Choi, W. and Hoffmann, M. R. (1995) Photo-Induced Electron Transfers to CCl_4 and its Degradation Mechanism on TiO_2 Particles. Abstracts of Papers of the American Chemical Society, 209 . 200-ENVR. ISSN 0065-7727. https://resolver.caltech.edu/CaltechAUTHORS:20151215-093807476
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Abstract
The photoreductive degradation of CCl_4 in TiO_2 particulate suspensions in the presence of a variety of organic electron donors (alcohols, carboxylic acids, and benzene derivatives) has been examined. CHCl_3, C_2Cl_4, and C_2Cl_6 are detected as intermediates during photolysis. The rate of CCl_4 dechlorination can be enhanced significantly when alcohols and organic acids are used as electron donors. Kinetic isotope effects and structure-reactivity relationships show that hydrogen-abstraction by hydroxyl radicals plays an important role in the hole-scavenging mechanism. The pH of the TiO_2 suspension influences the rate of CCl_4 reduction either by altering the electrostatic interactions of electron donors on the TiO_2 surface or by changing the reduction potential of the conduction band electron in a Nernstian fashion. Since dissolved oxygen is shown to be nonessential for the complete mineralization of CCl_4, a mechanism, which involves dichlorocarbene formation through a two-electron transfer, is proposed.
Item Type: | Article | ||||
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Additional Information: | © 1995 American Chemical Society. | ||||
Record Number: | CaltechAUTHORS:20151215-093807476 | ||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20151215-093807476 | ||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||
ID Code: | 62923 | ||||
Collection: | CaltechAUTHORS | ||||
Deposited By: | Tony Diaz | ||||
Deposited On: | 15 Dec 2015 18:01 | ||||
Last Modified: | 03 Mar 2020 13:01 |
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