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RFSS: Lecture 13 Neptunium Chemistry

RFSS: Lecture 13 Neptunium Chemistry. From: Chemistry of actinides http://radchem.nevada.edu/classes/rdch710/lectures%20and%20chapters.html Nuclear properties and isotope production Aqueous phase chemistry Separation and Purification Metallic state Compounds

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RFSS: Lecture 13 Neptunium Chemistry

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  1. RFSS: Lecture 13 Neptunium Chemistry • From: Chemistry of actinides • http://radchem.nevada.edu/classes/rdch710/lectures%20and%20chapters.html • Nuclear properties and isotope production • Aqueous phase chemistry • Separation and Purification • Metallic state • Compounds • Structure and coordination chemistry • Analytical Chemistry

  2. Neptunium nuclear properties • 22 known Np isotopes • 237Np longest lived • Neutron irradiation of U • Consecutive neutron capture on 235U • 238U(n,2n)237U237Np + b- • Alpha decay of 241Am • Used at target for 238Pu production by neutron irradiation • Reaction with 23 MeV and 30 MeV electrons to produce 236Pu • Critical mass is 73 kg • 2500 kg in environment from fallout • 238,239Np • Short half-life, useful radiotracers • From neutron irradiation of 237Np and 238U • 235,236Np • Cyclotron irradiation of 235U • 235U(d,n)236Np • 235U(p,n)235Np • Np isotopes formed in Earth’s crust • Dynamic equilibrium established

  3. http://www.webelements.com/webelements/elements/text/Np/redn.htmlhttp://www.webelements.com/webelements/elements/text/Np/redn.html Np solution chemistry and oxidation states • Np exists from 3+ to 7+ • Stable oxidation state favored by acidity, ligands, Np concentration • 5+ and 6+ forms dioxocations • Redox potentials • Basic solutions • Difficulty in understanding data • Chemical forms of species • Determine ratios of each redox species from XANES • Use Nernst equation to determine potentials

  4. Np solution chemistry • Disproportionation • NpO2+ forms Np4+ and NpO22+ • Favored in high acidity and Np concentration • 2NpO2+ +4 H+Np4+ + NpO22+ + 2H2O • K for reaction increased by addition of complexing reagents • K=4E-7 in 1 M HClO4 and 2.4E-2 in H2SO4 • Suggested reaction rate • -d[NpO2+]/dt=k[NpO2+][H+]2 • Control of redox species • Important consideration for experiments

  5. Np solution chemistry • Oxidation state control • Redox reagents • Adjustment from one redox state to another • Best for reversible couples • No change in oxo group • If oxo group change occurs need to know kinetics • Effort in PUREX process for controlled separation of Np focused on organics • HAN and derivates for Np(VI) reduction • Rate 1st order for Np in excess reductant • 1,1 dimethylhydrazine and tert-butylhydrazine selective of Np(VI) reduction over Pu(IV)

  6. Np solution chemistry • Applied to Np(III) to Np(VII) and coordination complexes • Np(V) spin-orbit coupling for 5f2 • Absorption in 2 M HClO4 • Np(III): 786 nm, e=45Np(IV): 960 nm, e=160 • Np(V): 980 nm, e=395 • Np(VI): 1223 nm, e=45 • Np(VII) only in basic media • NpO65- • 2 long (2.2 Å) and 4 short (1.85 Å) • Absorbance at 412 nm and 620 nm • O pi 5f • Number of vibrational states • Between 681 cm-1 and 2338 cm-1 • Range of complexation constants available • Oxidation state trends same as hydrolysis • Stability trends for inorganic • F->H2PO4->SCN->NO3->Cl->ClO4- • CO32->HPO42->SO42- • NpO2+ forms cation-cation complexes • Fe>In>Sc>Ga>Al

