Strategies for the preparation of compounds of alkali metal anions

Journal Article · Thu Dec 18 04:00:00 EST 1975 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100593a056· OSTI ID:7296200

Dye, J L; Andrews, C W; Mathews, S E

By using alkali cation complexing agents of the crown and cryptand classes (C) and appropriate solvents, solutions can be prepared which contain essentially only M/sup +/C and M/sup -/ in equal concentrations. From estimates of the metal solubility in the absence of the complexing agent and of the cation complexation constant, the solubility in the presence of the complexing agent can be predicted. If, in the metal solution with C absent, the e/sub solv//sup -//M/sup -/ ratio is appreciable, then when C is used and the solution is allowed to contact excess metal, this ratio will remain nearly the same. Therefore, in addition to MC/sup +/ and M/sup -/, the solution may contain relatively high concentrations of e/solv//sup -/. Examples of the application of these equilibrium considerations to various metal-solvent combinations are described. Only Na/sup +/C.Na/sup -/, in which C is 2,2,2 cryptand was prepared as a crystalline solid. Gold-colored solid films were obtained by rapid evaporation of solutions of Na, K, Rb, and Cs in one or more of the solvents methylamine (MA), ethylamine (EA), and tetrahydrofuran (THF) when the complexing agent 2,2,2 cryptand is present. In addition, gold-colored films are obtained with Na and K when 18-crown-6 is used. The former metal gives the film when MA is the solvent while the latter gives it with THF. In these cases, the gold film apparently yields the metal plus 18-crown-6 when the solvent vapors are removed. The criteria for thermodynamic vs. kinetic stability of salts of M/sup -/ are considered. (auth)

• Research Organization: Michigan State Univ., East Lansing
• OSTI ID: 7296200
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 79:26; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPOUNDS
ANIONS
CHARGED PARTICLES
CHEMICAL PREPARATION
COMPLEXES
CRYSTALS
ELECTRONS
ELEMENTARY PARTICLES
EXTRACTION
FERMIONS
FILMS
IONS
LEPTONS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
SEPARATION PROCESSES
SODIUM COMPOUNDS
SOLUBILITY
SOLVENT EXTRACTION
SYNTHESIS