2. Chemistry and Physics of Transuranium Elements
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^/-*-.*£ -'si* ' ORML46Si U04 - Chwsmtry «c. r^? DIVISIWAftMttAL PROGRESS REPOT f FOR l*RI0t> ENDING MAY 20,1970 =*T.V IK* •T' vrV"*"** " a^fr-J *" Sb*-"3*?—i (~ % , 3v "r *& *v - „k 4»- 3 f"£ - v; OAK aiDOI NATIONAL LABORATORY operated by ' f&# ' UNION CARBIDE CORPORATION tor the U.S. ATOMIC ENERGY COMMISSION ^* T>EtflIBXmON OF THIS DOCUMENT TS UNUJMTEO LANK PAGE >>^ _ j.» —— "••* - - fc* *£- in *• tftstteei 3*3** «f AtMrie*. AttitaM* fiwa CS+artn&mem 1m **mm,t •v BLANK PAGE k ORNl-4581 *^>otract Nc. W- 70&«r!o-26 CHEMISTR V DIVISION ANNUAL PROGRESS REPORT for Period Ending May 20.1970 E. H. Taylor, Director SheWon Datz, Associate Director Ralph Livingston, Associate Director B. H. Keteile, Assistant Drector G. E. Moore, Editor of Annual Report LEGAL NOTICE This report was prepared as an account of work sponsored by the United States Gowt- meat. Neither u;? United States nor the United States Atomk Energy Commission, nor any of their employees, nor any of their contractors, subcontractors, or tfces employees, makes any warranty, express or impbec, or assumes any legal Uab'lhy or nsponsibflrty for the accuracy, com pleteness or usefulness of any information, apparatus, product or process disclosed, or represents that its use would not infringe privately owned rights. SEPTEMBER 1970 OAK RIDGE NATIONAL LABORATORY Oak Ridge, Tennessee opyttiby UNION CARBIDE CORPORATION forth* U. G. ATOMIC ENERGY COMMISSION I>i.vn:ir,I.Tl.,N0«- rHJ.SJ;«.(:!:Mr;vT;;,rNfJMm.i BLANK PAGE \ Reports previously issued in this series are as follows: ORNl-2386 Period Ending June 20,1957 ORNL-2584 Period Ending June 20,1958 ORNL-27S2 Period Ending June 20,1959 GRNL-2983 Period Ending June 20,1960 ORNL-3176 Period Ending June 20,1961 ORNL-3320 Period Endi^s June 20, :%2 ORNL-3488 Period EndmgJunc20,I963 ORNL-3679 Period Ending June 20,1964 ORNL-3832 Period Ending May 20,1965 ORNL-3<*94 Period Ending May 20,1966 ORNL-4164 Period Ending May 20,1967 ORNL-4306 Period Ending May 20.1968 ORNL-4437 Period Endir^ May 20,1969 Contents INTRODUCTION ix 1. Nuclear Chemistry A Reexamination of the Decay of 4* na 1 Energy Levels in "Sr from the Decay cf 14.6-hr 86 Y ! Search for the 0* Memler of the Two-Phonon Triplet in '' °Cd 3 Properties of'' °Cd L*veb f'opuhted in the Decay of 69-min ' i0*In 4 Decay of* 37Nd. ,3*N& and13*Pr 6 Search for the Occurrence of * **Sm in Na ure 6 Production of Rare-Earth Alpha Emitters with Energetic 'He PartkSes 7 New Isotopes: ISI Er. ,56Yb.and ,57Yb 10 Alpha-Decay Energy SystematJcs 13 Coulomb ExciUtion of l$4Gd. I5'Gd,and ,6'Er 14 Coulomb Excitation Experiments at OR!C 15 Some Properties of Vibrational Bands in ' s*Gd and ' 5*Gd 15 Ml Admixture in the 2* •* 2* Transition in ' 78Hf 17 Fragment Energy Correlation Measurements for the Fission of *32Th by 8- to 13-MeV Protons 18 Fiagment Energy Correlation Measurements in the Fission of Spontaneously Fissioning Isomers 21 Primordial Radionuclide Abundances. Solar-Proton and Cosmic-Ray Effects, and Ages of Apollo 11 Lunar Samples 23 Radionuclide Concentrations in Apollo 12 Lunar Samples by Nondestructive Gamma-Ray Spectrometry 25 in \ iv 