Tomáš Opravil

By Petr Ptáček, Magdaléna Nosková, František Šoukal, Tomáš Opravil, Jaromír Havlica and Jiří Brandštetr

Part of the book: Atomic Absorption Spectroscopy

By Petr Ptáček, Jiří Brandštetr, František Šoukal and Tomáš Opravil

Part of the book: Materials Science

By Petr Ptáček, Tomáš Opravil and František Šoukal

This chapter provides the information about the concept of effective mass and effective velocity of the activated complex and its connection to the transition state theory. Therefore, these parameters are of essential importance for the field of homogenous as well as heterogeneous kinetics. They also prove to be useful for the calculation of many other properties of activated state, such as momentum, energetic density, mass flux, etc., as will be demonstrated on the example of thermal decomposition of calcite and aragonite. Since the activation energy and the momentum of activated state enable to complete the characterization of motion of this instanton (pseudoparticle) alongside the reaction coordinate, these parameters can be then considered as two quantum numbers of activated complex. The quantum numbers of activated state, that is, the activation energy and momentum, also explain the relation of activated complex to Planck energy, length and time, as well as to the Gravitational constant. This idea was also applied to derive the wave function of activated complex pseudoparticle, which is affected by the isotopic composition of the sample and polymorphism as well. Furthermore, the findings introduced in this chapter enable to derive and propose the modified Kissinger equation and experimental solution for the approximation parameter in the Doyle equation of temperature integral.

Part of the book: Introducing the Effective Mass of Activated Complex and the Discussion on the Wave Function of this Instanton

By Petr Ptáček, František Šoukal and Tomáš Opravil

The transition state theory (TST), which is also known as theory of absolute reaction rates (ART) and the theory of activated state (complex), is essentially a refined version of crude collision theory, which treats the reacting molecules as the rigid spheres without any internal degree of freedom. The theory explains the rate of chemical reaction assuming a special type of chemical equilibrium (quasi-equilibrium) between the reactants and activated state (transition state complex). This special molecule decomposes to form the products of reaction. The rate of this reaction is then equal to the rate of decomposition of activated complex. This chapter also explains the limitation of TST theory and deals with the kinetics isotope effect.

Part of the book: Introducing the Effective Mass of Activated Complex and the Discussion on the Wave Function of this Instanton

By Petr Ptáček, Tomáš Opravil and František Šoukal

This chapter begins with a general overview of the content of this work, which explains the structure and mutual relation between discussed topics. The following text provides brief historical background to chemical kinetics, lays the foundation of transition state theory (TST), and reaction thermodynamics from the early Wilhelmy quantitative study of acid-catalyzed conversion of sucrose, through the deduction of mathematical models to explain the rates of chemical reactions, to the transition state theory (absolute rate theory) developed by Eyring, Evans, and Polanyi. The concept of chemical kinetics and equilibrium is then introduced and described in the historical context.

Part of the book: Introducing the Effective Mass of Activated Complex and the Discussion on the Wave Function of this Instanton