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Mechanistic investigations with Bromamine-T: Kinetics of oxidation of thiocyanate ion

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Abstract

The kinetics of oxidation of thiocyanate ion by Bromamine-T (BAT) has been investigated in alkaline medium. The rate of reaction is first order in [OH−] and zero order in [NCS−]. The pseudo-first order rate constants decrease with increase in [BAT]. Addition of the reaction products p-toluenesulfonamide, Br− and neutral salts has no significant effect on the rate. The rate increases with either increase in ionic strength or decrease in dielectric constant of the medium. The activation parameters have been computed. A mechanism consistent with the experimental results has been proposed and the rate law derived. The rate constants predicted from the rate law for the variation of [BAT] are in excellent agreement with the observed rate constants.

Abstract

Кинетика окисления тиоцианатного иона Бромамином-Т (BAT) исследована в щелочной среде. Скорость реакции имеет первый порядок по [OH−] и нулевой порядок по [NCS−]. Константы скорости псевдопервого порядка уменьшаются с увеличением [BAT]. Добавление продуктов реакции п-толуолсульфонамида, Br− и нейтральных солей не оказывает значительного влияния на скорость. Скорость увеличивается с увеличением ионной силы или с уменьшением диэлектрической константы среды. Параметры активации были рассчитаны на ЭВМ. Предложен механизм, соответствующий экспериментальным результатам, откуда выведено уравнение скорости. Константы скорости, предсказанные, исходя из уравнения скорости на основе изменения [BAT]o, находятся в превосходном согласии с наблюдаемыми константами скорости.

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Authors and Affiliations

  1. Department of Post-graduate Studies and Research in Chemistry, Mangalore University, 574199, Mangalagangothri, India

    B. Thimme Gowda

  2. Department of Chemistry, Govinda Dasa College, Suratkal, 574158, D. K., Karnataka, India

    J. Ishwara Bhat

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  1. B. Thimme Gowda
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  2. J. Ishwara Bhat
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Gowda, B.T., Bhat, J.I. Mechanistic investigations with Bromamine-T: Kinetics of oxidation of thiocyanate ion. React Kinet Catal Lett 31, 461–468 (1986). https://doi.org/10.1007/BF02072989

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  • DOI: https://doi.org/10.1007/BF02072989

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