caa a22 4500 445328347 CHVBK 20180317142729.0 cr unu---uuuuu 170323e20110401xx s 000 0 eng 10.1007/s10953-011-9675-5 doi (NATIONALLICENCE)springer-10.1007/s10953-011-9675-5 Experimental Study of a Closed System in the Chlorine Dioxide-Iodine-Ethyl Acetoacetate-Sulfuric Acid Oscillation Reaction by UV-vis and Online FTIR Spectrophotometric Methods [Elektronische Daten] [Fang Guo, Laishun Shi, Luyan Wang] The appearance of oscillations for the closed system ClO2-I2-ethyl acetoacetate depends critically on the pH in the absence of sulfuric acid, and was investigated by determining changes in the absorbance of $\mathrm{I}_{3}^{ -}$ with reaction time at the wavelength 280nm. The pH should be 2.2-3.8 for this reaction. The initial concentrations of ethyl acetoacetate, chlorine dioxide, iodine and sulfuric acid have great influences on the oscillations observed at wavelengths of 280nm or 350nm. The oscillations at 280nm occur as long as the reactants are mixed. However, at 350nm the oscillation is preceded by a pre-oscillatory or induction period. The oscillation curve is more regular and smooth at 350nm than that at 280nm. The amplitude and the number of oscillations are associated with the initial concentration of each reactant. (1)The higher the initial concentration of ethyl acetoacetate, the greater is the amplitude while the number of oscillations becomes smaller. The amplitude is small at the beginning stage but increases with reaction time. An opposite influence exists for chlorine dioxide. Finally, the oscillation suddenly ceases. (2)When the initial concentration of iodine is higher, the amplitude is small at the beginning stage but then increases with reaction time. When the initial concentration of iodine is lower, the amplitude is large at the beginning stage and then decreases with reaction time. An opposite influence exists for sulfuric acid. Equations for the triiodide ion reaction rate were obtained as functions of reaction time and initial concentrations at the oscillation stage. The intermediates were detected by 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. Springer Science+Business Media, LLC, 2011 Chlorine dioxide nationallicence Oscillation reaction nationallicence Closed reaction system nationallicence UV-vis spectrophotometry nationallicence Online FTIR nationallicence Ethyl acetoacetate nationallicence Guo Fang School of Chemistry and Chemical Engineering, Shandong University, South Campus, 250061, Jinan, P.R. China aut Shi Laishun School of Chemistry and Chemical Engineering, Shandong University, South Campus, 250061, Jinan, P.R. China aut Wang Luyan School of Chemistry and Chemical Engineering, Shandong University, South Campus, 250061, Jinan, P.R. China aut Journal of Solution Chemistry Springer US; http://www.springer-ny.com 40/4(2011-04-01), 587-607 0095-9782 40:4<587 2011 40 10953 https://doi.org/10.1007/s10953-011-9675-5 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10953-011-9675-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Guo Fang School of Chemistry and Chemical Engineering, Shandong University, South Campus, 250061, Jinan, P.R. China aut NATIONALLICENCE 700 1- Shi Laishun School of Chemistry and Chemical Engineering, Shandong University, South Campus, 250061, Jinan, P.R. China aut NATIONALLICENCE 700 1- Wang Luyan School of Chemistry and Chemical Engineering, Shandong University, South Campus, 250061, Jinan, P.R. China aut NATIONALLICENCE 773 0- Journal of Solution Chemistry Springer US; http://www.springer-ny.com 40/4(2011-04-01), 587-607 0095-9782 40:4<587 2011 40 10953 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer