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Kinetic Description of Ascorbic Acid Decomposition in Redox Initiator Systems for Polymerization Processes
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2019-07-12 , DOI: 10.1021/acs.iecr.9b00710 Baldur Schroeter 1 , Sven Bettermann 1 , Henning Semken 1 , Timo Melchin 2 , Hans-Peter Weitzel 2 , Werner Pauer 1
Industrial & Engineering Chemistry Research ( IF 3.8 ) Pub Date : 2019-07-12 , DOI: 10.1021/acs.iecr.9b00710 Baldur Schroeter 1 , Sven Bettermann 1 , Henning Semken 1 , Timo Melchin 2 , Hans-Peter Weitzel 2 , Werner Pauer 1
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The temperature dependent redox decomposition rate constants of ascorbic acid (AsAc) in aqueous solutions were quantified in the presence of ammonium iron(III) sulfate dodecahydrate (Fe-cat) and tert-butylhydroperoxide (TBHP). Decomposition rates were determined in a temperature range from 35–75 °C with respect to the component ratios. First-order kinetics were observed up to specific conversions (∼20–80%) for AsAc decomposition. The application of a flexible Weibull model provided a good and comparable description (R2 ≥ 0.992) of decomposition processes up to high AsAc conversions (96%) at all studied reaction conditions. The activation energy was determined as a function of AsAc and Fe-cat ratios (38–79 kJ mol–1). Statistical modeling facilitated the prediction of rate constants. Thus, it was possible to adjust the reaction rate of emulsion copolymerizations of vinyl acetate and Versa10 in a broad temperature range (10–70 °C) by variation of the Fe-cat content.
中文翻译：
用于聚合过程的氧化还原引发剂系统中抗坏血酸分解的动力学描述
在十二水合硫酸铁铵（Fe-cat）和叔丁基氢过氧化物（TBHP）的存在下，定量测定了水溶液中抗坏血酸（AsAc）的温度依赖性氧化还原分解速率常数。相对于组分比率，分解速率是在35-75°C的温度范围内确定的。观察到一级动力学直至AsAc分解达到特定的转化率（约20–80％）。柔性维泊尔模型的应用提供了良好的和可比较的描述（- [R 2分解≥0.992）处理直至在所有被研究的反应条件高ASAC的转化率（96％）。确定活化能为AsAc和Fe-cat比的函数（38–79 kJ mol –1）。统计建模促进了速率常数的预测。因此，通过改变Fe-cat含量，可以在很宽的温度范围（10-70°C）中调节乙酸乙烯酯和Versa10的乳液共聚反应速率。
更新日期：2019-07-13
中文翻译：
用于聚合过程的氧化还原引发剂系统中抗坏血酸分解的动力学描述
在十二水合硫酸铁铵（Fe-cat）和叔丁基氢过氧化物（TBHP）的存在下，定量测定了水溶液中抗坏血酸（AsAc）的温度依赖性氧化还原分解速率常数。相对于组分比率，分解速率是在35-75°C的温度范围内确定的。观察到一级动力学直至AsAc分解达到特定的转化率（约20–80％）。柔性维泊尔模型的应用提供了良好的和可比较的描述（- [R 2分解≥0.992）处理直至在所有被研究的反应条件高ASAC的转化率（96％）。确定活化能为AsAc和Fe-cat比的函数（38–79 kJ mol –1）。统计建模促进了速率常数的预测。因此，通过改变Fe-cat含量，可以在很宽的温度范围（10-70°C）中调节乙酸乙烯酯和Versa10的乳液共聚反应速率。
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