Electron-transfer reactions of the halogens and their compounds : Limiting conditions for the quantitative reaction of bromate with arsenic(iii) and antimony(iii)

The limits of hydrochloric acid concentration within which the titrimetric determination of antimony(III) and arsenic(III) with bromate is quantitative within the normal precision of careful volume measurement (0.04%), are defined for both visual indication with rosaniline hydrochloride and potentiometric indication, in media initially containing no or 0.l M bromide. These reactions are independent of the nature of the reductant, the rate-controlling step being the fourth-order reaction producing the active oxidising species. Rate constants and energy of activation were determined. The kinetic and potentiometric investigations were used to elucidate the origins of the errors arising under conditions outside the ranges of quantitative reaction.