Pure chemical kinetics

The general goal of chemical kinetics is the study of the rates and mechanisms of chemical reactions. In moving from fundamental towards more and more applied fields, it is convenient to distinguish pure chemical kinetics, applied chemical kinetics and chemical reaction engineering. 

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Belles [29] essentially established a pure chemical-kinetic-thermodynamic approach to estimating detonation limits. Questions have been raised about the approach, but the line of reasoning developed is worth considering. It is a fine example of coordinating various fundamental elements discussed to this point in order to obtain an estimate of a complex phenomenon. 

It seems that the simulation of diffusion controlled reactions of groups on polymer chains developed by Muthukumar et al. ( ) that takes into account the bond formation by determined conformational rearrangement, can be adapted for the equilibrium situation, i.e. for systems controlled by pure chemical kinetics. 

Pure chemical kinetics is concerned with the theory of elementary processes and reaction mechanisms. Several books deal with the general problems of chemical kinetics [1—6], whereas others are oriented more towards homogeneous chemical kinetics [7—13]. 

A reaction mechanism is a sequence of elementary processes proposed to account for experimental kinetic results. Pure chemical kinetics proposes a classification of various types of mechanism (non-chain mechanisms, straight-chain and branched-chain mechanisms, etc.), establishes relationships between the properties of a global reaction and those of the elementary processes involved in the corresponding mechanism, and provides rules for writing a priori a reaction mechanism from a knowledge of the thermochemical and kinetic characteristics of the... 

Applied chemical kinetics, based on the concepts and models of pure chemical kinetics, is the methodology of experimentation in chemical kinetics and of the analysis and modelling of kinetic phenomena. Table 1... 

The analysis of kinetic data and their interpretation by models have been discussed in books dealing with pure chemical kinetics [1—15],... 

A further complication arises in the case of heterogeneous catalysis where the activity of the catalyst can change with time on stream or with reactant composition. Changes of this kind are themselves time-dependent processes that are overlaid on the time-dependent kinetics of the chemical transformations. The untangling of all these effects so that pure chemical kinetics can be studied is an important aspect of mechanistic studies using kinetics. See section on catalyst instabilities later in this chapter.)... 

The study of elementary steps is the proper domain of pure chemical kinetics. The general theory of the rate of elementary steps is absolute rate theory or the theory of the transition state. As elementary steps can be so varied from a chemical standpoint it might seem that a general theory of their rates would be, if it exists at all, so general as to be almost useless. Such is not the case. The main results of this general theory will be presented insofar as they provide an answer to the basic question How does the rate of an elementary step depend on temperature, pressure (or volume) and composition of the system ... 

In an earlier discussion (Sect. 3.4) it was mentioned that the electrode reactions of proteins could be governed by radial-type diffusion, even at a macroscopically planar electrode surface, because of specificity for electroactive sites having microscopic dimensions. Deviation from linear diffusion behaviour depends upon the size and density of these sites [125,126]. Thus while the differences in waveshape between native and Ru couples that was noted in these studies may have a purely chemical-kinetic origin, the interesting possibility also arises that there exists different effective mass transport behaviour for the electrode reactions of each redox centre contained in a multi-centred macromolecule. Further evidence for this suggestion is presented in Sect. 5.2. 

The capacitive relationship and the expression of the purely chemical kinetic constant are borrowed from case study E4 in Chapter 8 ... 

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