DOCSLIB.ORG

Technetium Sulfide: Fundamental Chemistry for Waste Storage Form's

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Technetium Sulfide: Fundamental Chemistry for Waste Storage Form's UNLV Theses, Dissertations, Professional Papers, and Capstones 12-1-2014 Technetium Sulfide: undamentalF Chemistry for Waste Storage Form's Application Maryline Ghislaine Ferrier University of Nevada, Las Vegas Follow this and additional works at: https://digitalscholarship.unlv.edu/thesesdissertations Part of the Radiochemistry Commons Repository Citation Ferrier, Maryline Ghislaine, "Technetium Sulfide: undamentalF Chemistry for Waste Storage Form's Application" (2014). UNLV Theses, Dissertations, Professional Papers, and Capstones. 2259. http://dx.doi.org/10.34917/7048578 This Dissertation is protected by copyright and/or related rights. It has been brought to you by Digital Scholarship@UNLV with permission from the rights-holder(s). You are free to use this Dissertation in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s) directly, unless additional rights are indicated by a Creative Commons license in the record and/or on the work itself. This Dissertation has been accepted for inclusion in UNLV Theses, Dissertations, Professional Papers, and Capstones by an authorized administrator of Digital Scholarship@UNLV. For more information, please contact [email protected]. TECHNETIUM SULFIDE: FUNDAMENTAL CHEMISTRY FOR WASTE STORAGE FORM’S APPLICATION By Maryline Ferrier Bachelor of Science in Chemistry Institut National des Sciences Appliquées de Rouen, France 2006 Master of Science in Chemistry Institut National des Sciences Appliquées de Rouen, France 2008 A dissertation submitted in partial fulfillment of the requirements for the Doctor of Philosophy - Radiochemistry Department of Chemistry College of Sciences The Graduate College University of Nevada, Las Vegas December 2014 Copyright by Maryline Ferrier, 2015 All Rights Reserved We recommend the dissertation prepared under our supervision by Maryline Ferrier entitled Technetium Sulfide: Fundamental Chemistry for Waste Storage Form’s Application is approved in partial fulfillment of the requirements for the degree of Doctor of Philosophy - Radiochemistry Department of Chemistry Kenneth Czerwinski, Ph.D., Committee Chair Frederic Poineau, Ph.D., Committee Member Alfred Sattelberger, Ph.D., Committee Member Ralf Sudowe, Ph.D., Graduate College Representative Kathryn Hausbeck Korgan, Ph.D., Interim Dean of the Graduate College December 2014 ii ABSTRACT Technetium Sulfide: Fundamental Chemistry for Waste Storage Form’s Application By Maryline Ferrier Dr. Kenneth Czerwinski, Advisory Committee Chair Professor of Chemistry University of Nevada, Las Vegas Technetium is the lightest radioelement. Thirty four isotopes are known, the two 99m 99 99m main isotopes being Tc and Tc. The isotope Tc (T1/2 = 6.01 hours, γ = 140.5 keV) is 99 5 used for diagnostics in nuclear medicine, while Tc (T1/2 = 2.13 x 10 years, β = 294 keV) is a major fission product of the nuclear industry with about 6% yield from 235U by thermal neutrons. Technetium exhibits nine oxidation state (-I to VII) and an extensive set of mixed oxidation states due to polynuclear complex formation. Under oxidizing conditions between pH 0 and 14, the aqueous chemistry of Tc(VII) is dominated by the - TcO4 which is highly mobile in the environment. The high production rate, mobility, long half-life and radiotoxicity make 99Tc an isotope of concern in nuclear waste management. Despite its important role in radiopharmaceuticals and in the nuclear fuel cycle, the fundamental chemistry of technetium is not as well developed as that of the iii neighboring transition metals; one of the most striking examples being its sulfide chemistry. Only two technetium sulfide compounds had been reported: Tc2S7 and TcS2. Even though technetium heptasulfide was studied, with some uncertainty in its solid state characterization, the speciation of the supernate during the reaction had never been explored. Reactions of pertechnetate in various sulfuric acid molarities with hydrogen sulfide were studied. Precipitates, Tc2S7, were analyzed by Energy Dispersive X-ray (EDX) and X-ray Absorption Fine Structure (XAFS) spectroscopy and compared to previous studies and other transition metal sulfide characterizations. Analyses of the supernates by UV-Visible and XAFS spectroscopies were able to suggest speciation of pertechnetate in sulfuric acid under reducing conditions. While TcS2 has been unambiguously characterized and synthesized, new routes of synthesis were explored and the solids obtained were analyzed by XAFS spectroscopy. Synthesis of ternary technetium sulfides in acetonitrile with bis(trimethylsilyl) sulfide was also examined. Those studies related to the synthesis and behavior