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Mechanistic studies related to the metal catalyzed reduction of carbon monoxide to hydrocarbons. Progress report, April 1, 1979-March 31, 1980

Description: The stoichiometric reactions of metal complexes which parallel probable steps in the metal catalyzed reduction of CO are being investigated. It is hoped that the study of these model reactions will lead to an understanding of the structural factors influencing these individual reaction steps. The information obtained should be useful in the design and discovery of homogeneous catalysts for the reduction of CO to hydrocarbons. We have studied metal formyl complexes which may be involved in the initiation step in CO reduction and have compared metal formyl compounds with metal acetyl compounds. We have found that the structure and kinetic stability of metal formyl compounds are very similar to metal acetyl compounds. However, metal formyl compounds are thermodynamically much less stable than metal acetyl compounds towards decarbonylation. Hydride donation reactions of metal formyl compounds have been discovered. A neutral metal formyl compound has been discovered and its reactions have been investigated. Preparation of (C/sub 5/H/sub 5/)Re(CO)(NO)(CH/sub 2/OH), the first authentic example of a hydroxymethyl metal compound, was accomplished and studies of its reactions with acid, with base, with CO, and with H/sub 2/ were begun.
Date: April 1, 1980
Creator: Casey, C. P.
Partner: UNT Libraries Government Documents Department

Organometallic chemistry of bimetallic compounds

Description: This report consists of six sections: heterobimetallic dihydrides, early-late transition metal heterobimetallic compounds, amphiphilic carbene complexes and hydroxycarbene complexes, diiron compounds with bridging hydrocarbon ligands, diphosphine chelates with natural bite angles near 120 degrees, and synthesis and reactions of M=M compounds. (WET)
Date: July 1, 1991
Creator: Casey, C.P.
Partner: UNT Libraries Government Documents Department

Organometallic chemistry of bimetallic compounds

Description: Hydrogenation of alkynes by the heterobimetallic compound C{sub 5}H{sub 5}(CO){sub 2}Re({mu}-H)Pt(H)(PPh{sub 3}){sub 2} is being studied. The compound C{sub 5}Me{sub 5}(CO){sub 2}Re{double bond}Re(CO){sub 2}C{sub 5}Me{sub 5} was synthesized; its chemistry is being studied. Compounds discovered in a reinvestigation of a spurious report of (C{sub 5}Me{sub 5})Co{double bond}Co(C{sub 5}Me{sub 5}), are being studied. The deuterioformylation of alkenes using wide bite angle phosphines will be studied.
Date: July 1, 1992
Creator: Casey, C.P.
Partner: UNT Libraries Government Documents Department

Argonne National Laboratory, east hazardous waste shipment data validation

Description: At the request of EM-331, the Radioactive Waste Technical Support Program (TSP) is conducting an evaluation of data regarding past hazardous waste shipments from DOE sites to commercial TSDFs. The intent of the evaluation is to find out if, from 1984 to 1991, DOE sites could have shipped hazardous waste contaminated with DOE-added radioactivity to commercial TSDFs not licensed to receive radioactive material. A team visited Argonne National Laboratory, East (ANL-E) to find out if any data existed that would help to make such a determination at ANL-E. The team was unable to find any relevant data. The team interviewed personnel who worked in waste management at the time. All stated that ANL-E did not sample and analyze hazardous waste shipments for radioactivity. Waste generators at ANL-E relied on process knowledge to decide that their waste was not radioactive. Also, any item leaving a building where radioisotopes were used was surveyed using hand-held instrumentation. If radioactivity above the criteria in DOE Order 5400.5 was found, the item was considered radioactive. The only documentation still available is the paperwork filled out by the waste generator and initialed by a health physics technician to show no contamination was found. The team concludes that, since all waste shipped offsite was subjected at least once to health physics instrumentation scans, the waste shipped from ANL-E from 1984 to 1991 may be considered clean.
Date: September 1, 1995
Creator: Casey, C.; Graden, C. & Coveleskie, A.
Partner: UNT Libraries Government Documents Department

