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.

This work is addressed to the phenomenon of catalyst deactivation taking place during the repeated uses in the reaction of Suzuki-Miyaura (S-M) cross-coupling, which is widely applied in industry for C-C bond formation. Ligandless catalysts based on Pd(0) NPs supported on hyper-cross-linked polystyrene (HPS) of two types (non-functionalized and bearing tertiary amino groups) were studied in a model S-M reaction between 4-bromoanisole and phenylboronic acid. Synthesized catalysts were shown to be highly active under mild reaction conditions. HPS allows stabilization of Pd(0) NPs and prevents their agglomeration and detectable Pd leaching. However, the loss of catalytic activity was observed during recycling. The deactivation issue was assigned to the hydrophobic nature of non-functionalized HPS, which allowed a strong adsorption of cross-coupling product during the catalyst separation procedure. A thorough washing of Pd/HPS catalyst by hydrophobic solvent was found to improve to the big extent the observed catalytic activity, while the replacement of non-functionalized HPS by a one containing amino groups increased the catalyst stability at the expense of their activity.

Despite numerous works devoted to the cellulose hydrogenolysis process, only some of them describe reaction kinetics. This is explained by the complexity of the process and the simultaneous behavior of different reactions. In this work, we present the results of the kinetic study of glucose hydrogenolysis into ethylene- and propylene glycols in the presence of Ru@Fe₃O₄/HPS catalyst as a part of the process of catalytic conversion of cellulose into glycols. The structure of the Ru-containing magnetically separable Ru@Fe₃O₄/HPS catalysts supported on the polymeric matrix of hypercrosslinked polystyrene was studied to propose the reaction scheme. As a result of this study, a formal description of the glucose hydrogenolysis process into glycols was performed. Based on the data obtained, the mathematical model of the glucose hydrogenolysis kinetics in the presence of Ru@Fe₃O₄/HPS was developed and the parameter estimation was carried out. The synthesized catalyst was found to be characterized by the enhanced magnetic properties and higher catalytic activity in comparison with previously developed catalytic systems (i.e., on the base of SiO₂). The summarized selectivity towards the glycols formation was found to be ca. 42% at 100% of the cellulose conversion in the presence of Ru@Fe₃O₄/HPS.

The kinetics of propylene oxide hydration in the presence of bis(ethane-1,2-diol)molybdate is reported. A mathematical description of PO disappearance and propylene glycol formation is suggested. The most probable scheme for the process is presented. The basic kinetic constants are calculated.

During the last decades, palladium nanoparticles (Pd(0) NPs) and Pd(II) compounds were shown to be attractive catalysts for fine organic synthesis. Nanostructured Pd(0) or Pd(II) catalysts have a relatively low environmental impact, but, at the same time, they are indispensable for such processes as Suzuki cross-coupling. This paper describes the preparation of Pd(0) or Pd(II) supported/embedded in hyper-cross-linked polystyrene (HPS) and compares their activity in Suzuki cross-coupling between phenylboronic acid and 4-bromoanisole. Obviously, the palladium charge (Pd(0) ↔ Pd(II)) changes continuously during the reaction catalytic cycle. It would seem that the use of the starting palladium in the form of Pd(0) or Pd(II) should not affect the reaction’s kinetic laws for both catalysts, but their special individuality is manifested between them. Nanoparticulate Pd(0) catalysts are stable during the reaction. In contrast, catalysts based on Pd(II) are extremely active in the initial period of the reaction, but then the “hot form” of the catalyst is rapidly converted into the form of Pd(0), whose activity is identical to that of the preliminarily reduced catalyst. This work discusses the possible nature of this phenomenon. A mathematical model for Suzuki cross-coupling reaction was suggested that was able to adequately describe experimental data. The level of reliability (R²) of the correlation between the experimental and calculated data was R² = 0.97–0.99.