1,2,4-丁三醇稀溶液缩醛反应的热力学和动力学特征（英文）

发布时间：2018-06-05 04:23

  本文选题：缩醛反应 + 热力学　； 参考：《过程工程学报》2017年06期

【摘要】：以正丁醛、正戊醛和正己醛为反应底物,研究了催化剂用量、醛醇比、反应温度等对1,2,4-丁三醇缩醛反应的影响,通过热力学平衡研究,获得了热力学平衡常数、反应焓变、反应熵变、反应吉布斯自由能变化等热力学参数,建立了该反应的动力学模型,利用线性自由能关系定量分析了醛的烷基链长度对缩醛反应的影响.结果表明,在298~323 K温度范围内,该反应为放热反应,明显受热力学限制.所建模型能很好地描述缩醛反应过程,反应的表观活化能为51.1~52.3 k J/mol.缩醛反应的平衡常数和反应速率均与极性效应常数(σ*)有良好的线性关系.
[Abstract]:The effects of the amount of catalyst, the ratio of aldehyde to alcohol and the reaction temperature on the acetal reaction of 1-butanediol 4-butanol were studied with n-butyraldehyde, n-pentaldehyde and n-hexaldehyde as the reaction substrates. The thermodynamic equilibrium constant and enthalpy change of the reaction were obtained through the thermodynamic equilibrium study. The kinetic model of the reaction was established by changing the reaction entropy and Gibbs free energy. The effect of alkyl chain length of aldehydes on acetal reaction was quantitatively analyzed by linear free energy relationship. The results show that the reaction is an exothermic reaction in the temperature range of 298 ~ 323K, which is obviously limited by thermodynamics. The model can describe the process of acetal reaction well, and the apparent activation energy of the reaction is 51.1 ~ 52.3 k / mol. There is a good linear relationship between the equilibrium constant and the reaction rate of acetal reaction and the polar effect constant.
【作者单位】： 中国科学院过程工程研究所绿色过程工程重点实验室;中国科学院大学化学化工学院;中国科学院青岛生物能源与过程研究所;
【基金】：Supported by Taishan Scholars Climbing Program of Shandong(No.tspd20150210) National Natural Science Foundation of China(No.21506221,21676283)
【分类号】：O621.25
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本文编号：1980498