Abstract:

Thermal safety parameters obtained by heat flow chemical reaction calorimetry test such as target reaction heat(ΔH), specific heat capacity of reaction system(c_p ) and maximum heat accumulation(X_ac) etc. are indispensable key parameters in safety risk assessment of fine chemical reactions. The accuracy(precision and trueness) of the test results affects the process risk classification of chemical reactions directly. At present, there is no report on accuracy and effectiveness of thermal safety parameters of chemical reactions. In order to solve this problem, the acetic anhydride and the water were proposed as reference materials. The“coefficient of variation(CV) method”and“Grubbs test method”were used to verify the repeatability and reproducibility deviation of parameters such as ΔH, c_p, and X_ac, which was obtained by the hydrolysis reaction of acetic anhydride measured by the heat flow reaction calorimetry. The“t verification method”was used to evaluate the accuracy of the specific heat capacity of water measured by the heat flow reaction calorimetry. The results showed that the repeatability standard deviation of parameters such as ΔH, c_p, and X_ac in the same laboratory and the reproducibility standard deviation compared with the other four laboratories met the requirements, which was obtained from the reaction rate of acetic anhydride hydrolysis measured by heat flow chemical reaction calorimetry test. There was no substantial bias between the specific heat capacity data of 25℃ water obtained by heat flow calorimetry and the standard specific heat capacity value t. Therefore,both the precision and the trueness of heat flow calorimetry were validated satisfied.

Key words: safety, chemical reaction, hydrolysis, heat flow calorimetry, precision, trueness

摘要：

热流法化学反应量热测试获取的目标反应热（ΔH）、反应体系比热容（c_p）和最大热累积度（X_ac）等热安全参数是精细化工反应安全风险评估中不可或缺的关键参数，其测试结果的准确度（即正确度与精密度）直接影响化学反应的工艺危险度分级。目前关于测得的化学反应热安全参数准确度和有效性的研究未见报道。为解决这一问题，提出了以醋酸酐和水作为参考物质，采用“变异系数（CV值）法” 和“道格拉斯（Grubbs）检验法”分别验证热流法反应量热测试醋酸酐水解反应的ΔH、C_p 、X_ac等参数的精密度（即重复性和再现性偏差），采用“t验证法”评估热流法反应量热测试水的比热容的正确度。研究结果表明：热流法反应量热测试醋酸酐水解反应的ΔH、C_p 、X_ac等参数在同一实验室内的重复性标准偏差和与其他4家实验室比对的再现性标准偏差均满足要求；采用热流法量热测试得到25℃水的比热容数据与标准比热容值t验证结果不存在实质性偏倚。因此，测试结果的精密度和正确度均满足要求。

关键词: 安全, 化学反应, 水解, 热流法, 精密度, 正确度