I. The thermolysis of acetyl peroxide. II. The photosensitized decomposition of acetyl peroxide in solution

Citation

Moses, Francis Guy (1965) I. The thermolysis of acetyl peroxide. II. The photosensitized decomposition of acetyl peroxide in solution. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-10022002-083657

Abstract

Part I.

The mechanism of the thermal decomposition of acetyl peroxide has been reinvestigated. The intermediacy of acetoxyl radicals has been demonstrated by a scavenging technique and evidence is presented which strongly suggests that the rate constant for acetoxyl radical decarboxylation is of the order of 2 x 10[superscript 9] sec.[superscript -1]. A primary process involving mainly simple 0_0 bond scission followed by acetoxyl radical decarboxylation at a rate competitive with diffusive separation of the radicals satisfies the results quite consistently.

Part II.

The photosensitized decomposition of acetyl peroxide by certain aromatic hydrocarbons and ketone has been studied. The evidence suggests that the extent of "primary" decarboxylation is a function of the triplet state energy of sensitizer. A second major mode of destruction of peroxide appears to be operative in the decompositions sensitized by ketones. Mechanisms are suggested to explain these processes.

Thesis Files