Isoparametricity paradox in the pyridine-catalyzed reaction of phenyloxirane with 3-nitrobenzoic acid

Shpan'ko, I. V.; Sadovaya, I. V.

doi:10.1134/s0036024413120224

Cited by 6 publications

(2 citation statements)

References 15 publications

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“…In this way, during the transition of operating temperatures through T iso occurs a complete inversion of the influence of the parameters (compare the lines of f (T 3 ) and f (T 4 ) in Figure 2). This results, for example, in the order of the influence of the substituents in pyridines, which catalyze the reaction of phenyloxirane with nitrobenzoic acid [84,85]. A similar fact was established when studying the activity of a number of heterogeneous catalysts [86] or enzymes [87].…”

Section: The Effect Of the Temperature On The Impact Of Variable Parameter σ Imentioning

confidence: 53%

“…We want to emphasize that this conclusion arises from a mathematical analysis of the obtained dependencies, assuming that they are preserved when passing through a point T iso . To date, there is almost no experimental evidence for this [84][85][86][87], and more experimental evidence is clearly needed.…”

Section: The Effect Of the Temperature On The Impact Of Variable Parameter σ Imentioning

confidence: 99%

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The Basic Theorem of Temperature-Dependent Processes

Сапунов

Saveljev

Voronov

et al. 2021

Thermo

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The basic theorem of isokinetic relationships is formulated as “if there exists a linear correlation “structure∼properties” at two temperatures, the point of their intersection will be a common point for the same correlation at other temperatures, until the Arrhenius law is violated”. The theorem is valid in various regions of thermally activated processes, in which only one parameter changes. A detailed examination of the consequences of this theorem showed that it is easy to formulate a number of empirical regularities known as the “kinetic compensation effect”, the well-known formula of the Meyer–Neldel rule, or the so-called concept of “multi-excitation entropy”. In a series of similar processes, we examined the effect of different variable parameters of the process on the free energy of activation, and we discuss possible applications.

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