重氮盐水解制备对苯二酚的热力学分析

Thermodynamic analysis for preparation of hydroquinone by hydrolysis of diazonium salts

由对氨基苯酚重氮盐水解制备对苯二酚的反应由于缺乏热力学数据和反应的热力学分析,给水解反应器的设计、工艺控制等带来困难。文中采用ABWY法、Cardozo基团贡献法、Kopp规则、Dulong-Petit规则和基希霍夫公式估算了该反应体系相关物质的基础数据及热力学数据,并进行了系统的热力学分析。考察了反应焓变、Gibbs自由能、反应平衡常数与温度的关系,结果显示:反应焓变随温度的增大而减小且恒小于0,Gibbs自由能随温度的增加而减小且恒小于0,反应平衡常数数量级大于40。热力学数据的估算可为重氮盐水解反应的工艺条件提供理论依据。

As the reaction of hydroquinone preparation with p-aminophenol diazonium salt solution lacks the thermodynamic data and reaction thermodynamics analysis, it brings difficulties to the hydrolysis reactor design and process control. By using ABWY method, Cardozo group contribution method, Kopp rules, Dulong-Petit rules and Kirchhoff formula, the basic data and thermodynamic data of the related substances in the system were calculated, and the thermodynamic analysis of the reaction was made. The relationships of reaction enthalpy change, Gibbs free energy,reaction equilibrium constant and reaction temperature were studied. The results show that the reaction enthatpy change and Gibbs free energy both decrease and are constant less than 0 with the rise of temperature, and the order of reaction equilibrium constant is greater than 40. The estimation of thermodynamic data can provide a theoretical basis for the process conditions of heavy nitrogen brine solution reaction.