International Journal of Chemical Kinetics p. 431 - 442 (1995)
Update date:2022-08-24
Topics:
Rabai, Gyula
Hanazaki, Ichiro
The stoichiometry, equilibrium, and kinetics of the photo-induced disproportionation of iodomalonic acid to I-, I2, and tartronic acid have been studied by means of spectrophotometry and iodide selective electrode at 20.0 +/- 0.2 deg 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 100percent conversion.At pH < 2.9, I2 and malonic acid are also formed and the reaction stops at a conversion rate less than 100percent.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: (M1) ICH(COOH)2 + hν <-> I. + .CH(COOH)2, (M2) I2 + hν <-> 2I..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 I2.
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