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[11] viXra:2406.0185 [pdf] submitted on 2024-06-29 07:54:33
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 32 Pages.
The review article shows the evolutionary path that turnover frequency (TOF) and turnover number (TON) have passed from "Boreskov`s Rule" to their modern definitions. From the equation catalysis rate, the second method for calculating TOF is obtained using the characteristics of catalyst material. Was prooved the possibility of obtaining TOF in two ways - using the characteristics of catalysis process and using the characteristics of the catalyst and reagents. The equivalence of two methods of TOF calculation is proved. It turned out that TOF is not a complete and unambiguous characteristic of the catalyst, as it was usually believed. TOF is only partially dependent on the characteristics of the catalyst material. It turned out that TOF is not a characteristic of a catalyst, but of a "catalyst + reagents" system, and its value directly depends on the state of their oxidation. It is proposed to use the list of oxidation states of chemical elements as the main tool in the selection of catalysts. The Sabatier principle limits the TOF and TON values by limiting the multielectron transitions when the oxidation state of the active sites of the catalyst changes. An explanation for the effect of overcoming the Sabatier prohibition is given, in which external synchronous action on the catalyst makes it possible to achieve a catalytic reaction speed higher than the Sabatier maximum.
Category: Chemistry
[10] viXra:2406.0181 [pdf] submitted on 2024-06-29 21:20:52
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 16 Pages.
The mechanism of heterogeneous catalysis taking into account the influence of temperature is briefly considered in the development of the concept "electron as a catalyst". Here the catalytic cycle includes the heat transfer and electron generation besides the mass transfer. The mechanism of temperature influence in heterogeneous catalysis is realised through the generation of electrons in a positive feedback loop. This mechanism involves the Edison and Seebeck thermoelectronic effects. The catalytic cycle of heterogeneous catalysis is supplemented with a thermoelectronic stage. The thermoelectronic stage of catalysis involves heat transfer and electron generation. Energy transfer to the active centre of the catalyst is an integral part of the catalytic cycle. Energy transfer is considered as a positive temperature feedback loop. The generation of electrons in the positive feedback loop and their transfer to the reactants leads to an increase in reactivity of the reactants. The positive temperature feedback loop leads to an exponential (sigmoidal) dependence of the reaction rate. Keywords: "electron as a catalyst" concept, thermoelectronic stage of catalysis, positive feedback loop, donor-acceptor mechanism of catalysis, Seebeck effect, Edison effect.
Category: Chemistry
[9] viXra:2406.0180 [pdf] submitted on 2024-06-29 21:20:00
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 26 Pages.
The discovery of electron and electric field catalysis led to the need to clarify and change the basic postulates of catalysis. The emergence of the "electron as a catalyst" concept revealed the contradictions of the current catalysis paradigm. The concept made it possible to formulate a new paradigm of catalysis. The article focuses on the most important aspects of the new paradigm of catalysis. The features of the general mechanism of catalytic reactions are considered. The origin of the laws of catalysis from the mechanisms of catalysis has been considered. In the model of the unified mechanism of catalysis, the stages of fundamental interaction and the stage of chemical interaction of the participants are distinguished. At the stage of fundamental interaction, the redox cycle of catalysis is realized. At this stage, there is an increase in the reactivity of the reagents. From the mechanisms of catalysis, the laws of catalysis as a function of the substance characteristics of the participants of the catalytic reaction are derived. Key words: redox cycle, the concept of "electron as a catalyst", the concept of two fundamental catalysts, the concept of the oxidation state, the relay donor-acceptor mechanism of catalysis, the laws of catalysis, the universal law of catalysis, the new paradigm of catalysis.
Category: Chemistry
[8] viXra:2406.0179 [pdf] submitted on 2024-06-29 21:21:32
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 12 Pages.
The proton donor-acceptor mechanism of catalysis makes it possible to study catalytic reactions at the elementary particle level, which made it possible to obtain the laws of homogeneous catalysis. The main characteristics of homogeneous catalysis were obtained from the rate law. The main parameter in the formulas of the laws of homogeneous catalysis is the total electric charge obtained by the reactants. It was shown that in such dissimilar and different types of catalysis as homogeneous and field catalysis, the same mechanism of catalysis is realized. This mechanism is based on the transfer of electric charges to the reagents by means of protons and electrons. The proton and electron donor-acceptor mechanisms are charge-symmetric mechanisms of catalysis. The difference between the proton donor-acceptor mechanism of homogeneous catalysis and the electronic donor-acceptor mechanism of field catalysis lies in the electrical charge carriers. The donor-acceptor mechanism claims to be a universal mechanism of catalysis. The key factor leading to a decrease in the activation energy of a chemical reaction is the change in the charge state of the reactants. A generalized law is obtained, from which the laws of homogeneous and field catalysis follow as particular results.
