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Photocatalysis of Chloroform Decomposition by Tetrachlorocuprate ( II ) on Dowex 2‐X8
Author(s) -
Harvey Brent M.,
Hoggard Patrick E.
Publication year - 2014
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/php.12336
Subject(s) - chemistry , chloroform , photodissociation , polystyrene , photochemistry , phosgene , photocatalysis , catalysis , decomposition , ion exchange , polymer chemistry , ion , polymer , organic chemistry
Heterogenized on a polystyrene anion exchange resin and in the presence of oxygen, CuCl 4 2 −catalyzes the photodecomposition of chloroform at wavelengths above 345 nm with greater efficiency than an equivalent amount in homogeneous solution. The reaction is proposed to proceed in two stages, the first stage yielding CC l 4 and HO 2 − as products, the second consisting of a chain reaction resulting from the CuCl 4 2 − ‐catalyzed photodissociation of CC l 4 , yielding phosgene with CC l 3 radicals as chain carriers. Photodecomposition is retarded by added Cl − , CH 3 CN , C 6 H 12 or C 2 H 5 OH , which is ascribed to the displacement of CHC l 3 molecules from the vicinity of the copper by attraction to the polystyrene matrix or to the alkylammonium cation sites.