Chemical Kinetics in a Bi-Palladium Complex

Abstract

Using mathematical techniques developed over the course of the 20th Century this thesis analyses a contemporary chemical reaction that is of interest to modern chemists. The reaction involves a novel bimetallic palladium complex with unusual oxidation states. Because of its common use as a catalyst, palladium chemistry has been, and continues to be of great importance. This thesis presents the development and analysis of a mathematical model based on computational work by Ariafard et al. (2011). Attempts to include a fast equilibrium as proposed by Powers & Ritter (2009) resulted in unrealistic predictions, as did the inclusion of a pool-chemical approximation. Converting the model into one that describes a continuous-flow stirred tank reactor allowed for the reaction rate to be easily controlled and set to a realistic value. The model predicts that one pathway, the dissociative pathway, is favoured at low temperatures and the other, the direct pathway, at higher temperatures. The model also provides a range of other predictions including: a range of ambient temperatures at which multiple equilibria are present; conditions under which small changes in ambient temperature result in drastic changes in the equilibrium temperature and concentrations; and the variation of concentrations and temperature through time. The model is consistent with experimental results presented by Deprez & Sanford (2009), Powers & Ritter (2009) and Powers et al. (2010). The ease with which the model fits the experimental data provides evidence to support the mechanism proposed by Ariafard et al. (2011). This thesis provides a number of predictions that can be tested in future experimental work.

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