Cisneros Lizbeth O, Rogers William J, Mannan M S
Chemical Engineering Department, Texas A&M University, College Station, TX 77843-3122, USA.
J Hazard Mater. 2002 Nov 11;95(1-2):13-25. doi: 10.1016/s0304-3894(02)00163-2.
This paper presents experimental measurements of 50 mass% hydroxylamine (HA)/water thermal decomposition in air and vacuum environments using an automatic pressure tracking adiabatic calorimeter (APTAC). Overall kinetics, onset temperatures, non-condensable pressures, times to maximum rate, heat and pressure rates versus temperature, and mixture vapor pressures for the experiments in vacuum were similar when compared to the corresponding data for HA decomposition in air. Determined was an overall activation energy of 119+/-8 kJ/mol (29+/-2 kcal/mol), which is low compared to 257 kJ/mol (61.3 kcal/mol) required to break the H(2)N-OH bond reported in the literature. The availability of oxygen from air did not affect detected runaway decomposition products, which were H(2), N(2), N(2)O, NO, and NH(3), for samples run in vacuum or with air above the sample. A delta H(rxn) of -117 kJ/mol (28 kcal/mol) was estimated for the HA decomposition reaction under runaway conditions.
本文介绍了使用自动压力跟踪绝热量热仪（APTAC）对50质量%羟胺（HA）/水在空气和真空环境中的热分解进行的实验测量。与空气中HA分解的相应数据相比，真空中实验的整体动力学、起始温度、不可冷凝压力、达到最大速率的时间、热速率和压力速率与温度的关系以及混合物蒸气压均相似。确定的整体活化能为119±8 kJ/mol（29±2 kcal/mol），与文献报道的断裂H(2)N-OH键所需的257 kJ/mol（61.3 kcal/mol）相比很低。空气中氧气的存在并不影响检测到的失控分解产物，对于在真空或样品上方有空气的情况下运行的样品，分解产物为H(2)、N(2)、N(2)O、NO和NH(3)。在失控条件下，HA分解反应的ΔH(rxn)估计为-117 kJ/mol（28 kcal/mol）。
