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By Chan Young Park and Allan J. Jacobson

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Extra resources for Electrical Conductivity and Oxygen Nonstoichiometry of La0.2Sr0.8Fe0.55Ti0.45O3-d

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Rate constants for certain reactions can be predicted a priori from statistical mechanical considerations, but this is an extremely difficult and error-prone task, especially if the molecules involved have any significant degree of complexity. Typically, rate constants are measured experimentally from a determination of concentration vs. time in a single experiment or from analysis of rate data for a range of initial concentrations. Determining the Fundamentals 19 rate laws and rate constants of a large number of chemical reactions has been one of the major accomplishments of chemical kinetics in the past century.

In Chapter 5, we shall study several examples of mechanisms for complex reactions, examine how to construct such mechanisms, and consider how well they do in explaining the results of experiments. 2 Stability Analysis In analyzing the dynamical behavior of a chemical system, it is useful to begin at the end. This seemingly paradoxical observation is meant to point out that it is essential to understand the asymptotic, or long-term, behavior of a system if we are to characterize its evolution in time.

Another simplification that often arises in complex mechanisms occurs when an elementary step and its reverse both occur at relatively rapid rates. 18). 18). 17): and, thus, The reaction is still autocatalytic in X. One more scenario is worth mentioning. Often, an intermediate in a mechanism is present at a very low concentration that changes little during most of the reaction. Typically, the intermediate is absent initially, then builds up rapidly to a nearly constant level at which it remains before dropping back to zero at the completion of the reaction.

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