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model to do just that. The model builds on Arrhenius’ concept that only “hot” molecules can react (Moore and Pearson, 1982). The model assumes that the rate of reaction is equal to the rate of collisions of molecules. The main weakness of the Trautz-Lewis version of collision theory is that it ignores the fact that one needs a special geometry in order for a reaction to occur. Given this weakness the Trautz- Lewis model, it does not always give a good prediction of the rate. Another weakness of the model is that it does not explain activation barriers. Neither Arrhenius, nor Trautz, nor Lewis was able to explain why reactants needed to be “hot” in order for reaction to occur. Trautz and Lewis just assumed - without explaining this assumption - that reactions had barriers. It was transition state theory that came later to cover this gap. 2.4 BASIC TRANSITION-STATE THEORY 2.4.1 The concept of transition-state theory The original transition-state theory developed by Eyring as the principal contributor is based on two fundamentals postulates. One first assumption the existence of a molecular aggregate called the ‘activated complex’ T , which may have a geometry corresponding to that of the transition state. Second, the hypothetical complex T is assumed to be in quasi-equilibrium with the initial state during the entire course of a reaction. A substitution reaction, for example, can be understood by a scheme as follows: A + BC T# AB + C The activated complex was regarded as being ‘similar to an ordinary molecule, possessing all the usual thermodynamic properties, with the exception that the motion in one direction, i.e., along the reaction coordinate, would lead to decomposition at a 14PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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