Category: Chemistry
[7] viXra:2406.0178 [pdf] submitted on 2024-06-29 21:25:43
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 22 Pages.
Based on the generalization of experimental and theoretical studies in the field of catalysis, three basic laws of heterogeneous catalysis were discovered. From the formula of the catalysis rate law, the most important characteristics of catalysis are obtained - the reaction output, TOF and TON. Formulas for calculating the characteristics of catalysis using the characteristics of catalyst substance are given. A new concept of heterogeneous catalysis has been developed, in which the role of catalysts in the mechanism of accelerating chemical reactions has been revised. The oxidation states of the reactants and active sites of the catalyst are used as parameters in the formulas of the laws of catalysis. It follows from the laws of catalysis that oxidation states are such important characteristics of catalyst substance and reagents, that they directly affect the mechanism of catalysis itself and set the values of the most important characteristics of catalysis. As the main tool in the selection of catalysts, it is necessary to use the list of oxidation states of chemical elements known in chemistry. Based on the laws of catalysis, new definitions of catalyst and catalysis are given. The class of catalysts is expanded. Material catalysts are complemented by field catalysts. The substantiation of catalysis as a fundamental direction in science is given.
Category: Chemistry
[6] viXra:2406.0177 [pdf] submitted on 2024-06-29 21:23:18
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 17 Pages.
The article explores a new type of catalysis - electric field catalysis. The laws of field catalysis are given. The characteristics of the electric field are determined, which set the values of the characteristics of the field catalysis. Field catalysis and field catalyst do not fit into the traditional definition of catalysis and catalyst, which may require a revision of the terminology of catalysis. The field is a more versatile catalyst compared to material catalysts, both in terms of its application to a wider range of chemical reactions, and in the ability to control the rate and selectivity. It is shown that a common donor-acceptor mechanism of catalysis is realized in heterogeneous and field catalysis. Generalized formulas are obtained, from which, as partial results, the laws of heterogeneous and field catalysis follow. New definitions of catalyst and field catalysis are given. The class of material catalysts has been expanded and supplemented with field catalysts.
Category: Chemistry
[5] viXra:2406.0110 [pdf] submitted on 2024-06-22 02:07:27
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 16 Pages.
Electrolysis throughout its history has not been studied for the relationship between the nature of electrolysis and the nature of catalysis. The article makes a generalization of catalysis and electrolysis and reveals common features for these two fundamental processes. The concept of "electron as a catalyst" substantiates that electrolysis is a type of catalysis. The catalysts in electrolysis are electrons. A comparison of the mechanisms of electrolysis and catalysis is made. The mechanisms of electrolysis and catalysis are the same type of mirror-symmetric donor-acceptor mechanisms. In these mechanisms, the transfer of electric charges is realized. Electrolysis, as a catalytic process, has characteristics that are inherent to catalysis. These characteristics are the law of rate of electrolysis, the TOF of electrolysis, and the TON of electrolysis. Catalysis and electrolysis share common laws and a common genesis of laws. Faraday's law of electrolysis follows directly from the universal law of catalysis. Confirmation of the common nature of catalysis and electrolysis has been obtained. Electrolysis, as a type of catalysis, creates prerequisites for the creation of a general theory of catalysis and electrolysis.
Category: Chemistry
[4] viXra:2406.0109 [pdf] submitted on 2024-06-22 02:06:31
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 18 Pages.
The general sign and general mechanism of catalytic reactions based on the transfer of electric charges to reagents has been revealed. This mechanism of catalysis is realized on the fundamental level - on the level of interaction of elementary particles (electrons and protons). The choice of this mechanism of catalysis made it possible to obtain the general law of catalysis and private laws for other types of catalysis. The main parameter in the equation of the generalized law of catalysis is the total electric charge obtained by the reactants. In catalysis, the donor-acceptor mechanism is realized, which leads to a change in the oxidation state of the reactants and to a decrease in the activation energy of the chemical reaction. The main active factor in the donor-acceptor mechanism of catalysis is the electrical charge that transfers the catalyst to the reactants. The electric charge is a quantitative characteristic in the formula for the universal law of catalysis. From the universal law of catalysis, the laws of heterogeneous, homogeneous, combined, field catalysis, and Faraday's law of electrolysis follow as private results.