2. Chemistry and Physics of Transuranium Elements Large Yields for Charged-Partide Emission in Reactions of Protons with Actinide Targets 28 Inclusion of Charged-Partide Emission and Fission in Nudear Reaction Calculations 30 The Decay of the Isomers of 240Np and 244Cm snd the Resultant States of 240Pu 32 A Two-Phonon Octupole Vibrational Band in 240Pu 34 Long-lived Spontaneous-Fission Isomerism in 24! Pu? 36 The Fission Thermai-N-uiron Cross Section and Resonance Integral of 2*s Cm, 247Cm, and 249Cf 37 Energy Spectrum of Delayed Neutrons from the Spontaneous Fission of 2S2Cf 40 Alpha-Decay Studies of Neutron Deficient Californium Isotopes 41 States in 2S0Bk Populated in the Alpha Decay of 2$4Es 43 The Neutron Absorption Cross Section of 2S7Fm 4? Studies on the Separation of Recoil Atoms of Heavy Elements 44 K X Rays of the Higher Ac ainides 45 Studies of Pleodiroic Halos 45 Search forSuperheavy Elements in Nature: Ekaptatinum 46 Search for Superheavy Elements in Nature: Ekaosrraum 46 Ekctron-Transter Absorption in Some ActimdHUl) and Laathanide(Iir) Tricydopentadienides and the Standard IMC Cation Oxidation Potentials 48 Theory of the Tetrad Effect in the Lanthanide (IH) and Actinide (III) Series 48 Investigations on the OrganometaBic Chemistry of Actinides and Lanthanides 52 An Improved Synthesis of Tricydopentadienyl Complexes in ftfcroquantities 52 The Formation of Dkydopentadienyfberkelium Chloride 53 Rare-Earth and Americium Chdates 55 Reaction of Aqueous Lanthanide Chloride Solutions with 2,2-Dirnethoxypropane 55 2> Photochemical Reactions Initiated by U02 . Reaction of Butyraldehyde with Diethyl Makate 55 The Crys'al and Molecuhr Structure of Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)- neodymium(III) and -ameridum(II0 56 Trisindenylsamarium: Synthesb and Crystal Structure 57 Crystallographic Studies of Anhydrous Transplutonium Trichlorides 57 The Transuranium Research Laboratory Isotope Separator 58 A Mass Indicator for Sector Isotope Separators 58 A Fail-Closing Valve to Protect ORIC from Radioactive Contamination 59 3. Isotope Chemistry Deuterium Enrichment 62 Fractionation of Carbon Isotopes: The CYANEX System 62 The CYANEX BenchScale Pilot Plan* 63 170 Facility 63 Photochemical Separation of Isotopes 64 Molecular Spectroscopy 65 Isotooic Mass Soectrometrv Preparation of' 3C0 69 4. Radiation Chemistiy Flash Photolysis of Aqueous Nitric Oxide Solutions 70 Pulse Radioiysis of Sodium Nitrate Crystals 70 Pulse Radiolysis of Gases 71 Density and Reflectivity of Amoiphous Ice 72 Reduction of CeriumflV) in Aqueous 4.0 MH2S04 Solutions Induced by Hydrolysis of Peroxydisulfuric Acid 73 Kinetic Evidence for a Primary Yield of N03 Radicals in the Radiolysis of Aqueor* Nitric Acid Solutions 74 Primary Processes in the Radiolys* of Water 75 Energy Transfer and the Radiolysis cf Liquid Aliphatic Carboxyljc Acids 76 RADUTION AND HOT ATOM CHEMISTRY OF INORGANIC CRYSTALLINE SOUDS Chemistry' of' 28I and ' 3°I Recoik in Neutron-Irradiated Crystalline Potassium lod*te and Potsssium Periodate 78 Investigations on the Thermal and Radiolytic Decomposition of Anhydrous Crystalline Potassium Chlorite 78 Further Observations on Products Formed in the Radiolysis of Alkali-Metal Halates and Perhalates by 60Cc Gamma Rays 79 Microanalyiical Method for the Determination of Perbromate !on in the Presence of Macro Amounts of Other Bromine Anions 82 ! Radiolysis of "O-Enricbed Po'ycrystalline KN03 82 5. Organic Chemistry Preparation and Deamination of S-exo-Plienyl-S-hydroxy^-fx^-norboniylamine and 5-ena0-Phenyl-5-hydroxy-2-*x<?