Infrared photochemistry of bis(trifluoromethyl) peroxide

Abstract

Bis(trifluoromethy1) peroxide is readily dissociated by multiple infrared photon excitation at COz laser wavelengths. The primary dissociation product is CF30; approximately 85% of the nascent radicals are further dissociated in the laser field to form CFzO and F. The F atoms then react with the remaining CF30 to produce CF30F. The formation of CF3OF is strongly inhibited by addition of HI, which reacts preferentially with the F atoms.

A reexamination of the pyrolysis of bis trifluoromethyl peroxide

“…However, the nonchain mechanism does seem the more plausible. The essenti,al features of this mechanism are confirmed by the very recent work of ]Francisco, Findeis, and Steinfeld [24]. As discussed previously, analysis of the first mechanism leads to the result for the rate of reaction (12):…”

“…Taking CX3 to be CF3 as an ex,ample, the most likely fate is addition to oxygen: (24) CF3 + 0 2 -CF3O2…”

Fluorocarbon oxy and peroxy radicals

“…Also an IR multi-photon dissociation experiment was carried out [108] that showed the same products.…”

Multiple infrared photon dissociation and kinetics of CF3O radicals

“…This gives a gas-kinetic collision rate at 300 K which is the upper limit for the rate of recombination of CF30 with F, equal to 1.7 X 1011 L mol"1 s"1. The value found for fe3, which is 4-5 times smaller than this, suggests that a modest orientational requirement exists for the collision to be reactive, similar to (but less restrictive than) that observed in the recombination of CF3 radicals.15 Introduction Photochemical solar energy conversion is an important and highly active area of research.2'14 Much attention has been focussed upon the photosensitized reduction (by an electron relay, R) of methyl viologen, MV2+, since the oxidized relay, Rox, can be regenerated by a suitable electron donor, D, and since reduced methyl viologen, MV+-, in the presence of a suitable catalyst is reoxidized to MV2+ with concurrent water splitting MV H2 Y catalyst (1) MV* HzO Hydrogen is, therefore, photogenerated from water at the expense of a sacrificial donor (eq 1).…”