Anomalous Reaction Rate near the Critical Point

本文研究了液-液和气-液两种系统在临界点附近的关系率增强问题。并对其增强机理进行了探讨。(1)在正己烷-硝基苯混合物的稀溶液中，异戊二烯-马来酸酐反应在液-液临界点附近反应速率的异常增强是难以识别的。这一事实与文献数据相矛盾，似乎在临界点附近提高反应速率的研究中非常重要。由过渡态理论导出的反应速率方程与用汽液平衡数据计算二元相互作用参数的正则溶液模型相结合，可以很好地关联得到的反应速率。研制了一种测量高压气相反应速率的装置。用该装置测定了异戊二烯-马来酸酐在超临界二氧化碳稀释条件下的反应速率。所得反应速率与文献数据吻合。系统的测量仍然是必需的。

In the present work, the relation rates enhancement near the critical points of both liquid-liquid and gas-liquid systems were studied. And the enhancement mechanism was considered.(1) An anomalous enhancement of reaction rate near the liquid-liquid critical point is difficult to recognize for an isoprene-maleic anhydride reaction in a dilute solution of the hexane-nitrobenzene mixture. This fact is contradictory with the literature data and seems to be very important in a study of reaction rate enhancement near the critical point. The reaction rates obtained can be well correlated by a reaction rate equation derived from the transition state theory coupled with the regular solution model in which the binary interaction parameters are evaluated by using vapor-liquid equilibrium data.(2) An apparatus for measuring the reaction rates in high pressure gaseous phase was developed. By using the apparatus, reaction rates of an isoprene-maleic anhydride reaction in a dilute condition of supercritical carbon dioxide were measured. The reaction rate obtained in coincident with the literature data. A systematic measurement is still required.