  7. Np solution chemistry • Np hydrolysis • Np(IV)>Np(VI)>Np(III)>Np(V) • For actinides trends with ionic radius • Np(III) • below pH 4 • Stable in acidic solution, oxidizes in air • Potentiometric analysis for determining K • No Ksp data • Np(IV) • hydrolyzes above pH 1 • Tetrahydroxide main solution species in equilibrium with solid based on pH independence of solution species concentration • Np(V) • not hydrolyzed below pH 7 • Np(VI) • below pH 3-4 • Np(VII) • No data available • Most separation methods exploit redox chemistry of Np

  8. PUREX separations • Np(V) not extracted in PUREX • Np(V) slowly disproportionates in high acid • Formation of extractable Np(IV,VI) • Variation of Np behavior based on redox • Need to understand redox kinetics • Reduction of Np(VI) by a range of compounds • Back extraction of Np(V) can be used to separate from Pu and U • Controlled Np(VI) reduction in presence of Pu(III) • Hydrazine derivatives • N-butyraldehyde • Hydroxamic acids • Acetohydroxamic acid shows preferential complexation with tetravalent Np and Pu

  9. Np solvent extraction • Tributylphosphate • NpO2(NO3)2(TBP)2 and Np(NO3)4(TBP)2 are extracted species • Extraction increases with increase concentration of TBP and nitric acid • 1-10 M HNO3 • Separation from other actinides achieved by controlling Np oxidation state • CMPO (Diphenyl-N,N-dibutylcarbamoyl phosphine oxide) • Usually used with TBP • Nitric acid solutions • Separation achieved with oxidation state adjustment • Reduction of Pu and Np by Fe(II) sulfamate • Np(IV) extracted into organic, then removed with carbonate, oxalate, or EDTA

  10. HDEHP Np solvent extraction • HDEHP (Bis(2-ethyl-hexyl)phosphoric acid ) • In 1 M HNO3 with addition of NaNO2 • U, Pu, Np, Am in most stable oxidation states • Np(V) is not extracted • Oxidized to Np(VI) then extracted • Reduced to Np(V) and back extracted into 0.1 M HNO3 • Tri-n-octylamine • Used for separation of Np from environmental samples • Extracted from 10 M HCl • Back extracted with 1 M HCl+0.1 M HF

  11. Metallic Np • First synthesis from NpF3 with Ba at 1473 K • Current methods • NpF4with excess Ca • NpO2 in a molten salt process • Can also use Cs2NpO2Cl4 and Cs3NpO2Cl4 • LiCl/KCl as electrolyte at 723 K • NpC reduction with Ta followed by volatilization of Np • Electrodepostion from aqueous solution • Amalgamation with Hg from 1 M CH3COOH and 0.3 M CH3COONa at pH 3.5 • Distillation to remove Hg

  12. Metallic Np data • Melting point 912 K • Boiling point estimated at 4447 K • Density 19.38 g/mL • Three metallic forms • Enthalpies and entropies of transitions • ab • Transition T 553 K • ΔS=10.1 JK-1mol-1 • ΔH=5.607 kJmol-1 • bg • Transition T 856 K • ΔS=6.23 JK-1mol-1 • ΔH=5.272 kJmol-1

  13. Neptunium oxides • Two known anhydrous oxides • Np2O5 and NpO2 • NpO2 • From thermal decomposition of a range of Np compounds • Isostructural with other actinides • Fluorite lattice parameter • Stable over a range of temperatures • Phase change from fcc to orthorhombic at 33 GPa • Stable to 2.84 MPa and 673 K • Np2O5 • From thermal decomposition of NpO3.H2O or NpO2OH(am) • Np2O5 decomposes to NpO2 from 693 K to 970 K

  14. Np halides • Fluorides • NpF3, NpF4, NpF5, and NpF6 • Prepared from reactions with HF at 773 K • NpO2+1/2H2+3HFNpF3 + 2H2O • NpF3+1/4O2+HF NpF4 + 1/2H2O • NpO2+4HFNpF4 + 2H2O • 10NpF6+I210NpF5+2IF5 • Other route where Np(VI) is reduced • NpF6 is volatile • Melting point at 327.8 K • Higher vapor pressure that U and Pu compound • Can form Np(V) species upon reaction with NaF • NpF6+3NaFNa3NpF8 + 1/2F2 • U will stay as hexavalent compound • Range of monovalent species with Np fluorides • Synthesis similar to U compound • NpO2F2 intermediate species • KrF2 used as fluorinating agent for some synthetic routes

