Date of Award

1981

Document Type

Dissertation

Degree Name

Doctor of Philosophy (Ph.D.)

Department

Chemistry

First Advisor

Patrick R. Jones

First Committee Member

Richard P. Dodge

Second Committee Member

Silvio Rodriguez

Third Committee Member

Herschel Frye

Fourth Committee Member

Carl Wulfman

Abstract

We have studied the reactions of O(1D) with CC13F, CC12F2 and CC1F3 in CO2, SF6 and N2O matrices, and in neat mixtures. Photolysis of cryogenic mixtures of ozone and the chlorofluoromethanes in various matrix hosts resulted in production of O(1D) which migrated through the matrix to react with the Freon molecules. Products were detected by infrared spectroscopy of the matrix deposits, with assignments confirmed by comparison of 16O and 18O absorption bands with literature values. Evidence for oxygen atom insertion into a C-C1 bond to form a hypochlorite intermediate was obtained. In the case of CC13F, the first stable product to be formed was COC1F, but this subsequently photo-oxidized to give COF2 and CO2. In addition, evidence for fluorine atom reactions with the substrate was found in the formation of CC12F2 from CC13F. In the case of the reactant CC12F2, the major products were COF2 and CO2, followed by the product of F-atom reactions, CC1F3. For both of these chlorofluoromethanes, since COF2 does not react with O(1D), the most likely source of F-atom chemistry was concluded to be the reaction that also forms CO2. In the case of the reactant CC1F3, the major product was COF2, which would form together with C1F, thus providing a source for flourine atoms. CO(,2) was also found in the deposit after photolysis, although its presence cannot be explained definitively. Additional new features in the spectra of the product mixtures for this system have been tentatively assigned to CF3OC1 and CF3OOCF3.

Pages

170

Included in

Chemistry Commons

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