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

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00217a036· OSTI ID:5897392

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