Ion-ion-solvent interactions in solution. 8. Spectroscopic studies of the lithium perchlorate/N,N-dimethylformamide system

1984 ◽  
Vol 88 (3) ◽  
pp. 637-642 ◽  
Author(s):  
David W. James ◽  
Raymond E. Mayes
Keyword(s):  
Lithium Perchlorate ◽  
Spectroscopic Studies ◽  
Solvent Interactions

Spectroscopic studies of solute–solute and solute–solvent interactions in solutions containing N,N-dimethylformamide

1988 ◽  
Vol 85 (0) ◽  
pp. 211-224 ◽  
Author(s):  
Vivian M. Shelley ◽  
April Talintyre ◽  
Jack Yarwood ◽  
Richard Buchner
Keyword(s):  
Spectroscopic Studies ◽  
Solvent Interactions

Ion Ion Solvent Interactions in Solution .XI. Spectroscopic Studies of Group-2 Perchlorates in Acetone

1986 ◽  
Vol 39 (1) ◽  
pp. 149 ◽  
Author(s):  
DW James ◽  
PG Cutler
Keyword(s):  
Raman Spectra ◽  
Spectroscopic Studies ◽  
Solvent Interactions ◽  
Solvation Numbers ◽  
Steric Crowding ◽  
Component Band ◽  
Group 2 ◽  
Association Equilibria ◽  
High Level ◽  
Ion Species

Solutions of Mg(ClO4)2 and Sr (ClO4)2 in acetone have been studied at various concentrations up to saturation by using infrared absorption, Raman scattering and multinuclear n.m.r (1H, 13C, 17O, 25Mg, 35Cl). Solvation numbers of c. 4.5 (Mg2+) and c. 5.5 (Sr2+) were determined from component band analysis of the c. 800 cm-1 acetone band in the Raman spectra. The solvent shell about the Mg2+ had a high level of steric crowding. There was a small amount of solvent-shared ion-pair formation at all oncentrations in solutions of Mg(ClO4)2 which showed little concentration dependence. In solutions of Sr (ClO4)2 there was evidence for the formation of both solvent-shared associated-ion species and ion-contact species. The solvent-shared species appeared to have two alternative configurations in one of which the anion was both polarized and highly hindered. There was a salt-promoted reaction in which the perchlorate was reduced to chloride and the solution darkened. This reaction prevented the use of Raman spectra to quantify the association equilibria.

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