of different technetium materials will permit an increase in the scientific knowledge related to technetium sulfide chemistry. They will improve the fundamental understanding of behavior of 99Tc in repository conditions, which are potentially varied, and thus improve waste forms development. iv ACKNOWLEDGMENTS This work would not have been possible without the help of my advisor, Pr. Kenneth Ronald Czerwinski, who I thank for being a great advisor these few years. I would like also to thank him and all the committee members for giving me the opportunity to participate to the radiochemistry program at UNLV. It was a real pleasure to be a part of this team again. Thank you to my committee members for their inputs and suggestions. Specially, I would like to thank Dr. Frédéric Poineau, research professor within Ken’s team for providing me with useful and helpful assistance and contribution throughout my laboratory work. I also would like to thank Dr. Alfred Sattelberger for his help by giving me new ideas to explore and reviewing the papers for publication. I appreciate the radiochemistry group as a whole, and especially Julie Bertoia and Trevor Low for making the laboratory works efficiently. And thank you to my labmates for their advice, help and friendship. Finally, thank you to my family and friends for their support during all of those hours of doubt and stress. v TABLE OF CONTENTS ABSTRACT ...................................................................................................................... iii ACKNOWLEDGMENTS .................................................................................................... v TABLE OF CONTENTS..................................................................................................... vi LIST OF TABLES .............................................................................................................. xi LIST OF FIGURES ......................................................................................................... xvii CHAPTER 1: INTRODUCTION ......................................................................................... 1 1.1 Background....................................................................................................... 1 1.2 Technetium background .................................................................................. 5 1.3 Sulfur Chemistry ............................................................................................... 8 1.4 Transition metal sulfides ................................................................................ 12 1.4.1 Tetrathio-metallates ............................................................................... 13 1.4.2 d0 configuration for transition metal sulfides ......................................... 14 1.4.3 Disulfides ................................................................................................. 15 1.4.4 Technetium sulfides ................................................................................ 17 1.4.5 Transition metals comparison ................................................................. 19 1.5 Redox potential for manganese, technetium and rhenium .......................... 21 CHAPTER 2: Materials and Methods ........................................................................... 23 vi 2.1 Materials and methods used ......................................................................... 23 2.1.1 Synthesis of starting compounds ............................................................ 24 2.1.1.1 Tc(VII) ............................................................................................... 24 2.1.1.1.1 Preparation of NH4TcO4 ............................................................ 25 2.1.1.1.2 Preparation of KTcO4 ................................................................. 25 2.1.1.1.3 Preparation of (Bu4N)TcO4 ........................................................ 26 2.1.1.2 Tc(VI) ................................................................................................ 26 2.1.1.3 Tc(V) ................................................................................................. 27 2.1.1.4 Tc(IV) ................................................................................................ 28 2.1.1.4.1 Preparation of K2TcCl6 ............................................................... 28 2.1.1.4.2 Preparation of TcCl4 .................................................................. 29 2.1.1.5 Tc(0) .................................................................................................. 31 2.2 Characterization techniques .......................................................................... 32 2.2.1 Primary techniques ................................................................................
