Chlorine Dioxide–Iodine–Acetylacetone Oscillation Reaction Investigated by UV–Vis and Online FTIR Spectrophotometric Methods

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• 作者：Demei Li ; Laishun Shi ; Jingjing Chen ; Jian Gao
• 关键词：Chlorine dioxide ; Oscillation reaction ; UV–Vis spectrophotometry ; Online FTIR ; Apparent activation energy ; Acetylacetone
• 刊名：Journal of Solution Chemistry
• 出版年：2016
• 出版时间：January 2016
• 年：2016
• 卷：45
• 期：1
• 页码：81-94
• 全文大小：718 KB
• 参考文献：1.Dolnik, M., Epstein, I.R.: A coupled chemical burster: the chlorine dioxide–iodide reaction in two flow reactors. J. Chem. Phys. 98, 1149–1155 (1993)CrossRef
  2.De Kepper, P., Epstein, I.R., Kustin, K., Orbán, M.: Batch oscillations and spatial wave patterns in chlorite oscillating systems. J. Phys. Chem. 86, 170–171 (1982)CrossRef
  3.De Kepper, P., Epstein, I.R.: A mechanistic study of oscillations and bistability in the Briggs–Rauscher reaction. J. Am. Chem. Soc. 104, 49–55 (1982)CrossRef
  4.De Kepper, P., Boissonade, J., Epstein, I.R.: Chlorite–iodide reaction: a versatile system for the study of nonlinear dynamical behavior. J. Phys. Chem. 94, 6525–6536 (1990)CrossRef
  5.Lengyel, I., Rábai, G., Epstein, I.R.: Batch oscillation in the reaction of chlorine dioxide with iodine and malonic acid. J. Am. Chem. Soc. 112, 4606–4607 (1990)CrossRef
  6.Lengyel, I., Rábai, G., Epstein, I.R.: Experimental and modeling study of oscillations in the chlorine dioxide–iodine–malonic acid reaction. J. Am. Chem. Soc. 112, 9104–9110 (1990)CrossRef
  7.Lengyel, I., Li, J., Kustin, K., Epstein, I.R.: Rate constants for reactions between iodine- and chlorine-containing species: a detailed mechanism of the chlorine dioxide/chlorite–iodide reaction. J. Am. Chem. Soc. 118, 3708–3719 (1996)CrossRef
  8.Lengyel, I., Epstein, I.R.: Modeling of turing structures in the chlorite–iodide–malonic acid–starch reaction system. Science 251(4994), 650–652 (1991)CrossRef
  9.Lengyel, I., Kadar, S., Epstein, I.R.: Transient turing structures in a gradient-free closed system. Science 259(5094), 493–495 (1993)CrossRef
  10.Fabian, I., Gordon, G.: The kinetics and mechanism of the chlorine dioxide–iodide ion reaction. Inorg. Chem. 36, 2494–2497 (1997)CrossRef
  11.Szalai, I., De Kepper, P.: Turing patterns, spatial bistability, and front instabilities in a reaction–diffusion system. J. Phys. Chem. A 108, 5315–5321 (2004)CrossRef
  12.Strier, D.E., De Kepper, P., Boissonade, J.: Turing patterns, spatial bistability, and front interactions in the [ClO2, I2, I−, CH2(COOH)2] reaction. J. Phys. Chem. A 109, 1357–1363 (2005)CrossRef
  13.Riaz, S.S., Ray, D.S.: Spiral pattern in chlorite–iodide–malonic acid reaction: a theoretical and numerical study. J. Phys. Chem. 123, 174506.1–174506.5 (2005)CrossRef
  14.Long, D.A., Chodroff, L., O’Neal, T.M., Hemkin, S.: A true chemical clock: serially coupled chlorite–iodide oscillators. Chem. Phys. Lett. 447, 340–344 (2007)CrossRef
  15.Shi, L., Li, W., Wang, F.: Experimental study of a closed system in the chlorine dioxide–iodine–malonic acid–sulfuric acid oscillation reaction by UV–Vis spectrophotometric method. J. Solution Chem. 38, 571–588 (2009)CrossRef
  16.Gao, J., Shi, L., Wei, Q., Li, X., Li, Z.: Chlorine dioxide–iodine–ethyl 2-chloroacetoacetate oscillation reaction investigated by UV–Vis and online FTIR spectrophotometric methods. J. Solution Chem. 43, 1078–1092 (2014)CrossRef
  17.Shi, L., Qian, Y., Lin, S., Yang, B., Li, N., Liu, J.: Sodium chlorite–iodine–methyl acetoacetate oscillatory reaction investigated by UV–Vis spectrophotometric method. J. Iran. Chem. Soc. 10, 21–28 (2013)CrossRef
  18.Shi, L., Li, N., Liu, J., Qian, Y., Yang, B., Lin, S.: Sodium chlorite–iodine–methyl acetoacetate oscillatory reaction investigated by UV–Vis spectrophotometry. Indian J. Chem. Sect. A 52, 226–231 (2013)
  19.Powling, J., Bernstein, H.J.: The effect of solvents on tautomeric equilibria. J. Am. Chem. Soc. 73, 4353–4356 (1951)CrossRef
  20.Wyman, D.P., Kaufman, P.R., Freeman, W.R.: The chlorination of active hydrogen compounds with sulfuryl chloride. II. Esters, nitriles, nitro compounds, and aldehydes. J. Org. Chem. 29, 2706–2710 (1964)CrossRef
  21.Cieciuch, R.F.W., Westheimer, F.W.: Halide catalysis in the bromination of deoxybenzoin. J. Am. Chem. Soc. 85, 2591–2595 (1963)CrossRef
  22.Chen, E.Y., Song, X.H., Zhang, X.H.: A Study on isomerization of acetylacetone’s two isomers. J. Qiqihar Teach. Coll. (Nat. Sci.) 15, 31–32 (1995)
  
• 作者单位：Demei Li (1)
  Laishun Shi (1)
  Jingjing Chen (1)
  Jian Gao (1)
  
  1. School of Chemistry and Chemical Engineering, South Campus, Shandong University, Jinan, 250061, People’s Republic of China
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Physical Chemistry
  Industrial Chemistry and Chemical Engineering
  Geochemistry
  Oceanography
  Inorganic Chemistry
  Condensed Matter
  
• 出版者：Springer Netherlands
• ISSN：1572-8927

文摘

In order to study the chemical oscillatory behavior and mechanism of a new chlorine dioxide–iodine–acetylacetone reaction system, a series of experiments were carried out by using UV–Vis and online FTIR spectrophotometric methods. The initial concentrations of acetylacetone, chlorine dioxide, iodine, sulfuric acid, and the pH value have considerable influence on the oscillations observed at wavelength of 350 nm for the starch–triiodide ion complex (\({\text{QI}{_{3}^-}}\)). There is a pre-oscillatory or induction stage, the amplitude and the number of oscillations are associated with the initial concentration of reactants. Equations were obtained for the starch–triiodide ion complex (\({\text{QI}{_{3}^-}}\)) reaction rate change with reaction time and the initial concentrations in the oscillation stage. The oscillation reaction can be accelerated by increasing the reaction temperature. The apparent activation energies at the induction stage and the oscillation stage are 45.64 and 12.39 kJ·mol−1, respectively. The intermediates were detected by the online FTIR analysis. Based upon the experimental data in this work and in the literature, a plausible reaction mechanism was proposed for the oscillation reaction.