Chemical kinetics, comparison with definition

Similar ideas will be further developed in the next section, along with some other criteria and requirements. In our opinion, a strict adherence to them would improve the efficiency of the interaction between experimentation and modeling. To conclude this section, let us formulate in brief the main tasks addressed concerning the comparison of modeling with experimental data as far as the optimization of the model targeted toward the studies of the reaction mechanism and process optimization over a wide range of parameters are concerned. In our opinion, such comparison must reveal the factors that have been underestimated and overestimated in the kinetic scheme. As to the values of kinetic parameters, they definitely can be optimized , but this optimization should be based on exact physical and chemical (experimental and theoretical) arguments, but not on formal mathematical procedures. 

Additional insights into the resonance effect on the stabilization of 72 comes from a consideration of the rate constants ki and k-i, or, more precisely, the intrinsic rate constants. The general definition of the intrinsic rate constant, ko, of a reaction with forward and reverse rate constants k and k-i, respectively, is ko = k = k-i when = 1 if dealing with free energies, one can define an intrinsic barrier, AGq, as AGq = AGj = AgIj when AG° = q H9,i20 significance of ko or AGq is that they are purely kinetic measures of chemical reactivity because they separate out thermodynamic effects from kinetic effects and hence they allow meaningful comparisons of reactivity between different reactions. 

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