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A kinetic model for the autocatalytic behavior of nitric acid/formic acid mixtures to predict induction period
Process Safety and Environmental Protection ( IF 7.8 ) Pub Date : 2021-05-10 , DOI: 10.1016/j.psep.2021.05.012
Mahoko Ando , Michiya Fujita , Yu-ichiro Izato , Atsumi Miyake

Prevention of runaway reactions is one of the ultimate goals of process safety engineering. However, the lack of knowledge for mechanism and kinetics of autocatalytic reactions enables to design safer processes handling reactive materials. The purpose of the present study was to accurately predict the induction period of autocatalytic reaction system composed by nitric acid and formic acid using a sophisticated kinetic model for the autocatalytic behavior. The reactions of nitric acid with organic compounds are autocatalytic and so can rapidly generate large amounts of heat and pressure without obvious warning signs. Thermal analyses were carried out using a reaction calorimeter while ion chromatography was employed to quantify reaction products. Exothermic reactions were observed to begin when the concentration of nitrous acid, which was identified as the autocatalyst, exceeded 4.6 ± 1.2 mmol L−1. A kinetic model was determined as d[HONO]/dt = 2.62 × 1012exp(1.06 × 104/T)・[HNO3]2.5±0.1[HCOOH]1.8±0.1[HONO]1.9±0.1. This model was in good agreement with other results obtained from reaction calorimetry.



中文翻译:

硝酸/甲酸混合物自催化行为预测诱导期的动力学模型

防止失控反应是​​过程安全工程的最终目标之一。但是,缺乏对自动催化反应机理和动力学的认识,使得设计出处理反应性材料的更安全的方法成为可能。本研究的目的是使用复杂的自催化行为动力学模型,准确预测由硝酸和甲酸组成的自催化反应系统的诱导期。硝酸与有机化合物的反应是自催化的,因此可以迅速产生大量的热量和压力,而没有明显的警告信号。使用反应量热仪进行热分析,同时使用离子色谱法定量反应产物。观察到放热反应开始于亚硝酸浓度,-1。动力学模型确定为d [HONO] / d t = 2.62×10 12 exp(1.06×10 4 / T)・ [HNO 3 ] 2.5±0.1 [HCOOH] 1.8±0.1 [HONO] 1.9±0.1。该模型与从反应量热法获得的其他结果非常吻合。

更新日期:2021-05-19
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