热动力学的滴定量热法研究——Ⅱ.考虑热滞后的一级反应精确热动力学

Titration Calorimetry Applied to the Study of Thermokinetics——Ⅱ. A Precise Titration Thermokinetics Model of First - order Reactions with Consideration of Thermal Inertia

建立了滴定热量计滴定期一级反应热动力学的精确数学模型,并在此基础上探讨了热滞后对此模型的影响.经过改进的模型大大提高了利用滴定热量计获取动力学数据的准确度,且扩大了滴定热量计研究的一级反应体系的范围,使其适用反应的半衰期可以小至十几秒.本文采用此模型,研究了去离子水溶剂中乙酸乙酯皂化反应的热动力学,实验结果验证了该模型研究一级反应热动力学的适用性.

With consideration of thermal inertia, we suggested a more accurate mathematical model for thermokinetics of first - order reactions in titration period by titration calorimetry. This model can be applied to more chemical reactions of which the half-value period time can be as small as about ten seconds. In this paper, thermokinetics of the saponification of ethyl acetate in doubly distilled water was studied by titration calorimetry. The reliability of this titration calorimetric model for studying thermokinetics of first - order reactions has been verified by the experimental results obtained.