摘要
采用Joback基团贡献法、Yoneda基团贡献法及Tyagi方程估算了无催化"两步法"合成油酸甲酯反应体系中油酸、油酰氯、油酸甲酯等物质的热力学数据,并结合可查取的物性实验数据,得到了该反应体系反应焓变ΔrHm、反应熵变ΔrSm、反应吉布斯自由能变ΔrGm及反应平衡常数K。结果表明:标准状态下酰氯化为吸热反应,且单独存在时较难进行,醇解为放热反应,且反应可进行完全。通过分析各热力学函数数值特点,结合整个两步反应的始末态热力学数据,依据近似原则和勒夏特列原理平衡移动原理,可以得出酰氯化反应在适当条件下是可正常进行的,且实际实验现象对此进行了验证。
The thermodynamic of methyl oleate synthesis was studied based on the two-step noncatalytic method including acylation reaction and aleoholysis reaction. The thermophysical properties of oleic acid, oleoyl chloride and methyl oleate were calculated by Tyagi equation and some popular group contribution methods, Joback method and Yoneda method. The enthalpy ArHm, entropy ArSm, free energy ArGm, and equilibrium constant K were estimated and these data were analyzed at different temperatures. Chemical reactions are determined by the laws of thermodynamics. The results showed that acylation reaction was endothermic and difficult to carry out separately under standard conditions for temperature and pressure, while alcoholysis reaction was exothermic and can proceed itself completely. Considered the thermodynamic data of whole two-step reaction at the beginning and end, acylation reaction can occur according to the approximate principle and Le Chatelier＇s principle, and it was testified by the actual experimental phenomenon.
出处
《化学工程》
CAS
CSCD
北大核心
2016年第2期35-40,共6页
Chemical Engineering(China)
关键词
油酸甲酯
油酰氯
基团贡献法
热力学
methyl oleate
oleoyl chloride
group contribution method
thermodynamics