Product assurance planning in an environment of increased need for accountability

Description: Projects producing data are too often providing a product that is neither defensible nor usable. Instead of planning for data of known and required quality, managers are too often asking for (and getting) the wrong thing. The problem is a lack of correct planning strategy. A planning strategy to produce usable, defensible data requires communication from the customer to top-level management and from top-level management to the project leader, who must then communicate with the technical experts who will run the project. EPA requires that data quality objectives (DQOs) be derived for RI/FS projects. The DQO process is a top-down planning process that requires two-way communication; some organizations do not have structures suited for implementing DQOs as mandated by EPA. This paper discusses specific tools for imposing structure that will make the DQO process easier to follow for many organizations. The tools include a steering committee, a test design team, and Quality Function Deployment (QFD) matrices. The steering committee is a strong technical forum that can develop technical issues systematically and break down technical issues into manageable pieces that can be stated as test objectives. The test design team plans each test, systematically designs the test matrix, and guides the completion of test documentation that will be used to defend the data collected. QFD matrices are used as tools by both steering committee and test design team as a highly structured, systematic means of relating top-level (customer) requirements to data quality needs and measurement system design.
Date: October 1, 1991
Creator: Esparza, V. & Casey, C.
Partner: UNT Libraries Government Documents Department

Savannah River Site offsite hazardous waste shipment data validation report. Revision 1

Description: The objective of this data validation is to verify that waste shipments reported in response to the US Department of Energy Headquarters data request are properly categorized according to DOE-HQ definitions. This report documents all findings and actions resulting from the independent review of the Savannah River Site data submittal, and provides a summary of the SRS data submittal and data validation strategy. The overall hazardous waste management and offsite release process from 1987--1991 is documented, along with an identification and description of the hazardous waste generation facilities. SRS did not ship any hazardous waste offsite before 1987. Sampling and analysis and surface surveying procedures and techniques used in determining offsite releasability of the shipments are also described in this report. SRS reported 150 manifested waste shipments from 1984 to 1991 that included 4,755 drums or lab packs and 13 tankers. Of these waste items, this report categorizes 4,251 as clean (including 12 tankers), 326 as likely clean, 138 as likely radioactive, and 55 as radioactive (including one tanker). Although outside the original scope of this report, 14 manifests from 1992 and 1993 are included, covering 393 drums or lab packs and seven tankers. From the 1992--1993 shipments, 58 drums or lab packs are categorized as radioactive and 16 drums are categorized as likely radioactive. The remainder are categorized as clean.
Date: May 1, 1995
Creator: Casey, C.; Kudera, D.E.; Page, L.A. & Rohe, M.J.
Partner: UNT Libraries Government Documents Department

Non-equilibrium fission processes in intermediate energy nuclear collisions

Description: We have measured the target fragment yields, angular and energy distributions for the interaction of 12-16 MeV/A/sup 32/S with /sup 165/Ho and /sup 197/Au and for the interaction of 32 and 44 MeV/A /sup 40/Ar with /sup 197/Au. The Au fission fragments associated with the peripheral collision peak in the folding angle distribution originate in a normal, ''slow'' fission process in which statistical equilibrium has been established. At the two lowest projectile energies, the Au fission fragments associated with the central collision peak in the folding angle distribution originate in part from ''fast'' (/tau//approximately//sup /minus/23/s), non-equilibrium processes. Most of the Ho fission fragments originate in non- equilibrium processes. The fast, non-equilibrium process giving rise to these fragments has many of the characteristics of ''fast fission'', but the cross sections associated with these fragments are larger than one would expect from current theories of ''fast fission. '' 14 refs., 8 figs.
Date: April 1, 1989
Creator: Loveland, W.; Casey, C.; Xu, Z.; Seaborg, G.T.; Aleklett, K. & Sihver, L.
Partner: UNT Libraries Government Documents Department