Category: Chemistry
[3] viXra:2406.0108 [pdf] submitted on 2024-06-22 02:05:52
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 27 Pages.
The model of the unified mechanism of catalytic reactions within the framework of a new paradigm of catalysis was proposed as the development of the conception "electron as a catalyst". The model of the unified mechanism of catalysis made it possible to obtain the universal law of the catalytic rate. From the universal law of catalysis, the laws of heterogeneous, homogeneous, field catalysis, and Faraday's law of electrolysis follow as particular results. The laws and equations of catalysis are the mathematical equivalents of the mechanism of catalysis. The laws of catalysis are represented by equations in which the characteristics of the substance of the catalyst and other reaction participants are parametres.
Category: Chemistry
[2] viXra:2406.0107 [pdf] submitted on 2024-06-22 02:05:09
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 31 Pages.
The article proposes a new paradigm of catalysis. It is developed as a natural continuation of the advanced concepts in catalysis, such as "electron as a catalyst", "proton as a catalyst", and "oxidation state concept". The goal of the new catalysis paradigm is to reveal the general mechanism of catalytic reactions and to derive the laws of catalysis. The new paradigm of catalysis is based on the idea that two universal catalysts exist in nature that can increase the reactivity of chemical substances. The catalysts in all types of catalysis are fundamental objects of the microcosm - elementary particles: the electron and the proton. In the new paradigm, numerous substances that have traditionally been considered catalysts are assigned the role of precursors of catalysts. In the reaction, they mediate the transfer of electrons and protons. The common mechanism in various types of catalysis is a mechanism based on the transfer of electric charges by electrons and protons and on the change in the oxidation state of the reactants with their participation. Changing the state of oxidation of reactants, the formation of radicals leads to an increase in their reactivity. A model of the relay donor-acceptor mechanism as a universal mechanism of catalysis was proposed. The new paradigm of catalysis has made it possible to reveal the universal mechanism of catalytic reactions and to solve the main problem of catalysis - to obtain a single universal law of catalysis. From the universal law of catalysis, the laws of heterogeneous, homogeneous, field catalysis, and Faraday's law of electrolysis follow as particular results. The laws of catalysis are represented not by empirical equations, but by mathematical relations in which the parameters are chemical and physical characteristics of the catalyst, precursor, and reagents. The new paradigm shows that catalysis is a universal and fundamental natural phenomenon. The concept of two fundamental catalysts leads to the conclusion that all chemical reactions are catalytic. They are realized by a single universal mechanism of catalysis. In those reactions that are carried out without the presence of additional substances and are not traditionally considered catalytic, the catalysts are an electron or a proton. In these reactions, one of the reactants plays the role of a precursor and a donor of elementary particles.
Category: Chemistry
[1] viXra:2406.0106 [pdf] submitted on 2024-06-22 02:04:26
Authors: Volodymyr Kaplunenko, Mykola Kosinov
Comments: 42 Pages.
The article presents a study of previously obtained laws of catalysis for their fundamental and interdisciplinary nature. It follows from the laws of catalysis that catalysis belongs to the class of chemical and physical phenomena. The laws of catalysis and the formulas for calculating TOF and TON are combinations of quantities of chemical and physical nature. The main mystery of catalysis for many years has been the undisclosed role of oxidation states in the mechanism of catalysis. The field of application of oxidation states in catalysis has expanded. The oxidation states have been used for a new purpose as parameters in the laws and formulas of catalysis. It has been shown that in catalysis it is necessary to consider not only the oxidation states of the catalyst, but also the oxidation states of the reactants. The concept of oxidation states as quantitative values proved to be the main missing link that made it possible to obtain the laws of catalysis. The key role of the oxidation states of the catalyst and reagents in the donor-acceptor mechanism of catalysis has been demonstrated. The list of oxidation states of chemical elements known in chemistry can be applied as a tool for the selection of catalysts. The role and place of electric charges in the mechanism of catalysis and in the laws of catalysis have been shown. A new field of application of Faraday's constant in chemistry is outlined. In addition to its well-known use in the law of electrolysis and in the Nernst and Goldman equations, the Faraday constant has marked itself in catalysis and is included as an interaction constant in the laws of catalysis. The signs of the fundamentality of catalysis are given and the place of the laws of catalysis in the family of fundamental physical laws is shown. The laws of catalysis complement the family of fundamental laws of Nature.
Category: Chemistry
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