Desolvation energies for rare-earth-metal perchlorate, chloride, and nitrate electrolytes from 0. 1 m to saturation

Journal Article · Wed Nov 06 00:00:00 UTC 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00217a036· OSTI ID:5897392

Onstott, E I

Work of desolvation values for rare-earth-metal perchlorate, chloride, and nitrate electrolytes across the rare-earth-metal series from 0.1 to 1 m are relatively uniform and are in the sequence of perchlorates > chlorides > nitrates. Changes in T..delta..S in this region are in the sequence of perchlorates > nitrate > chlorides and reveal a geometric anion obstruction factor that depends on anion size and complexity. Desolvation energies for 0.2 m increments for the region of 1 m to saturation show that negative values of T..delta..S persist to saturation for the perchlorate series but T..delta..S values for chlorides all change from negative to positive near saturation. For the nitrate series at saturation, incremental values of T..delta..S are negative for lanthanum through gadolinium, near zero for terbium, dysprosium, holmium, and erbium, and positive for thulium, ytterbium, and lutetium. Zero crossing of incremental T..delta..S is interpreted to be an indicator that outer-sphere ion pairing is complete, and positive T..delta..S is the result of ion compression of inner-sphere cation water and electrolyte destructuring on formation of inner-sphere ion pairs by water displacement. 42 references, 4 figures, 2 tables.

• Research Organization: Los Alamos National Lab., NM
• DOE Contract Number: NONE
• OSTI ID: 5897392
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:23; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

08 HYDROGEN
080102 -- Hydrogen-- Production-- Thermochemical Processes
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ANIONS
AQUEOUS SOLUTIONS
CATIONS
CHARGED PARTICLES
CHLORIDES
CHLORINE COMPOUNDS
DATA
DISPERSIONS
ELECTROLYTES
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
IONS
MIXTURES
NITRATES
NITROGEN COMPOUNDS
NUMERICAL DATA
OXYGEN COMPOUNDS
PERCHLORATES
PHYSICAL PROPERTIES
RARE EARTH COMPOUNDS
SATURATION
SOLUBILITY
SOLUTIONS
SOLVATION
THERMODYNAMIC PROPERTIES
WATER