-norbomylamine 84 Synthesif ?nd Deamination of 5-e.w-Hydroxy-5-phenyI-2-ewcto-norbornyl2rnine .. 84 Degradation of 2-ow-NorborneoI-' 4C 85 Deamination of 3-e«rfc-Phenyl-3-hydroxyl-2-evo-rf-2-ewt/^-norbornylamine 86 v« Anion Contol of Stereoselectivity During Deaminations 37 Determination of the Stereochemistry of 1,2 Glycols by Nuclear Magnetic Resonance 87 Isothermal Analysis of Graphite-Impregnated Teflon 88 Wet Oxidation of Cellulose 89 6. Physical Chemistry AQUEOUS SYSTEMS Free Energies of Electrolyte Mixtures 90 The Thermodynamic Properties of HCi-NaCi-MgCi2 Mixtures 93 Salt-Induced Critical-Type Transitions in Aqueous Solution. Heats of Dilution of the Lithium and Sodium Halides 97 Variation of Osmotic Coefficients of Aqueous Solutions of Tetraalky!ammonium Halides with Temperature. Thermal and Solute Effects on Solvent Hydrogen Bonding 98 Thermodynamic Studies on Aqueous Solutions of Salts of Carboxylic Acids 99 Tracer Diffusion Coefficients in Aqueous Solutions of Organic Ion Exchanger Model Compounds: Comparison of Aqueous Sodium p-Ethylbenzenesulfonate with Cross-Linked Polystyrenesulfonates 100 Mass Transfer in Ion Exchange Tubes 103 Mass Transfer in Shallow Ion Exchange Beds 104 Swelling of Low-Cross-Linked Ion Exchange Resins 106 Hyperfiltration with Dynamically Formed Membranes 108 Polymer Studies Ill Application of Cross-Flow Filtration to Pollution Control Problems 112 "Polywater," Raman and Infrared Spectra 112 On the Existence of So-Called "Anomalous Water" 115 MOLTEN SALTS AND RELATED NONAQUEOUS SYSTEMS Heat Content of Alkali Metal Fiuoroborates 116 The Solubility of Thorium Metal in Thorium Tetrafluoride 118 The System Yttrium Mctai-Yttrium Trichloride at High Temperatures 119 A Reference Electrode System for Use in Fluoride Melts 119 CALORIMETRY Low-Temperature Heat Capacity of Potassium Hexachlorotechnetate(IV) 121 Enthalpies of Fusion and Transition of Lead Fluoride 122 F»ee Energy and Enthalpy of Formation of K2ReBr6 123 ELECTROCHEMISTRY Kinetics of the Charge and Discharge of the Film of Superpassive Iron 123 T^e Electrochemistry of Technetium 124 vn Electrochemical Behavior of Titanium 125 Chronopotentiometry and Voltammetry of the Ag-AgCl Electrode in Flowing Streams - Experimental 126 Chronopotentiometry and Voltammetry of the Ag-AgCl Electrode in Flowing Stieams - Theoretical 129 Instrument and Cell Development for Rapid Chronopotentiometric Analysis of Chloride Ion 129 7. Chemical Physics NEUTRON AND X-RAY DIFFRACTION Interpretation »-f the Structures of Some Alkaline Earth Chlorides in Terms of Interionic Forces 131 Site Symmetry Restrictions of Thermal-Motion Tensor Coefficients 132 A New Structure-Factor Equation frr Analyzing Skewness and Kurtosis in Thermal-Motion Density Functions 133 A Preliminary Study of the Use of Position-Sensing Detectors in X-Ray and Neutron Diffraction Studies 134 A Least-Squares Method