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Understanding the Kinetics and Reduction of Methylene Blue Using NaBH4

  • KINETICS AND MECHANISM OF CHEMICAL REACTIONS, CATALYSIS
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Abstract—

The complete mechanism and kinetics of NaBH4 assisted methylene blue (MB) reduction are evaluated using density-functional theory calculations with B3LYP/6-311G(d, p) and M06-2X/6-311G(d, p) with implicit solvent model. Our calculations indicate that the reduction process initiates with a nucleophilic borohydride ion attack on the active site of MB, followed by proton abstraction with a hydroxyl ion attack released from water resulting in the formation of an intermediate species. The product formation is finally achieved by two pathways. The first pathway involves the direct hydrolysis on active site of an intermediate. Alternatively, the second pathway includes the interaction of BH3 with the intermediate in order to attain stability. Subsequently, the final product, i.e., leuco methylene blue (LMB) is formed via hydrolysis. The stabilization study of both the transition states was carried out by natural bond orbital (NBO) analysis at the same level of theory with implicit solvent model. Interactions between the transition states reveal that the latter pathway is more stable than the former. Our calculations indicate that the second step of the reaction, hydroxyl ion assisted proton abstraction, has the highest barrier height and thus will control the kinetics of the reaction. The estimated values of rate constant, at M06-2X level of theory, were in agreement with the experimental values.

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Authors and Affiliations

  1. Atharva College of Engineering, Malad West, Mumbai, India

    P. Patel

  2. Department of Chemistry, University of Mumbai, Vidyanagari, Santacruz, Mumbai, India

    P. J. Maliekal & P. M. Badani

  3. Chemistry Department, G. N. Khalsa College, Matunga, Mumbai, India

    S. Lingayat

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Patel, P., Maliekal, P.J., Lingayat, S. et al. Understanding the Kinetics and Reduction of Methylene Blue Using NaBH4. Russ. J. Phys. Chem. B 16, 869–876 (2022). https://doi.org/10.1134/S1990793122050074

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