Load more

Recommended publications
  • IR-3 Elements and Groups of Elements (March 04)
    1 IR-3 Elements and Groups of Elements (March 04) CONTENTS IR-3.1 Names and symbols of atoms IR-3.1.1 Systematic nomenclature and symbols for new elements IR-3.2 Indication of mass, charge and atomic number using indexes (subscripts and superscripts) IR-3.3 Isotopes IR-3.3.1 Isotopes of an element IR-3.3.2 Isotopes of hydrogen IR-3.4 Elements (or elementary substances) IR-3.4.1 Name of an element of infinite or indefinite molecular formula or structure IR-3.4.2 Name of allotropes of definite molecular formula IR-3.5 Allotropic modifications IR-3.5.1 Allotropes IR-3.5.2 Allotropic modifications constituted of discrete molecules IR-3.5.3 Crystalline allotropic modifications of an element IR-3.5.4 Solid amorphous modifications and commonly recognized allotropes of indefinite structure IR-3.6 Groups of elements IR-3.6.1 Groups of elements in the Periodic Table and their subdivisions IR-3.6.2 Collective names of groups of like elements IR-3.7 References IR-3.1 NAMES AND SYMBOLS OF ATOMS The origins of the names of some chemical elements, for example antimony, are lost in antiquity. Other elements recognised (or discovered) during the past three centuries were named according to various associations of origin, physical or chemical properties, etc., and more recently to commemorate the names of eminent scientists. In the past, some elements were given two names because two groups claimed to have discovered them. To avoid such confusion it was decided in 1947 that after the existence of a new element had been proved beyond reasonable doubt, discoverers had the right to IUPACsuggest a nameProvisional to IUPAC, but that only Recommendations the Commission on Nomenclature of Inorganic Chemistry (CNIC) could make a recommendation to the IUPAC Council to make the final Page 1 of 9 DRAFT 2 April 2004 2 decision.
    [Show full text]
  • China and Weapons of Mass Destruction: Implications for the United States
    China and Weapons of Mass Destruction: Implications for the United States China and Weapons of Mass Destruction: Implications for the United States 5 November 1999 This conference was sponsored by the National Intelligence Council and Federal Research Division. The views expressed in this report are those of individuals and do not represent official US intelligence or policy positions. The NIC routinely sponsors such unclassified conferences with outside experts to gain knowledge and insight to sharpen the level of debate on critical issues. Introduction | Schedule | Papers | Appendix I | Appendix II | Appendix III | Appendix IV Introduction This conference document includes papers produced by distinguished experts on China's weapons-of-mass-destruction (WMD) programs. The seven papers were complemented by commentaries and general discussions among the 40 specialists at the proceedings. The main topics of discussion included: ● The development of China's nuclear forces. ● China's development of chemical and biological weapons. ● China's involvement in the proliferation of WMD. ● China's development of missile delivery systems. ● The implications of these developments for the United States. Interest in China's WMD stems in part from its international agreements and obligations. China is a party to the International Atomic Energy Agency (IAEA), the Treaty on the Non-Proliferation of Nuclear Weapons (NPT), the Zangger Committee, and the Chemical Weapons Convention (CWC) and has signed but not ratified the Comprehensive Nuclear Test Ban Treaty (CTBT). China is not a member of the Australia Group, the Wassenaar Arrangement, the Nuclear Suppliers Group, or the Missile Technology Control Regime (MTCR), although it has agreed to abide by the latter (which is not an international agreement and lacks legal authority).
    [Show full text]
  • New Minerals Approved Bythe Ima Commission on New
    NEW MINERALS APPROVED BY THE IMA COMMISSION ON NEW MINERALS AND MINERAL NAMES ALLABOGDANITE, (Fe,Ni)l Allabogdanite, a mineral dimorphous with barringerite, was discovered in the Onello iron meteorite (Ni-rich ataxite) found in 1997 in the alluvium of the Bol'shoy Dolguchan River, a tributary of the Onello River, Aldan River basin, South Yakutia (Republic of Sakha- Yakutia), Russia. The mineral occurs as light straw-yellow, with strong metallic luster, lamellar crystals up to 0.0 I x 0.1 x 0.4 rnrn, typically twinned, in plessite. Associated minerals are nickel phosphide, schreibersite, awaruite and graphite (Britvin e.a., 2002b). Name: in honour of Alia Nikolaevna BOG DAN OVA (1947-2004), Russian crys- tallographer, for her contribution to the study of new minerals; Geological Institute of Kola Science Center of Russian Academy of Sciences, Apatity. fMA No.: 2000-038. TS: PU 1/18632. ALLOCHALCOSELITE, Cu+Cu~+PbOZ(Se03)P5 Allochalcoselite was found in the fumarole products of the Second cinder cone, Northern Breakthrought of the Tolbachik Main Fracture Eruption (1975-1976), Tolbachik Volcano, Kamchatka, Russia. It occurs as transparent dark brown pris- matic crystals up to 0.1 mm long. Associated minerals are cotunnite, sofiite, ilin- skite, georgbokiite and burn site (Vergasova e.a., 2005). Name: for the chemical composition: presence of selenium and different oxidation states of copper, from the Greek aA.Ao~(different) and xaAxo~ (copper). fMA No.: 2004-025. TS: no reliable information. ALSAKHAROVITE-Zn, NaSrKZn(Ti,Nb)JSi401ZJz(0,OH)4·7HzO photo 1 Labuntsovite group Alsakharovite-Zn was discovered in the Pegmatite #45, Lepkhe-Nel'm MI.
