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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Equilibrium Reactions in Supercritical Difluoromethane
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Equilibrium Reactions in Supercritical Difluoromethane

机译：超临界二氟甲烷中的平衡反应

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摘要

A dielectometry technique is used to follow the extent of two equilibrium reactions in supercritical difluoromethane (sc HFC32), and the validity of the technique is demonstrated in the liquid state and compared to results obtained using gas chromatography-mass spectroscopy (GC-MS). The apparent equilibrium constant for the acid-catalyzed esterification of benzoic acid with 1-butanol decreased as the pressure increased, and this was proposed to be due to clustering at lower solvent density. In supercritical carbon dioxide (sc CO2), the equilibrium constant was similar to that in sc HFC32, despite the large difference in the dielectric constant of the fluids. The solute had a significant effect on the solution dielectric constant, such that the two solutions were similar. An acid-catalyzed aldol condensation reaction was also studied, and the apparent equilibrium constant was observed to change in a manner similar to that observed for the esterification reaction. The overall change in equilibrium constant was less than that observed for the esterification reaction and this was rationalized, in terms of the different dipole moments of the reagents in the two reactions.
机译：使用介电法跟踪超临界二氟甲烷（sc HFC32）中两个平衡反应的程度，并在液体状态下证明了该技术的有效性，并将其与使用气相色谱-质谱（GC-MS）获得的结果进行了比较。苯甲酸与1-丁醇的酸催化酯化反应的表观平衡常数随压力的增加而降低，这被认为是由于在较低的溶剂密度下发生了聚集。尽管流体的介电常数差异很大，但在超临界二氧化碳（sc CO2）中，平衡常数与sc HFC32中的平衡常数相似。溶质对溶液的介电常数有显着影响，因此两种溶液相似。还研究了酸催化的醛醇缩合反应，并且观察到表观平衡常数以与酯化反应观察到的方式相似的方式变化。平衡常数的总体变化小于酯化反应所观察到的变化，并且根据两个反应中试剂的不同偶极矩，这是合理的。

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