Photochemical Reactions Involving the Double Bond Between Carbon Atoms. I. The Photochlorination and the Chlorine-Sensitized Photo-Oxidation of Gaseous Tetrachloroethylene. II. The Bromine-Sensitized Photodecomposition of Gaseous Dibromotetrachloroethane

Citation

Carrico, James Leon (1935) Photochemical Reactions Involving the Double Bond Between Carbon Atoms. I. The Photochlorination and the Chlorine-Sensitized Photo-Oxidation of Gaseous Tetrachloroethylene. II. The Bromine-Sensitized Photodecomposition of Gaseous Dibromotetrachloroethane. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/s0bt-z735. https://resolver.caltech.edu/CaltechTHESIS:11122024-220037716

Abstract

The express purpose of the work to be presented was to determine, in so far as possible, the products formed, the intermediates formed, the factors controlling the rate and the mechanism involved in the addition reaction of oxygen, on the one hand, and the addition of chlorine, on the other, at the double bond between the two carbon atoms of tetrachloroethylene, C₂ Cl₄. Interest was centered, perhaps, on the intricacies of the oxidation, and still is.

In attempting to study the bromine addition at the double bond of tetrachloroethylene, experimental facilities accentuated the study of the elimination of two bromine atoms from dibromotetrachloroethane, C₂ Cl₄ Br₂, and the accompanying double bond formation between two carbon atoms rather than the addition reaction study. It was highly probable that a study of the elimination of two halogen atoms from two adjacent carbon atoms would elucidate the processes involved in the addition of the two halogen atoms to the adjacent carbon atoms.

To be more explicit concerning the intermediate compounds involved, it was desirable to establish evidence for or against the existence of a Cl₃ or a Br₃ molecule postulated as a transient intermediate by certain investigators.

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