I. The Thermolysis of Acetyl Peroxide. II. The Photosensitized Decomposition of Acetyl Peroxide in Solution
<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 dec...
| Summary: | <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> |
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