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Rate Acceleration of Persulfate Anion-Mediated Oxidation of Hexacyanoruthenate(II) by Anionic Surfactant

  • CHEMICAL KINETICS AND CATALYSIS
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Abstract

The proposed study aimed to explore the kinetics of [Ru(CN)6]4– oxidation in an sodium lauryl sulfate (SLS) micellar media by persulfate anion (\({{{\text{S}}}_{{\text{2}}}}{\text{O}}_{8}^{{2 - }}\)). The increment in absorbance at 460 nm, which is indicative of the concentration of [Ru(CN)6]3–, was measured to determine the reaction rate. The reaction rate was analyzed as a function of [\({\text{Ru}}({\text{CN}})_{6}^{{4 - }}\)], [SLS], temperature, [\({{{\text{S}}}_{{\text{2}}}}{\text{O}}_{8}^{{2 - }}\)], ionic strength, and pH. The findings indicate that the pH of the medium and [SLS] are the crucial factor that significantly affects the rate of the reaction. The [Ru(CN)6]4– undergoes a 2 : 1 stoichiometric interaction with \({{{\text{S}}}_{{\text{2}}}}{\text{O}}_{8}^{{2 - }}\). The observed reaction exhibits first-order kinetics with regards to [\({\text{Ru}}({\text{CN}})_{6}^{{4 - }}\)] and [\({{{\text{S}}}_{{\text{2}}}}{\text{O}}_{8}^{{2 - }}\)], within the range of concentrations investigated. The observed invariance in reaction rate upon electrolyte’s introduction is suggestive of a zero salt effect. The electron transfer from [Ru(CN)6]4– to \({{{\text{S}}}_{{\text{2}}}}{\text{O}}_{8}^{{2 - }}\) proceeds via the formation of ion-pair, which leads to the formation of [Ru(CN)6]3–, sulfate ion, and sulfate radical ion. The formation of ion-pair is strengthened by the zero salt effect, while, the comparatively low activation energy and free radical test supports the formation of sulfate radical ion during the course of the reaction. The inclusion of SLS substantially enhances the rate of the process. After reaching its maximum rate, the reaction exhibits a very steady behavior even when the [SLS] is further increased. The observed decrease in SLS CMC could potentially be attributed to the diminished electrostatic repulsion among the anionic surfactant head groups, which is caused by the cationic H+. The outer-sphere electron transfer pathway, via the formation of ion-pair as proposed by us, is further supported by the negative entropy of activation value.

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DATA AVAILABILITY

The datasets generated or analyzed during the current study are available from the corresponding author on reasonable request.

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Funding

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Authors and Affiliations

  1. Department of Chemistry, GLA University, 281406, Mathura, U.P., India

    Abhishek Srivastava

  2. Department of Chemistry, D.D.U. Gorakhpur University, 273001, Gorakhpur, U.P., India

    Neetu Srivastava

  3. Department of Chemistry, Lucknow University, Lucknow, India

    Vinay Kumar Singh

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  1. Abhishek Srivastava
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  2. Neetu Srivastava
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Srivastava, A., Srivastava, N. & Singh, V.K. Rate Acceleration of Persulfate Anion-Mediated Oxidation of Hexacyanoruthenate(II) by Anionic Surfactant. Russ. J. Phys. Chem. 97, 3259–3267 (2023). https://doi.org/10.1134/S0036024424030038

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