Thermodynamic Analysis of Isomerization Equilibria of Chlorotoluenes and Dichlorobenzenes in a Biphasic Reaction Systems Containing Highly Acidic Chloroaluminate Melts

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• 作者：Sergey P. VerevkinJulia Messner ; Vladimir N. Emel’yanenko ; Mikhail G. Gantman ; Peter S. Schulz ; Peter Wasserscheid
• 刊名：Journal of Physical Chemistry B
• 出版年：2016
• 出版时间：December 29, 2016
• 年：2016
• 卷：120
• 期：51
• 页码：13152-13160
• 全文大小：362K
• ISSN：1520-5207

文摘

Thermodynamics and kinetics of the isomerization of chlorotoluenes and dichlorobenzene to the technically desired meta-isomers have been studied in the presence of highly acidic chloroaluminate melts with alkali metal and organic imidazolium cations. Enthalpies of four isomerization processes in reacting systems of chlorotoluenes and dichlorobenzene were obtained from temperature dependencies of the corresponding equilibrium constants in the liquid phase. Experimental reaction enthalpies, enthalpies of vaporization, and absolute vapor pressures of chlorotoluenes and dichlorobenzene have been used for the validation of quantum-chemical methods to predict thermodynamic functions of the four reactions under study successfully. Values of the standard Gibbs energies of formation, standard enthalpies and entropies of formation of chlorotoluenes and dichlorobenzenes in the liquid and in the gas phase have been derived. These values allow optimization of liquid–liquid biphasic manufacturing technologies for halogen-substituted benzenes.