Photosensitized Oxidation of Perfluoroolefins

In order to understand the mercury-sensitized oxidation, it is first necessary to discuss the sensitized reaction in the absence of 02. The reaction has been studied in a series of papers and the general overall mechanism has been developed 

The rate constants for reaction (4-39) have been found by competition with NaO. 

From the value of ke, and the ratio k39/k6, the value of k36 can be obtained. The values for several molecules of interest here are listed in Table XXI. 

Some Rate Constants for Reactions of Hg With Various Molecules Relative to N2Oa 

A temperature-dependent process can arise either from the energy distribution in the ground electronic state before excitation or from the energy distribution of the thermally equilibrated upper electronic state. The second possibility was eliminated by consideration of the results with 02 present.61 These results showed that the upper electronic state is not removed by collision with C3Fe thus, if the decomposition had occurred from the equilibrium distribution of this state, no pressure effect should have been observed. 

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