A Matrix Isolation Study Of The Reactions Of Oxygen(Singlet-D) With The Chlorofluoromethanes Fluorotrichloromethane, Dichlorodifluoromethane And Chlorotrifluoromethane

Author

Richard Thomason Burke, University of the Pacific

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

Recommended Citation

Burke, Richard Thomason. (1981). A Matrix Isolation Study Of The Reactions Of Oxygen(Singlet-D) With The Chlorofluoromethanes Fluorotrichloromethane, Dichlorodifluoromethane And Chlorotrifluoromethane. University of the Pacific, Dissertation. https://scholarlycommons.pacific.edu/uop_etds/3237