Anomalous Reaction Rate near the Critical Point

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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.