Kevill, Dennis N.
M.S. (Master of Science)
Department of Chemistry
Organosilver compounds; Solvolysis; Organochlorine compounds
The Grunwald-Winstein equation (m̲Y̲ equation), introduced by Grunwald and Winstein in 1948 to study the solvent ionizing power, has been extensively used, especially in studies of the solvolyses proceeding by the unimolecular mechanism. This equation is of the form log (k/kₒ) = m̲Y̲ and it is based on the solvolyses of t̲-butyl chloride at 25° 25°C. For the first order rate coefficients for the solvolyses of 2-adamantyl perchlorate (k₁) at 0.02°C, the log k₁ v̲s̲ Y̲ plots were usually close to linear for the various solvent systems studied. The m̲ values calculated, based on the standard (t̲-butyl chloride) Y̲-scale, are 1.06 for methanol-water, 1.01 for ethanol-water, 0.91 for dioxane water, 0.58 for acetone-water and 0.92 for 2,2,2-trifluoroethanol-water mixtures. The curvature in the log k₁ v̲s̲ Y̲ plot observed for ethanol-water, acetone-water and 2,2,2-trifluoroethanol-water mixtures is due in part to the variation in initial state solvation, which includes solvent sorting. The log k₁ v̲s̲ Y̲ plot for the solvolyses of 2-adamantyl perchlorate and methyl perchlorate in acetone-methanol mixtures both show a maximum. The explanation previously put forward for methyl perchlorate was that the solvolysis was S[sub N]1 in the acetone-methanol mixtures of low methanol content, but S[sub N]2 when the methanol concentration in the mixture was increased. Since 2-adamantyl perchlorate shows similar behavior and it cannot react by the S[sub N]2 mechanism, this explanation now appears to be unlikely.
Bahari, Mohd. Shahru, "The correlation of solvolysis rates for the solvolyses of 2-adamantyl perchlorate" (1981). Graduate Research Theses & Dissertations. 5385.
x, 75 pages
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