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Long-Lasting Complex Reaction Behavior in a Closed Ferroin–Bromate–Hydroxybenzenesulfonate System
The Journal of Physical Chemistry A ( IF 2.9 ) Pub Date : 2018-10-05 00:00:00 , DOI: 10.1021/acs.jpca.8b07766
Alexander Tang 1 , James R. Green 1 , Jichang Wang 1
Affiliation  

The bromate–phenolsulfonate reaction was found to exhibit spontaneous oscillations in a batch reactor, where the addition of small amounts of ferroin would result in nonoscillatory behavior. As the ferroin concentration was increased, the system produced very rich nonlinear behavior, including three isolated oscillatory regimes that were separated by as long as 48 h nonoscillatory period. The long-lasting nonlinear behavior may be attributed to the slow desulfonation of phenolsulfonate in an acidic solution, forming phenol-like intermediates. However, unlike the bromate–phenol oscillator, oxygen was found to greatly influence the reaction, and various complex oscillations could be observed by tuning the oxygen concentration. Mechanistic studies performed through employing 1H NMR spectroscopy and mass spectrometry to measure intermediate species at different stages of the reaction were able to identify 1,4-benzoquinone, 2-bromo-1,4-benzoquinone, 2,6-dibromo-1,4-benzoquinone, and 2,4,6-tribromophenol as major components during the reaction.

中文翻译:

封闭的铁-溴酸盐-羟基苯磺酸盐体系中的持久络合反应行为

发现溴酸盐-苯酚磺酸盐反应在间歇式反应器中表现出自发振荡,在其中添加少量的铁蛋白会导致非振荡行为。随着铁蛋白浓度的增加,该系统产生了非常丰富的非线性行为,包括三个孤立的振荡状态,它们被分开长达48小时的非振荡周期。长期的非线性行为可能归因于苯酚磺酸盐在酸性溶液中的缓慢脱磺作用,形成了类似苯酚的中间体。但是,与溴酸盐-苯酚振荡器不同的是,发现氧气会极大地影响反应,并且通过调节氧气浓度可以观察到各种复杂的振荡。通过雇用1进行的力学研究1H NMR光谱和质谱法可测量反应不同阶段的中间物种,从而能够鉴定1,4-苯醌,2-溴-1,4-苯醌,2,6-二溴-1,4-苯醌和2反应过程中,以4,6-三溴苯酚为主要成分。
更新日期:2018-10-05
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