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Photo‐induced disproportionation of iodomalonic acid
Author(s) -
RÁBai Gyula,
Hanazaki Ichiro
Publication year - 1995
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550270503
Subject(s) - chemistry , disproportionation , malonic acid , photochemistry , radical , iodide , visible spectrum , decomposition , kinetics , iodine , stoichiometry , reaction rate , rate equation , inorganic chemistry , catalysis , organic chemistry , physics , optoelectronics , quantum mechanics
Abstract The stoichiometry, equilibrium, and kinetics of the photo‐induced disproportionation of iodomalonic acid to I − , I 2 , and tartronic acid have been studied by means of spectrophotometry and iodide selective electrode at 20.0 ± 0.2°C, pH 2.0–4.0. At pH > 2.9, only I − and HOCH(COOH) 2 are detected as major products and the reaction reaches 100% conversion. At pH < 2.9, I 2 and malonic acid are also formed and the reaction stops at a conversion rate less than 100%. Both UV (band with a peak at 360 nm) and visible light (480 nm) have been found to be effective. Two primary photochemical processes are identified:While both reactions are sensitive to UV light, only (M2) can be affected by visible light. (M1) and (M2) are considered to initiate a chain reaction sequence in which I · radicals oxidize iodomalonic acid. Dual effects of reaction products on the reaction rate have been observed: while iodine increases the efficiency of visible light and accelerates the reaction, malonic acid inhibits the photo‐decomposition by mediating the recombination of I · radicals to I 2 . © 1995 John Wiley & Sons, Inc.