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Analysis of transition from low to high iodide and iodine state in the Briggs–Rauscher oscillatory reaction containing malonic acid using Kolmogorov–Johnson–Mehl–Avrami (KJMA) theory

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Abstract

The oscillatory behavior is not the only interesting nonlinear phenomena that appeared in the Briggs–Rauscher (BR) reaction. The BR reaction containing malonic acid may undergo a sudden transition from low (the state I) to high iodide and iodine (the state II) concentration states. This paper focuses on the mixture with an immutable [CH2(COOH)2]0/[IO3 −]0 = 1.5 value, where state I to state II transition occurs after a time delay and BR reaction ended with a solution abundant of solid iodine. The state I to the state II transition curves obtained at different temperatures were analyzed using the Kolmogorov–Johnson–Mehl–Avrami (KJMA) theory. The KJMA theory was applied for monitoring the crystallization process of isolated solid iodine product at various levels of operating temperatures. At T < 33.5 °C, we have one type of the process and iodine was formed by autocatalysis pathway. On the other hand, at T ≥ 33.5 °C, two processes occur. With the rise in operating temperature, the emergence of inhomogeneous distribution of nuclei was identified and it was established the primary and secondary crystallization processes of iodine. At elevated temperatures, it was also found that the strong influence of impingement mechanism exists. Results obtained are the first step toward elucidation of the complex reaction mechanism of the state I → state II transition.

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Acknowledgements

The present investigations were supported by The Ministry of Education, Science and Technological Development of the Republic of Serbia, under Project 172015.

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Authors and Affiliations

  1. Faculty of Physical Chemistry, University of Belgrade, Studentski Trg 12, Belgrade, Serbia

    Maja C. Pagnacco, Jelena P. Maksimović & Bojan Ž. Janković

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  1. Maja C. Pagnacco
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  2. Jelena P. Maksimović
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  3. Bojan Ž. Janković
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Correspondence to Maja C. Pagnacco.

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Pagnacco, M.C., Maksimović, J.P. & Janković, B.Ž. Analysis of transition from low to high iodide and iodine state in the Briggs–Rauscher oscillatory reaction containing malonic acid using Kolmogorov–Johnson–Mehl–Avrami (KJMA) theory. Reac Kinet Mech Cat 123, 61–80 (2018). https://doi.org/10.1007/s11144-017-1288-6

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