Synthesis, structure, and reactivity of high oxidation state silver fluorides and related compounds

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This thesis has been largely concerned with defining the oxidizing power of Ag(III) and Ag(II) in anhydrous hydrogen fluoride (aHF) solution. Emphasis was on cationic species, since in a cation the electronegativity of a given oxidation state is greatest. Cationic Ag(III) solv has a short half life at ordinary temperatures, oxidizing the solvent to elemental fluorine with formation of Ag(II). Salts of such a cation have not yet been preparable, but solutions which must contain such a species have proved to be effective and powerful oxidizers. In presence of PtF{sub 6}{sup {minus}}, RuF{sub 6}{sup {minus}}, or RhF{sub 6}{sup {minus}}, Ag(III) ... continued below

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139 p.

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Lucier, G.M. May 1, 1995.

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Description

This thesis has been largely concerned with defining the oxidizing power of Ag(III) and Ag(II) in anhydrous hydrogen fluoride (aHF) solution. Emphasis was on cationic species, since in a cation the electronegativity of a given oxidation state is greatest. Cationic Ag(III) solv has a short half life at ordinary temperatures, oxidizing the solvent to elemental fluorine with formation of Ag(II). Salts of such a cation have not yet been preparable, but solutions which must contain such a species have proved to be effective and powerful oxidizers. In presence of PtF{sub 6}{sup {minus}}, RuF{sub 6}{sup {minus}}, or RhF{sub 6}{sup {minus}}, Ag(III) solv effectively oxidizes the anions to release the neutral hexafluorides. Such reactivity ranks cationic Ag(III) as the most powerfully oxidizing chemical agent known as far. Unlike its trivalent relative Ag (II) solv is thermodynamically stable in acid aHF. Nevertheless, it oxidizes IrF{sub 6}{sup {minus}} to IrF{sub 6} at room temperature, placing its oxidizing potential not more than 2 eV below that of cationic Ag(III). Range of Ag{sup 2+} (MF{sub 6}{sup {minus}}){sub 2} salts attainable in aHF has been explored. An anion must be stable with respect to electron loss to Ag{sup 2+}. The anion must also be a poor F{sup {minus}} donor; otherwise, either AgF{sup +} salts or AgF{sub 2} are generated.

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139 p.

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OSTI as DE95016458

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  • Other Information: TH: Thesis (Ph.D.)

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  • Other: DE95016458
  • Report No.: LBL--37334
  • Grant Number: AC03-76SF00098
  • Office of Scientific & Technical Information Report Number: 101247
  • Archival Resource Key: ark:/67531/metadc623681

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  • May 1, 1995

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  • June 16, 2015, 7:43 a.m.

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  • April 5, 2016, 12:32 p.m.

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Lucier, G.M. Synthesis, structure, and reactivity of high oxidation state silver fluorides and related compounds, thesis or dissertation, May 1, 1995; California. (digital.library.unt.edu/ark:/67531/metadc623681/: accessed September 23, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.