Alt Title

Correlation of solvolysis rates of methyl perchlorate in hydroxylic solvents

Publication Date


Document Type


First Advisor

Kevill, Dennis N.||Russell, Morley||Daum, Peter H.

Degree Name

M.S. (Master of Science)

Legacy Department

Department of Chemistry


Methyl perchlorate; Solvolysis


The solvolysis of methyl perchlorate has been investigated at several temperatures in aqueous 80% ethyl alcohol and in methyl alcohol, ethyl alcohol, 2-propanol, and t-butyl alcohol. CH?OClO? + ROH - CH?OR + HC1O? The reaction rates were determined by titration, of the acid produced at appropriate time intervals. Enthalpies of activation, entropies of activation, energies of activation, and frequency factors have been computed. The isokinetic temperature for the solvolysis reaction was computed. A kinetic study has been also made, at 25.0°C, in several other aqueous-organic systems and solvolysis rates have been correlated by the Grimwald- Winstoin mY equation. The effect of added tetra-n-butylammonium perchlorate was studied. The solvolysis of methyl perchlorate was found to possess characteristics of a bimolecnlar substitution process. The failure to observe marked effects, due to changes in ionising power of the solvent,upon the solvolysis of of methyl perchlorate is evidence that the reaction is a bimolecular process and suggests that charges are very well dispersed internally within the transition state. This is also confirmed by the minor effect that the addition of tetra-n-butylammonium perchlorate has on the rate of solvolysis in methyl alcohol. The large negative entropy of activation values for the solvolysis reaction are consistent with a well-ordered bimolecular transition state. It was also found that the perchlorate ion is displaced with particular ease and is a better leaving group than tosylate and bromide ion. This suggests that the perchlorate ion is very well solvated in hydroxylic solvents and is capable of efficient internal charge dispersal.


Includes bibliographical references.||Includes illustrations.


v, 47 pages




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