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reaction as occurring via a transition-state species (in many presentations the term ‘transition state’ is used synonymously with activated complex). It is better to be avoided, however, because firstly the word ‘complex’ implies an entity, which has a chemically significant lifetime, which the transition state does not, and secondly, the collision complex, which may be formed when two molecules collide, is often called an activated complex. The chemical reaction rate is evaluated by statistical- mechanical methods. The earliest work on reaction rate theory came from Arrhenius (Arrhenius, 1889). Arrhenius was interested in why activation barriers arose in chemical reactions. He considered a simple reaction: AB and proposed that if one looked at a chemical system containing A and B, there were two kinds of A molecules in the system: reactive molecules (i.e., A molecules that had the right properties to react), and unreactive A molecules (i.e. A molecules did not have the right properties to react).At the time the work was done, there were many empirical rules to predict how rates vary with temperature. Arrhenius was the first person to derive a theoretical expression. When the expression was found to fit data, Arrhenius’ expression, which was renamed Arrhenius’ law, was universally adopted in kinetics. kke(E kBT) (2.7) o Arrhenius was never able to provide a model for ko in the above expression. Fortunately, Trauntz (Trautz, 1918) and Lewis (Lewis, 1918) independently proposed the collision theory of reactions. The objective of collision theory is to use knowledge of molecular collisions to predict the pre-exponential ko. Trautz and Lewis proposed a 13PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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