grained sandstone that ranges in thickness from 40 to 67 m (131 to 220 ft). Two elliptical cavities were formed during the two phases of the Hanna IV experiment. The larger cavity, Hanna IVa, is 45 x 15 m in plan and has a maximum height of 18 m (59 ft) from the base of the coal seam to the top of the cavity; the Hanna IVb cavity is 40 x 15 m in plan and has a maximum height of …
Date: November 1, 1984
Creator: Marcouiller, B.A.; Burns, L.K. & Ethridge, F.G.
Object Type: Report
System: The UNT Digital Library
Comparison of the Response of a Nai Scintillation Crystal With a Pressurized Ionization Chamber as a Function of Altitude, Radiation Level and RA-226 Concentration (open access)

Comparison of the Response of a Nai Scintillation Crystal With a Pressurized Ionization Chamber as a Function of Altitude, Radiation Level and RA-226 Concentration

The Grand Junction Uranium Mill Tailings Remedial Action-Radiological Survey Activities Group (UMTRA-RASA) program employs a screening method in which external exposure rates are used to determine if a property contaminated with uranium mill tailings is eligible for remedial action. Portable NaI detectors are used by survey technicians to locate contaminated areas and determine exposure rates. The exposure rate is calculated using a regression equation derived from paired measurements made with a pressurized ionization chamber (PIC) and a NaI detector. During July of 1985 extensive measurements were taken using a PIC and a NaI scintillator with both analogue and digital readout for a wide range of exposure rates and at a variety of elevations. The surface soil was sampled at most of these locations and analyzed for /sup 226/Ra. The response of the NaI detectors was shown to be highly correlated to radiation level but not to /sup 226/Ra concentration or elevation.
Date: January 1, 1986
Creator: Provencher, R.; Smith, G.; Borak, T.B. & Kearney, P.
Object Type: Article
System: The UNT Digital Library
Milk Production and Distribution in Nine Western States in the 1950s (open access)

Milk Production and Distribution in Nine Western States in the 1950s

This report provides information on milk distribution and dairy cattle feeding practices in Nevada, Utah and portions of seven other adjacent states during the 1950s. The information was gathered to support the US Department of Energy's ''Offsite Radiation Exposure Review Project (ORERP).'' This project is charged with providing radiation dose estimates for residents of Nevada, Utah, and surrounding states from nuclear weapons testing conducted at the Nevada Test Site from 1951 through 1962. The information on milk production and distribution is essential for assessment of the internal organ doses received by people as a result of ingesting radioactive fallout-contaminated foods. The information is used as input data for Colorado State University's PATHWAY computer code which estimates the ingestion of twenty radionuclides by people relative to a given level of fallout deposition.
Date: March 1, 1987
Creator: Ward, G. M. & Whicker, F. W.
Object Type: Report
System: The UNT Digital Library
Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes. Progress report, April 1, 1988--March 31, 1989 (open access)

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

We have obtained a neutron diffraction data set for Os{sub 2}(CO){sub 8}({mu}-C{sub 2}H{sub 4}). While the structure is still being solved, it is already clear that the hybridization at both of the ethylene carbons is sp{sup 3}. Our first interpretation of our liquid crystal NMR results had suggested a very acute H-C-H angle. We have also obtained {sup 13}C liquid crystal data for Os{sub 2}(CO){sub 8}({mu}-C{sub 2}H{sub 4}). Liquid crystal NMR ({sup 13}C as well as {sup 1}H) spectra have been obtained for Os(CO){sub 4}(C{sub 2}H{sub 4}) and its solution structure determined, in order to test our methodology on a molecule with a rigid structure. The normal modes of Os(CO){sub 4}({mu}-C{sub 2}H{sub 4}) and its deuterated and {sup 13}C-labelled isotopomers have been completely assigned. A partial vibrational analysis of Os{sub 2}(CO){sub 8}({mu}-propene), Os{sub 2}(CO){sub 8}(trans-2-butene), and Os{sub 2}(CO){sub 8}(1-butene) has been completed. We have prepared Os(CO){sub 4}({mu}-CH{sub 2}CH{sub 2}CH{sub 2}) and its 3,3-dideuterio analog. In the course of this work the reaction of Na{sub 2}Os(CO){sub 4} with a number of 1,3-propanediol derivatives has been examined. 1,3-Propanediol ditosylate afforded much better yields of the osmacycle than did either the ditriflate or diiodide. 2,2-Dideutero-1,3-propanediol ditosylate was used to prepare the deuterium-labelled osmacyclobutane.
Date: January 1, 1989
Creator: Norton, J. R.
Object Type: Report
System: The UNT Digital Library
Investigation of the Pathway of Contaminated Soil Transported to Plant Surfaces by Raindrop Splash (open access)