    [Show full text]
  • LTS Research Laboratories, Inc. Safety Data Sheet Rhenium Sulfide ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– 1
    LTS Research Laboratories, Inc. Safety Data Sheet Rhenium Sulfide ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– 1. Product and Company Identification ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– Trade Name: Rhenium Sulfide Chemical Formula: ReS2 Recommended Use: Scientific research and development Manufacturer/Supplier: LTS Research Laboratories, Inc. Street: 37 Ramland Road City: Orangeburg State: New York Zip Code: 10962 Country: USA Tel #: 855-587-2436 / 855-lts-chem 24-Hour Emergency Contact: 800-424-9300 (US & Canada) +1-703-527-3887 (International) ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– 2. Hazards Identification ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– Signal Word: None Hazard Statements: None Precautionary Statements: None HMIS Health Ratings (0-4): Health: 1 Flammability: 0 Physical: 1 ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– 3. Composition ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– Chemical Family: Ceramic Additional Names: Rhenium (IV) sulfide, Rhenium disulfide Rhenium Sulfide (ReS2): Percentage: 100 wt% CAS #: 12038-63-0 EC #: 234-873-3 ––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––– 4. First Aid Procedures –––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
    [Show full text]
  • Standard Thermodynamic Properties of Chemical
    STANDARD THERMODYNAMIC PROPERTIES OF CHEMICAL SUBSTANCES ∆ ° –1 ∆ ° –1 ° –1 –1 –1 –1 Molecular fH /kJ mol fG /kJ mol S /J mol K Cp/J mol K formula Name Crys. Liq. Gas Crys. Liq. Gas Crys. Liq. Gas Crys. Liq. Gas Ac Actinium 0.0 406.0 366.0 56.5 188.1 27.2 20.8 Ag Silver 0.0 284.9 246.0 42.6 173.0 25.4 20.8 AgBr Silver(I) bromide -100.4 -96.9 107.1 52.4 AgBrO3 Silver(I) bromate -10.5 71.3 151.9 AgCl Silver(I) chloride -127.0 -109.8 96.3 50.8 AgClO3 Silver(I) chlorate -30.3 64.5 142.0 AgClO4 Silver(I) perchlorate -31.1 AgF Silver(I) fluoride -204.6 AgF2 Silver(II) fluoride -360.0 AgI Silver(I) iodide -61.8 -66.2 115.5 56.8 AgIO3 Silver(I) iodate -171.1 -93.7 149.4 102.9 AgNO3 Silver(I) nitrate -124.4 -33.4 140.9 93.1 Ag2 Disilver 410.0 358.8 257.1 37.0 Ag2CrO4 Silver(I) chromate -731.7 -641.8 217.6 142.3 Ag2O Silver(I) oxide -31.1 -11.2 121.3 65.9 Ag2O2 Silver(II) oxide -24.3 27.6 117.0 88.0 Ag2O3 Silver(III) oxide 33.9 121.4 100.0 Ag2O4S Silver(I) sulfate -715.9 -618.4 200.4 131.4 Ag2S Silver(I) sulfide (argentite) -32.6 -40.7 144.0 76.5 Al Aluminum 0.0 330.0 289.4 28.3 164.6 24.4 21.4 AlB3H12 Aluminum borohydride -16.3 13.0 145.0 147.0 289.1 379.2 194.6 AlBr Aluminum monobromide -4.0 -42.0 239.5 35.6 AlBr3 Aluminum tribromide -527.2 -425.1 180.2 100.6 AlCl Aluminum monochloride -47.7 -74.1 228.1 35.0 AlCl2 Aluminum dichloride -331.0 AlCl3 Aluminum trichloride -704.2 -583.2 -628.8 109.3 91.1 AlF Aluminum monofluoride -258.2 -283.7 215.0 31.9 AlF3 Aluminum trifluoride -1510.4 -1204.6 -1431.1 -1188.2 66.5 277.1 75.1 62.6 AlF4Na Sodium tetrafluoroaluminate
    [Show full text]
  • The WMS Model
    Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is © the Owner Societies 2018 S-1 ELECTRONIC SUPPLEMENTARY INFORMATION OCT. 8, 2018 Extrapolation of High-Order Correlation Energies: The WMS Model Yan Zhao,a Lixue Xia,a Xiaobin Liao,a Qiu He,a Maria X. Zhao,b and Donald G. Truhlarc aState Key Laboratory of Silicate Materials for Architectures,International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, People’s Republic of China. bLynbrook High School, 1280 Johnson Avenue, San Jose, California 95129 cDepartment of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, MN 55455-0431 TABLE OF CONTENTS Table S1: Calculated classical barrier heights (kcal/mol) for the DBH24-W4 database S-2 Table S2: RMSE of the scalar relativistic contribution in WMS (kcal/mol) S-3 Table S3: RMSE of the composite methods for the W4-17 database (kcal/mol) S-4 Table S4: Calculated Born-Oppenheimer atomization energy (kcal/mol) for the W4-17 database S-5 Table S5: Example input file for a WMS calculation: the H2O molecule S-11 Table S6: Example input file for a WMS calculation: the CH3 radical S-12 Table S7. perl scripts for performing WMS calculations S-13 S-2 Table S1: Calculated classical barrier heights (kcal/mol) for the DBH24-W4 database (The ZPE contributions are excluded.) Reactions Best Est. WMS Hydrogen Atom Transfers ! ∆E! 6.35 6.25 OH + CH4 → CH3 + H2O ! ∆E! 19.26 19.28 ! ∆E! 10.77 10.88 H + OH → O + H2 ! ∆E! 13.17
    [Show full text]
  • Reference Guide to Odor Thresholds for Hazardous Air Pollutants Listed in the Clean Air Act Amendments of 1990
    United States Office of Research and EPAl600!R-92/047 Environmental Protection Development March 1992 Agency Washington, DC 20460 PB92-239516 SEPA Reference Guide to Odor Thresholds for Hazardous Air Pollutants Listed in the Clean Air Act Amendments of 1990 ---AIR RISK INFORMATION SUPPORT CENTER ---- REPRODUCED BY U.s. DEPARTMENT OF COMMERCE NATIONAL TECHNICAL INFORMATION SERVICE SPRINGFIELD, VA 22161 TECHNICAL RE~RT DATA (Pkae read Instructions 011 the ,e~ene befort compler' 1. REPORT NO. 2 ~. PB92-239516 1 • EPA/6001R-92/047 <t. TITLE ANO SUBTITLE 5. REPORT DATE March 1992 Reference Guide to Odor Thresholds for Hazard- ous Air Pollutants Listed in the Clean Air Act IS. PERFORMING ORGANIZATION CODE Amendments of 1990. 600/23 7. AUTHOR(S) I. PERFORMING ORGANIZATION REPORT NO. See List of Authors ECAO-R-0397 19. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT NO. Environmental Criteria and Assessment Office (MD-52) Office of Health and Environmental Assessment, ORD 11. CONTRACT/QRANT NO. U.S. Environmental Protection Agency Research Triangle Park, North Carolina 27711 12. SPONSORING AGENCY NAME AND ADDRESS 13. TYPE OF REPORT AND PERIOD COVERED Office of Health and Environmental Assessment (RD-689) Office of Research and Development 1<t. SPONSORING AGENCY CODE U. S. Environmental Protection Agency vJashington, D.C. 20460 600/21 1S. SUPPLEMENTARY NOTES 16. ABSTRACT In response to numerous requests for information related to odor thresholds, this document was prepared by the Air Risk Information Support Center in its role in providing technical assistance to State and Local government agencies on risk assessment of air pollutants. A discussion of basic concepts related to olfactory function and the measurement of odor thresholds is presented.
