I. The Thermolysis of Acetyl Peroxide. II. The Photosensitized Decomposition of Acetyl Peroxide in Solution

• Main Author: Moses, Francis Guy
• Format: Others
• Language: en
• Published: 1967
• Online Access: https://thesis.library.caltech.edu/3859/1/Moses_fg_1967.pdf; Moses, Francis Guy (1967) I. The Thermolysis of Acetyl Peroxide. II. The Photosensitized Decomposition of Acetyl Peroxide in Solution. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/0whd-rp13. https://resolver.caltech.edu/CaltechETD:etd-10022002-083657 <https://resolver.caltech.edu/CaltechETD:etd-10022002-083657>

<p>Part I.<br /> 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.</p> <p>Part II.<br /> 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.</p>