Investigation of the Pathway of Contaminated Soil Transported to Plant Surfaces by Raindrop Splash

The environmental transport pathway of soil-borne radioisotopes to vegetation surfaces via raindrop splash was studied. The data show that soil can significantly contribute to the contamination found on plants. Further detailed study is needed to calculate the rate constant for the raindrop splash and retention pathways. 8 references, 1 figure. (ACR)
Date: October 21, 1983
Creator: Dreicer, M.; Hakonson, T. E.; Whicker, F. W. & White, G. C.
Object Type: Article
System: The UNT Digital Library
Variability Within the Ocean-Atmospheric System Over the North Pacific (open access)

Variability Within the Ocean-Atmospheric System Over the North Pacific

Characteristics of the oceanic mixed layer over the North Pacific were examined utilizing a number of statistical methods. Based on the analyses of twelve years of data, a quasi-meridional differentiation (QMD) in sea surface temperature (SST) spectra across the North Pacific was observed. The SST spectra became increasingly red as an increasing function of latitude. A strong 21 to 26 day cycle in SST anomalies is discussed which may be a reflection of heat fluxes. These fluxes also vacillate significantly on this time-scale in conjunction with cycles observed in the atmospheric energy modes of available potential and kinetic energy. Examination of an oceanic heat budget on a spatial and temporal basis suggest that the impact of latent and sensible heat fluxes upon ..delta..SST is partially a function of the magnitude of the heat fluxes as well as of the depth to which their effects are mixed. The heat budget analyses and the fitting of power spectra of SST anomalies over the North Pacific to a two-parameter oceanic model, suggest that SST behavior over the mid-oceanic regions of the North Pacific is dominated by the influence of latent and sensible heat fluxes. On the other hand, over the remainder of the …
Date: January 1, 1980
Creator: Ciesielski, P E
Object Type: Report
System: The UNT Digital Library
Pathway: A Simulation Model of Radionuclide-Transport Through Agricultural Food Chains (open access)

Pathway: A Simulation Model of Radionuclide-Transport Through Agricultural Food Chains

PATHWAY simulates the transport of radionuclides from fallout through an agricultural ecosystem. The agro-ecosystem is subdivided into several land management units, each of which is used either for grazing animals, for growing hay, or for growing food crops. The model simulates the transport of radionuclides by both discrete events and continuous, time-dependent processes. The discrete events include tillage of soil, harvest and storage of crops,and deposition of fallout. The continuous processes include the transport of radionuclides due to resuspension, weathering, rain splash, percolation, leaching, adsorption and desorption of radionuclides in the soil, root uptake, foliar absorption, growth and senescence of vegetation, and the ingestion assimilation, and excretion of radionuclides by animals. Preliminary validation studies indicate that the model dynamics and simulated values of radionuclide concentrations in several agricultural products agree well with measured values when the model is driven with site specific data on deposition from world-wide fallout.
Date: January 1, 1982
Creator: Kirchner, T. B.; Whicker, F. W. & Otis, M. D.
Object Type: Article
System: The UNT Digital Library
Cross-Spectral Study of the Spatial Relationships in the North Pacific Sea-Surface Temperature Anomaly Field. Report No. 23 (open access)

Cross-Spectral Study of the Spatial Relationships in the North Pacific Sea-Surface Temperature Anomaly Field. Report No. 23

Cross-spectral analysis is used to examine the dependence of the temporal covariation of sea-surface temperature (SST) anomalies at pairs of spatially separated points in the North Pacific on (1) the time scale of the variations, (2) the relative displacement of the points and (3) their location within the North Pacific basin. Spatial scales considered here range from 1000 kilometers up to the width of the basin. The study focuses on cross-spectral estimates for the interannual frequency band, 0.125-0.75 yr/sup -1/ although estimates for three other bands spanning higher frequencies are also examined.
Date: March 1, 1980
Creator: Middleton, John W.
Object Type: Report
System: The UNT Digital Library