By J. F. Coetzee, D. Frollini (auth.), Gleb Mamantov (eds.)

This ebook comprises contributions via contributors within the Symposium "Spectroscopic and Electrochemical Characterizat.ion of Solute Species in Non~Aqueous Solvents" which came about on the American Chemical Society assembly, department of Analytical Chemistry, August 31 and September I, 1976, San Francisco, California. The manuscripts have been submitted to the editor through the first 1/2 1977 and, often, symbolize reports of chosen examine issues within the wide zone of characterization of solute species in non~aqueous solvents. In organizing this Symposium, i tried to assemble a considerably huge staff of study employees concerned about spectro­ scopic and electrochemical reviews within the 3 huge sessions of non-aqueous solvents ~ natural solvents, covalent inorganic sol­ vents and molten salts. The experimental apprcaches and difficulties, akin to avoidance of lines of moisture and oxygen, are often related for every type of non-aqueous solvents. it truly is was hoping that this quantity should be valuable to all fascinated by chemistry in non-aqueous solvents. Gleb l>lamantov , Contents 1. identity AND SYSTEMIZATION OF SOLVENT houses occupied with THE LIGAND SUBSTITUTION KINETICS OF LABILE COMPLEXES OF NICKEL(II) J. F. Coetzee, D. Frollini, C. G. Karakatsanis, E. J.

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Eigen, (13) R. M. Fuoss, (14) Chin-Tung Lin and D. B. Rorabacher, Inorg. , (1973) . (15) T. J. Swift and R. E. Connick, J. Chem. , 37, 307 (1962). ~. 1, Ser. , No. ,~, ~, 18 (1969). 45 (1970). 408 (1970). Phys. Chem. , 176 (1954). ~. Amer. Chem. , 80, 5059 (1958). F. COETZEE ET AL. (16) R. E. Connick and D. Fiat, (17) J. W. Neely and R. E. Connick, 8646 (1972). (18) D. Rablen and G. Gordon, Inorg. , (19) A. G. Desai, H. W. Dodgen and J. P. ,2l, 5001 (1969). (20) Z. Luz and S. Meiboom, (21) F. W.

Tong, Canad. J. , (1975) . (88) J. S. Fritz, F. W. , and G. F. Smith, J. Arner. Chern. , 2480 (1949). , Wayne C. Boring, Merton R. Olds, and Reynold T. Iwamoto Department of Chemistry, University of Kansas Lawrence, Kansas 66045 Studies on the nature and behavior of inorganic species in nonaqueous media, over the years, have dealt primarily with monofunctional solvents such as acetonitrile, acetone, dimethyl sulfoxide, dimethylformamide, and ethanol. In this paper, we describe some of our work on the nature and behavior of inorganic species in difunctional solvents where there is the possibility of monocoordination by either or both functional groups.

ET AL. 70 V E~~Cl),CU vs. 52 V These potentials indicate that copper(l) ion is more strongly solvated in acetonitrile than in ethanol and copper(ll) ion is slightly more strongly solvated in ethanol than in acetonitrile. The potentials for the copper couples in 1:1 ethanol-acetonitrile mixture support this information with regard to the solvation of copper(ll) and copper(l) ions in ethanol and in acetonitrile. 46 V The nearly identical negative potential of the copper(I), copper couple in 1:1 ethanol-acetonitrile compared with that in acetonitrile points to acetonitrile coordination of copper(I) ion in the mixture, and the more negative potential of the copper(II), copper(I) couple in the mixture compared to that in acetonitrile is consistent with ethanol coordination of copper(II) ion.

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