Publication Date

1981

Document Type

Dissertation/Thesis

First Advisor

Kevill, Dennis N.

Degree Name

M.S. (Master of Science)

Legacy Department

Department of Chemistry

LCSH

Organosilver compounds; Solvolysis; Organochlorine compounds

Abstract

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.

Comments

Includes bibliographical references.||Includes illustrations.

Extent

x, 75 pages

Language

eng

Publisher

Northern Illinois University

Rights Statement

In Copyright

Rights Statement 2

NIU theses are protected by copyright. They may be viewed from Huskie Commons for any purpose, but reproduction or distribution in any format is prohibited without the written permission of the authors.

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Text

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