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Kinetics of the bromate–bromide reaction at high bromide concentrations

par Schmitz, Guy
Référence International journal of chemical kinetics, 39, 1, page (17-21)
Publication Publié, 2007-01

Article révisé par les pairs

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Résumé :

At bromide concentrations higher than 0.1 M, a second term must be added to the classical rate law of the bromate-bromide reaction that becomes -d[BrO3-]/dt = [BrO3-][H+]2(k1[Br-] + k2[Br-]2). In perchloric solutions at 25°C k1 = 2.18 dm3.mol-3.s-1 and k2 = 0.65 dm4.mol-4.s-1 at 1 M ionic strength and k1 = 2.60 dm3.mol-3.s-1and k2 = 1.05 dm4.mol-4.s-1 at 2 M ionic strength. A mechanism explaining this rate law, with Br2O2 as key intermediate specie, is proposed. Errors that may occur when using the Guggenheim method are discussed.