Electrochemistry of Solutes in Chloroaluminate Melts and the Development of Related Electrochemical Methodology.
Abstract
Molten haloaluminates were investigated as solvent systems for the study of electrochemical reactions. The particular interest has been in the fact that systems, such as the molten terachloroaluminates, show significant acid-base dependent behavior which is reflected in solute electrochemistry. In the NaCl:AlCl3 system (sodium tetrachloraluminate), the acid-base chemistry of oxides and chalcogenides was investigated. The electrochemistry of Mo, Se and Te was investigated; Mo was studies in the basic melt (excess NaCl) while Se and Te were investigated as a function of melt acidity and a variety of acidity dependent electrochemicalr eactions were uncovered. The electrochemistry of NI(II) was also investigated, and it was found that NiCl2 was insoluble in the neutral and basic melt. At 175 C the melt becomes saturated with NaCl at about 1% excess. Although not subject to detailed investigation, it was found that oxygen reduction in this melt could be catalyzed by the presence of metal cations, such as Cu(I) and Mo(V). The electrochemistry of a number of aromatic polynuclear hydrocarbons was studied across the acidity range. All were shown to undergo a one-electron oxidation to the radical cation that was independent of melt acidity and, compared to ferrocene, oxidized at the same relative potential as in acetonitrile. The electrochemistry of a number of metal carbonyls was investigated in another room temperature melt, a 2:1 mixture of aluminum chloride and ethypyridinium bromide.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1979
- Accession Number
- ADA078242
Entities
People
- Janet G. Osteryoung
- Robert A. Osteryoung
Organizations
- Colorado State University