Different Theories of Bimolecular Rate Constants Experimental Activation Energies

Comparison of Different Theories of Bimolecular Rate Constants Experimental Activation Energies 

We have seen in Sec. IV.4 that for thermodynamic consistency a specific rate constant should be capable of being represented in the form 

If we now inspect the results of the various theories we have just considered, we will see that they can all be cast into the form demanded by Eq. (XII.5.1), and the thermodynamic significance of the terms can now be interpreted in terms of the equilibria proposed by the various models. From laboratory experiments we can calculate specific rate constants at different temperatures, and following the Arrhenius method we can define an experimental energy of activation by the equation 

When the rate constant can be decomposed into a product of two terms, one of them being of the form where E is a constant, we refer to 

In Table XII.1 we list the values of the specific rate constants for bi-molecular reactions and their experimental activation energies and preexponential factors as defined in the foregoing. 

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