Non-Metal Redox Kinetics: Hypobromite and Hypobromous AcidReactions with Iodide and with Sulfite and the Hydrolysis of Bromosulfate.-The rate constants of the reactions shown in the scheme are measured using the pulsed-accelerated-flow method, because the reactions are too fast to be measured by stopped-flow spectrophotometry. A mechanism is proposed, which includes parallel paths with Br+ transfer to the nucleophile via solvent-assisted reaction with OBr-and diffusion-determined reactions between HOBr and these nucleophiles. The OBr-reactions are shown to be faster than the previously studied OCl-reactions by a factor of 4.4·103 for SO2-3 and by a factor of ¿ 2.3·104 for I-. From the mechanistic point of view this can be explained with the greater ease of Br+-transfer compared to Cl+-transfer reactions. The reactivity of HOBr is substantially greater than that of OBr-a finding that is again associated with the easier Br+ transfer to the nucleophiles. The BrSO-3 formed in the reactions with SO2-3 hydrolyzes with a very high rate constant compared to the other halosulfates (BrSO-3 ¿¿ IO-3 .simeq.
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