    [Show full text]
  • Hydrogen Bridging in the Compounds X2h (X = Al, Si, P, S
    HYDROGEN BRIDGING IN THE COMPOUNDS X 2H (X = AL, SI, P, S) by ZACHARY THOMAS OWENS (Under the Direction of Henry F. Schaefer III) ABSTRACT X2H hydrides (X=Al, Si, P, and S) have been investigated using coupled cluster theory with single, double, and triple excitations, the latter incorporated as a perturbative correction [CCSD(T)]. These were performed utilizing a series of correlation-consistent basis sets augmented with diffuse functions (aug-cc-pVXZ, X = D, T, Q). Al 2H and Si 2H are determined to have H-bridged C 2v structures in their ground states: the Al 2H ground 2 state is of B1 symmetry with an Al-H-Al angle of 87.6°, and the Si 2H ground state is of 2 A1 symmetry with a Si-H-Si angle of 79.8°. However, P 2H and S 2H have non-bridged, 2 bent C s structures: the P 2H ground state is of A' symmetry with a P-P-H angle of 97.0°, 2 and the S 2H ground state is of A'' symmetry with an S-S-H angle of 93.2°. Ground state geometries, vibrational frequencies, and electron affinities have been computed at all levels of theory. INDEX WORDS: computational chemistry, coupled cluster, hydrogen bridging, quantum chemistry, Al2H, Si2H, P2H, S2H, electron affinities HYDROGEN BRIDGING IN THE COMPOUNDS X 2H (X = AL, SI, P, S) by ZACHARY THOMAS OWENS B. S., University of Toledo, 2002 A Thesis Submitted to the Graduate Faculty of The University of Georgia in Partial Fulfillment of the Requirements for the Degree MASTER OF SCIENCE ATHENS, GEORGIA 2006 © 2006 Zachary Thomas Owens All Rights Reserved HYDROGEN BRIDGING IN THE COMPOUNDS X 2H (X = AL, SI, P, S) by ZACHARY THOMAS OWENS Major Professor: Henry F.
    [Show full text]
  • Quantum Mechanical Calculations Of: I
    Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1968 Quantum Mechanical Calculations Of: I. Azabenzenes, II. Ethylene; IIi. Hydrogen-Disulfide. Brent J. Bertus Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Bertus, Brent J., "Quantum Mechanical Calculations Of: I. Azabenzenes, II. Ethylene; IIi. Hydrogen-Disulfide." (1968). LSU Historical Dissertations and Theses. 1378. https://digitalcommons.lsu.edu/gradschool_disstheses/1378 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. This dissertation has been microfilmed exactly as received 68-10, 720 BERTUS, Brent J ., 1939- QUANTUM MECHANICAL CALCULATIONS OF: L AZABENZENES; IL ETHYLENE; m. HYDROGEN DISULFIDE. Louisiana State University and Agricultural and Mechanical College, Ph. D., 1968 Chemistry, physical University Microfilms, Inc., Ann Arbor, Michigan QUANTUM MECHANICAL CALCULATIONS OF I. AZABENZENES II. ETHYLENE III. HYDROGEN DISULFIDE A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Brent J. Bertus B.S., Louisiana State University in New Orleans, 1963 January, 1968 ACKNOWLEDGMENT The author wishes to acknowledge the inspiration of Dr. S.P. McGlynn, for it was through Dr. McGlynn that the direction and environment necessary for this work was achieved. A debt of gratitude must be expressed to Dr.
    [Show full text]
  • Sulfur Oxygenase Reductases - a Structural and Biochemical Perspective
    Sulfur Oxygenase Reductases - A Structural and Biochemical Perspective vom Fachbereich Biologie der Technischen Universität Darmstadt zur Erlangung des akademischen Grades eines Doctor rerum naturalium genehmigte Dissertation vorgelegt von Dipl. Biol. Andreas Veith aus Seeheim-Jugenheim 1. Referent: Dr. habil. Arnulf Kletzin 2. Referent: Prof. Dr. Felicitas Pfeifer Eingereicht am 21.07.2011 Tag der mündlichen Prüfung: 16.09.2011 Darmstadt 2011 D 17 "Trying to determine the structure of a protein by UV spectroscopy was like trying to determine the structure of a piano by listening to the sound it made while being dropped down a flight of stairs." -- Francis Crick Die vorliegende Arbeit wurde als Promotionsarbeit am Institut für Mikrobiologie und Genetik des Fachbereichs Biologie der Technischen Universität Darmstadt unter Leitung von Herrn Dr. Arnulf Kletzin in der Abteilung von Frau Prof. Felicitas Pfeifer im Zeitraum von Mai 2007 bis Juli 2011 angefertigt. Ein Teil der vorliegenden Arbeit wurde in Portugal am Instituto de Tecnologia Químicia e Biológica, Universidade Nova de Lisboa (ITQB/UNL), Oeiras, Portugal in der Arbeitsgruppe von Dr. Carlos Frazão, Dr. Cláudio M. Gomes und Prof. Miguel Teixeira im Rahmen einer Kooperation durchgeführt. Ehrenwörtliche Erklärung Ich erkläre hiermit ehrenwörtlich, dass ich die vorliegende Arbeit selbstständig angefertigt habe. Sämtliche aus fremden Quellen direkt oder indirekt übernommenen Gedanken sind als solche kenntlich gemacht. Die Arbeit wurde bisher keiner anderen Prüfungsbehörde vorgelegt und noch nicht veröffentlicht. Darmstadt, den 21.07.2011 Andreas Veith Acknowledgements First and foremost I would like to thank my supervisor Dr. Arnulf Kletzin for giving me the opportunity to step into the fascinating world of proteins.
