ChemInform Abstract: BEDEUTUNG DER CHLORIDIONEN BEI DER OX. VON BROMIDEN DURCH BROMATE

Wrońska, M.; Cyfert, M.

doi:10.1002/chin.197227055

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“…In the first study of reaction 1, Judson and Walker found that it follows the fourth-order rate law, eq 3 This rate law has been confirmed by several authors. − In addition, the possibility for a fifth-order rate law at high bromide concentration arising from a second-order term in bromide was pointed out by Skrabal 15 and by Bray and Liebhafsky . A higher order for bromide ion was also found by Rábai et al., who were the first to use visible spectroscopy to follow this reaction at the Br 2 /Br 3 - isosbestic point.…”

Section: Introductionmentioning

confidence: 78%

“…Another point we must consider is the possibility that bromate, after two protonations, loses water and forms the BrO 2 + species as has been considered by other authors. , However, this possibility has been ruled out by the results , on the rate of exchange of isotopic oxygen between the oxy-anions XO 3 - (X = Cl, Br) and water as these rates are significantly lower than the reactions of these oxy-anions with X - (X = Cl, Br, I).…”

Section: Discussionmentioning

confidence: 95%

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Kinetics and Mechanism of Bromate−Bromide Reaction Catalyzed by Acetate

Côrtes

Faria

2004

Inorg. Chem.

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The initial rate of the bromate-bromide reaction, BrO3- + 5Br- + 6H+ --> 3Br2 + 3H2O, has been measured at constant ionic strength, I = 3.0 mol L(-1), and at several initial concentrations of acetate, bromate, bromide, and perchloric acid. The reaction was followed at the Br2/Br3- isosbestic point (lambda = 446 nm) by the stopped-flow technique. A very complex behavior was found such that the results could be fitted only by a six term rate law, nu = k1[BrO3-][Br-][H+]2 + k2[BrO3-][Br-]2[H+]2 + k3[BrO3-][H+]2[acetate]2 + k4[BrO3-][Br-]2[H+]2[acetate] + k5[BrO3-][Br-][H+]3[acetate]2 + k6[BrO3-][Br-][H+]2[acetate], where k1 = 4.12 L3 mol(-3) s(-1), k2 = 0.810 L4 mol(-4) s(-1), k3 = 2.80 x 10(3) L4 mol(-4) s(-1), k4 = 278 L5 mol(-5) s(-1), k5 = 5.45 x 10(7) L6 mol(-6) s(-1), and k6 = 850 L4 mol(-4) s(-1). A mechanism, based on elementary steps, is proposed to explain each term of the rate law. This mechanism considers that when acetate binds to bromate it facilitates its second protonation.

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