Isokinetic relationship derivation

FIGURE 1. Isokinetic relationship derived from an enthalpy/entropy plot compensation effect... 

It was not until the 1970s that the statistics of the isokinetic relationship was satisfactorily worked out.Exner first took this approach Let k, and 2 be the rate constants for a member of a reaction series at temperatures T, and T2, with T2 > T, and let k° and k° be the corresponding values for the reference member of the series. Then Eqs. (7-76) and (7-77) are easily derived for the reaction series. 

Several doubts about the correctness of the usual statistical treatment were expressed already in the older literature (31), and later, attention was called to large experimental errors (142) in AH and AS and their mutual dependence (143-145). The possibility of an apparent correlation due only to experimental error also was recognized and discussed (1, 2, 4, 6, 115, 116, 119, 146). However, the full danger of an improper statistical treatment was shown only by this reviewer (147) and by Petersen (148). The first correct statistical treatment of a special case followed (149) and provoked a brisk discussion in which Malawski (150, 151), Leffler (152, 153), Palm (3, 154, 155) and others (156-161) took part. Recently, the necessary formulas for a statistical treatment in common cases have been derived (162-164). The heart of the problem lies not in experimental errors, but in the a priori dependence of the correlated quantities, AH and AS. It is to be stressed in advance that in most cases, the correct statistical treatment has not invalidated the existence of an approximate isokinetic relationship however, the slopes and especially the correlation coefficients reported previously are almost always wrong. 

Another simple approach assumes temperature-dependent AH and AS and a nonlinear dependence of log k on T (123, 124, 130). When this dependence is assumed in a particular form, a linear relation between AH and AS can arise for a given temperature interval. This condition is met, for example, when ACp = aT" (124, 213). Further theoretical derivatives of general validity have also been attempted besides the early work (20, 29-32), particularly the treatment of Riietschi (96) in the framework of statistical mechanics and of Thorn (125) in thermodynamics are to be mentioned. All of the too general derivations in their utmost consequences predict isokinetic behavior for any reaction series, and this prediction is clearly at variance with the facts. Only Riietschi s theory makes allowance for nonisokinetic behavior (96), and Thorn first attempted to define the reaction series in terms of monotonicity of AS and AH (125, 209). It follows further from pure thermodynamics that a qualitative compensation effect (not exactly a linear dependence) is to be expected either for constant volume or for constant pressure parameters in all cases, when the free energy changes only slightly (214). The reaction series would thus be defined by small differences in reactivity. However, any more definite prediction, whether the isokinetic relationship will hold or not, seems not to be feasible at present. 

An attempt to derive the isokinetic relationship still more generally considering a temperature-dependent a (2) is not quite correct. Equation (72), corresponding to eq. (4), p. 317, of (2), then has a solution... 

It follows that for a special value of one parameter, the observed value of y is independent of the second parameter. This happens at Ii= a2/ai2 or I2 = -ai/ai2 any of these values determines y= a -aia2/ai2, the so called isoparametrical point. The argument can evidently be extended to more than two independently variable parameters. Experimental evidence is scarce. In the field of extrathermodynamic relationships, i.e., when j and 2 are kinds of a constants, eq. (84) was derived by Miller (237) and the isoparametrical point was called the isokinetic point (170). Most of the available examples originate from this area (9), but it is difficult to attribute to the isoparametrical point a definite value and even to obtain a significant proof that a is different from zero (9, 170). It can happen—probably still more frequently than with the isokinetic temperature—that it is merely a product of extrapolation without any immediate physical meaning. 

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