    [Show full text]
  • ABSTRACT LUISO, SALVATORE. Co/Fe-Doped
    ABSTRACT LUISO, SALVATORE. Co/Fe-doped MoS2 Nanoparticles on Carbon Support as a Catalyst for Hydrogen Evolution Reaction. (Under the direction of Dr. Peter S. Fedkiw). The challenge to replace fossil fuel with clean and renewable energies has led the scientific community to research alternative sources of energy. Because of the low- environmental impact and high-specific energy of hydrogen, interest in sustainable ways of producing it has increased. Water electrolysis is the best method to generate high-purity hydrogen without pollutants, but it is an energy-intensive route. The existing platinum (Pt) catalysts are highly efficient, but the cost and rarity of Pt limits its use. Therefore, seeking high-efficient and cost-effective catalyst for mass production of hydrogen is critical to the utilization of hydrogen energy. In 2005, Nørskov et al. reported that molybdenum disulfide (MoS2) showed good activity for hydrogen evolution reaction (HER). The work in this thesis aims to develop high-efficient molybdenum sulfide catalysts. Molybdenum trisulfide (MoS3) was synthesized from acidification of ammonium tetrathiomolybdate [(NH4)2MoS4] with the addition of sodium sulfide (Na2S∙9H2O) to the reaction mixture. The synthesis parameters such as carbon support, S:Mo atomic ratio, solvent (H2O, ethylene glycol (EG)), dopants (Co/Fe) and pH were systematically studied. The physical and chemical properties of the prepared catalysts were characterized by microscopy (SEM, TEM), x-ray spectroscopy (XPS), and elemental analysis and mapping (ICP, CHNS, STEM). The electrochemical activity toward HER was studied using voltammetry and impedance tests. In the first section of the study, MoS3 nanoparticles were synthesized on three carbon supports (graphene nanoplatelets (GNP), Ketjenblack EJ-300 and Vulcan XC 72R) with various S:Mo atomic ratios (4:1, 5:1, 7:1, 10:1) using H2O and EG as solvents.
    [Show full text]
  • List of Lists
    United States Office of Solid Waste EPA 550-B-10-001 Environmental Protection and Emergency Response May 2010 Agency www.epa.gov/emergencies LIST OF LISTS Consolidated List of Chemicals Subject to the Emergency Planning and Community Right- To-Know Act (EPCRA), Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) and Section 112(r) of the Clean Air Act • EPCRA Section 302 Extremely Hazardous Substances • CERCLA Hazardous Substances • EPCRA Section 313 Toxic Chemicals • CAA 112(r) Regulated Chemicals For Accidental Release Prevention Office of Emergency Management This page intentionally left blank. TABLE OF CONTENTS Page Introduction................................................................................................................................................ i List of Lists – Conslidated List of Chemicals (by CAS #) Subject to the Emergency Planning and Community Right-to-Know Act (EPCRA), Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) and Section 112(r) of the Clean Air Act ................................................. 1 Appendix A: Alphabetical Listing of Consolidated List ..................................................................... A-1 Appendix B: Radionuclides Listed Under CERCLA .......................................................................... B-1 Appendix C: RCRA Waste Streams and Unlisted Hazardous Wastes................................................ C-1 This page intentionally left blank. LIST OF LISTS Consolidated List of Chemicals
    [Show full text]