Desolvation energies for rare-earth-metal perchlorate, chloride, and nitrate electrolytes from 0. 1 m to saturation
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
- OSTI ID:
- 5897392
- Journal Information:
- Inorg. Chem.; (United States), Vol. 24:23
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
08 HYDROGEN
CHLORIDES
SOLUBILITY
THERMODYNAMIC PROPERTIES
NITRATES
PERCHLORATES
RARE EARTH COMPOUNDS
ANIONS
AQUEOUS SOLUTIONS
CATIONS
ELECTROLYTES
EXPERIMENTAL DATA
SATURATION
SOLVATION
WATER
CHARGED PARTICLES
CHLORINE COMPOUNDS
DATA
DISPERSIONS
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
IONS
MIXTURES
NITROGEN COMPOUNDS
NUMERICAL DATA
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
SOLUTIONS
400201* - Chemical & Physicochemical Properties
080102 - Hydrogen- Production- Thermochemical Processes