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- Runaway reaction; calorimeter; quantum mechanical calculation
Chemical reactivity hazards have posed a significant challenge for industries that manufacture, store, and handle reactive chemicals. Without proper management and control of reactivity, numerous incidents have caused tremendous loss of property and human lives. The U.S. Chemical Safety and Hazard Investigation Board (CSB) reported 167 incidents involving reactive chemicals that occurred in the U.S. from 1980 to 2001. According to the report, 35 percent of the incidents were caused by thermal runaway reactions, such as incidents that involved hydroxylamine and hydroxylamine nitrate. The thermal stability of hydroxylamine system under various industrial conditions was studied thoroughly to develop an understanding necessary to prevent recurrence of incidents. The macroscopic runaway reaction behavior of hydroxylamine system was analyzed using a RSST (Reactive System Screening Tool) and an APTAC (Automatic Pressure Tracking Calorimeter). Also, computational chemistry was employed as a powerful tool to evaluate and predict the measured reactivity. A method was proposed to develop a runaway reaction mechanism that provides atomic level ofinformation on elementary reaction steps, in terms of reaction thermochemistry, activation barriers, and reaction rates. This work aims to bridge molecular and macroscopic scales for process safety regarding reactive chemicals and to understand macroscopic runaway reaction behaviors from a molecular point of view.