Using Temperature-Programmed Reaction for Kinetic Analysis of Reactions in Dilute Aqueous Solutions at High Pressure

摘要

The technique of temperature-programmed reaction (TPR) is shown to be a practical experimental method for determining reaction-rate expressions and kinetics parameters for reactions in dilute aqueous solutions under high ambient pressure. By sampling and measuring the extent of reaction during a rise in temperature, information normally obtained from a series of isothermal batch kinetics experiments can be found in a single TPR test. The use of nonlinear least-squares regression eliminates the need to achieve a constant rate of temperature rise, simplifies the experimental requirements for TPR results, and gives more accurate answers than does a linear analysis of TPR results. Numerical simulations of TPR tests in the presence of random concentration-measurement error is used to assess the accuracy of the technique and to identify the best values of crucial operating parameters. The results of two TPR experiments measuring the alkaline hydrolysis of ethyl acetate demonstrate the applicability of the technique to reactions in dilute aqueous solutions at high pressure. These preliminary experimental results, along with numerical simulations, allow us to chart a course for future TPR kinetics experiments on a large number of similar reactions. 16 refs., 6 figs., 8 tabs. (ERA citation 11:025932)