화학공학소재연구정보센터
Journal of Physical Chemistry, Vol.99, No.25, 10231-10236, 1995
Oxyhalogen-Sulfur Chemistry - Oxidation of Hydroxymethanesulfinic Acid by Bromate in an Acidic Medium
The reaction between hydroxymethanesulfinic acid, HOCH2SO2H (HMSA), and bromate ion has been studied in the pH range 0.3-2.0. The stoichiometry of the reaction in excess HMSA was determined as BrO3- + HOCH2SO2H --> Br + SO42- + HCOOH + 2H(+). In excess bromate the stoichiometry is 6BrO(3)(-) + 5HOCH(2)SO(2)H --> 3Br(2) + 5SO(4)(2-) + 5HCOOH + 4H(+) + 3H(2)O. In excess bromate, the reaction exhibits clock reaction behavior. An initial induction period in which there is no redox potential or absorbance (lambda = 390 nm) activity is followed by a sudden and rapid production of B-r2. This is explained via the coupling of three reactions : oxidation of HMSA, production of Bra, and consumption of B-r2. The consumption of B-r2 is so fast that the end of the induction period is an indicator that all the HMSA has been consumed. The rapid B-r2-HMSA reaction also precludes oligooscillatory behavior, which seems to de a usual feature of reactions between sulfur compounds and oxyhalogen ions.