  15. Np halides • NpCl4 • From the reaction of NpO2 with CCl4 • Addition of H2 yields NpCl3 • Similar to U reactions • Several melting point reported • Heating for NpOCl2 • NpBr4 • NpO2 with AlBr3 • Reaction of elements • Same for AlI3 for NpI3 • Synthesis reactions similar to U species • Measured data on Np compounds limited

  16. Np coordination compounds • Interests driven from different Np oxidation states and systematic studies of actinides • Np3+ • Very little data • Instable in aqueous solutions under air • Trivalent state stabilized by sodium formaldehyde sulfoxylate (NaHSO2.CH2O.2H2O) • Formation of oxalate and salicylate species • 2 Np, 3 ligands • No O2 in synthesis • Np4+ • Et4NNp(NCS)8 • Isostructural with U complex • Range of nitrate compounds • Np(V) • Exhibit cation-cation interaction • Na4(NpO4)2C12O12 • Dissolve neptunium hydroxide in solution with mellitic acid • Adjust to pH 6.5 with base • Slowly evaporate

  17. Np coordination compounds • Np(VI) • Some simple synthesis • Oxalic acid to Np(VI) solutions • Reduction of Np over time • Ammonium carbonate species • Excess (NH4)2CO3 to nitrate solutions of Np(VI) • Np(VII) • Some disagreement on exact species • Mixed species with Co, Li, NH3 and OH

  18. CP Np Organometallic compounds • Mainly cyclopentadienyl and cyclooctatetraenyl compounds • Np cyclopentadienyl • Reduction of Np4+ complex with Na • Np(C5H5)3Cl + Na  Np(C5H5)3.3THF + NaCl • Difficult to remove THF • Heating and vacuum • Np4+ • NpCl4+4KC5H5Np(C5H5)4+4KCl • Dissolves in benzene and THF • Less sensitive to H2O and O2 than tetravalent Pu and Am compound • Halide salt of Np compound reported • NpX4 + 3 KC5H5Np(C5H5)3X+3KX • Can use as starting material and replace X with ligands • Inorganic (other halides); NC4H4-, N2C3H3-, CH-

  19. Analytical methods • Environmental levels • General levels 1E-15 g/L • Elevated levels up to 1E-11 g/L • Radiometric methods • Alpha • 2.6E7 Bq/g • Isolation from seawater • Hydroxide co-precipitation, ion-exchange, LaF3, solvent extraction with HTTA • Liquid scintillation • Activation analysis • Formation of 238Np • 170 barns, 2.117 day half life for 238Np • 500 more sensitive than alpha spectroscopy

  20. Analytical methods • Spectrophotometric methods • Direct absorbance • Detection limit in M (1 cm cell, 0.02 absorbance) • Np(III) 5E-4, Np(IV) 1E-4, Np(V) 5E-5, Np(VI) 5E-4 • Laser induced photoacoustic spectroscopy (LIPAS) • Increase factor by over an order of magnitude • Indicator dyes • Fluorescence • New work in tetrachlorides and solids • Luminescence at 651 nm and 663 nm from Np in CaF2 at 77 K • X-ray fluorescence • Mass spectroscopy

  21. Analytical methods: 237Np Moessbauer spectroscopy • 68 ns excited state lifetime • Isomer shift suitable for analysis of chemical bonds • Can record radiation spectrum from absorber • 60 keV from 241Am • Shift correlated with oxidation state and number of 5f electrons present

  22. Review • Oxidation states of Np in solution • Role of different oxidation states in separations • Np separations • Distribution with ligands in solvent extraction • Synthesis of Np metal • Np oxides and fluorides • Coordination and organometallic compounds • Analytical methods

  23. Homework question • What are the forms of solid binary neptunium oxides compounds? • Provide comments on blog • Bring to next class or submit by e-mail

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