Alkali metal anions: an unusual oxidation state

Journal Article · Wed Jun 01 04:00:00 EDT 1977 · J. Chem. Educ.; (United States)

DOI:https://doi.org/10.1021/ed054p332· OSTI ID:5481606

Dye, J L

Background information concerning the M/sup -/ state of alkali metals is summarized. Pulse-radiolysis techniques used in various studies to verify the existence of the M/sup -/ species in certain solvents are discussed. Thermodynamics of the anion formation are considered: and using Na/sup +/I/sup -/ as a model, the lattice enthalpy of a hypothetical Na/sup +/Na/sup -/(s) has been computed to be 13.7 kcal/mole. Reactions with a complexing agent such as crown ethers and m,n,o cryptand which interacts strongly with the M/sup +/ from the M/sup +/M/sup -/ entity yielded solid salts of Na/sup -/. Free energy calculations are made; and the conclusion is drawn that, with the possible exception of Cs, suitable salts of all the alkali meal anions should be thermodynamically stable. The solid salt of Na/sup -/ with cryptand, Na/sup +/C.Na/sup -/, was prepared, isolated, and characterized with an overall stoichiometry of Na/sub 2/C/sub 18/H/sub 36/O/sub 6/N/sub 2/ being established. Powder conductivity measurements on the shiny, gold-colored material indicated that in spite of metallic appearance the material is probably a semiconductor. Crystallographic studies indicate that the solid may be viewed as essentially alternate layers in a hexagonally packed arrangement. NMR spectra of the compound in solutions are recorded, and the compound is proposed for use as a two-electron reducing agent. 98 references. (BLM)

• Research Organization: Michigan State Univ., East Lansing
• OSTI ID: 5481606
• Journal Information: J. Chem. Educ.; (United States), Journal Name: J. Chem. Educ.; (United States) Vol. 54; ISSN JCEDA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400600 -- Radiation Chemistry
ALCOHOLS
ALKALI METAL COMPOUNDS
ANIONS
CHARGED PARTICLES
CHEMICAL PREPARATION
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DECOMPOSITION
GLYCOLS
HYDROXY COMPOUNDS
IONS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC POLYMERS
PHYSICAL PROPERTIES
POLYETHYLENE GLYCOLS
POLYMERS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOLYSIS
RESONANCE
SODIUM COMPOUNDS
SYNTHESIS
THERMODYNAMIC PROPERTIES
VALENCE