Journal of Physical Chemistry, Vol.98, No.4, 1363-1367, 1994
Kinetics of Disproportionation and Pk(A) of Bromous Acid
The kinetics of the disproportionation reaction of bromine(III), 2Br(III) --> Br(I) + Br(V), was studied in phosphate buffer, in the pH range 5.9-8.0, by monitoring optical absorbance at 294 nm using stopped-flow. The dependences on alpha(H+) and [Br(III)] were of order 1 and 2, respectivley, and no dependence on [Br-] was found. The reaction was also studied in acetate buffer, in the pH range 3.9-5.6. Within experimental error, no evidence was found for a direct reaction between two Br-2(O)- ions. This study yields rate constants 39.1 +/- 2.6 M(-1) s(-1) for the reaction HBrO2 + BrO2- --> HOBr + BrO3- and 800 +/- 100 M(-1) s(-1) for the reaction 2HBrO(2) --> HOBr + BrO3- + H+ and an equilibrium quotient for HBrO2 reversible arrow H+ + BrO2- of 3.7 +/- 0.9 x 10(-4) M (pK(a) = 3.43) at ionic strength 0.06 M and 25.0 + 0.1 degrees C. The bromous acid dissociation constant is essentially identical to the value previously obtained from a kinetics study of the bromine(III)-I- reaction(J. Phys, Chem, 1992, 96, 6861).
Keywords:OSCILLATORS