Abstract

The increasing availability of electronic equipment for automatic experiment control and data acquisition, and the availability of computing facilities make high information kinetic studies feasible. This latter phrase is used to describe kinetic experiments in which stability determining factors (e.g. pH, ionic strength, etc.,) are programmed within an exp eriment rather than several tests being performed each at a different level of the stability determining factor. Thus much more information can be extracted from a single experiment, and this should ultimately lead to decreased experimental effort. This paper describes a non-isothermal, programmed acid concentration kinetic experiment through which the two rate constants and activation energies associated with the acid and solvent catalyzed hydrolysis of p-nitrophenyl acetate were simultaneously determined. Zero and infinite time assays were also estimated from the data. Results from this experiment were in close agreement with those from traditional (isothermal, fixed acid concentration) kinetic experiments and with estimates from non-isothermal fixed acid concentration tests. The mathematical model developed for this situation accounts for volume change due to acid addition, sampling and thermal volume expansion. With minor modification it is applicable to other situations (e.g. ionic strength programming).

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