Formal kinetic evaluation method

In the application of chemical kinetics, a formal kinetic evaluation method has been proposed (Schmid and Sapunov, 1982). An operation scheme is illustrated in Fig. 5.16 it uses two properties of c/t curves as decision criteria, called invariance I and invariance II. These properties concern the linear transformation capability of first- and second-order reactions. Kinetic curves with various initial concentrations Cj o can be superimposed over arbitrary standard curves (cj o)s by multiplying ordinates by ratios (cj o)s/Ci,o tbe case... 

The velocity of reactions in principle depends on the number of collisions per unit of time between the reactants. It may be assessed with the methods of physical chemistry. Yet, for practical applications it is determined experimentally. The experimental results are then evaluated using simplified model concepts. For this reason we speak of formal kinetics. 

For a quasireversible wave, 1/2 is not far removed from E and is sometimes used as a rough estimate of the formal potential. Better estimates can be made from fundamental equations after the kinetic parameters have been evaluated from the wave shape. The tables published by Mirkin and Bard for their method actually provide n(E /2 E ) with sets of k and a (33). 

Manipulations needed to relate heat flow hr to temperature changes through theoretical models for transitions, or through properties of calorimeters, are usually more conveniently done via such complex qualities. The value C can then lead directly to evaluations of real specific heat and parameters controlling kinetics. However, the use of complex notation does not imply a different theoretical treatment or method. It is simply a more convenient mathematical formalism. The terms real and imaginary heat capacity and phase-corrected reversing and kinetic heat capacities are interchangeable. 

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