**Part 2**

**Chemical Kinetics and Mechanism** 

28 Chemical Kinetics

Van't Hoff, J.H. (1885). L'Équilibre chimique dans les Systèmes gazeux ou dissous à I'État

Wilhelmy, L. (1850). *Über* das Gesetz, nach welchem die Einwirkung der Säuren auf den

Zambelli, S. (2010), Chemical kinetics and diffusion approach: the history of the Klein-

dilué, *Recueil des Travaux Chimiques des Pays-Bas* 4, 12, pp. 424-427

Rohrzucker stattfindet, *Pogg. Ann.* 81, pp. 413-433, Available from

http://gallica.bnf.fr/ark:/12148/bpt6k15166k/f427.table

Kramers equation, *Arch. Hist. Exact Sci*. 64, 4, pp. 395-428

**2** 

*Russia* 

**On the Interrelations Between Kinetics and** 

Existence of close and obligatory relations between kinetics and thermodynamics is the truth well known to experts. It is clear that propositions of the science based on the most general regularities of the macroscopic world (thermodynamics) should be used in the theories of macroscopic processes running over time (chemical and macroscopic kinetics). Application of general principles in solving specific kinetic problems in the majority of cases turns out to be related to specificity of their use. Observance of one or another principle or rule can require search for original both physicochemical statement of the problem, and mathematical model, and computational method. The art of thermodynamic analysis of kinetic equations was demonstrated in (Feinberg, 1972, 1999; Horn and Jackson, 1972; Gorban, 1984; Yablonsky et al., 1991) and works by other researchers. The character of relations between the theories of trajectories and theories of states changed qualitatively in the second half of the 20th century due to rapid development of computers and numerical methods of mathematical programming (MP). It became possible to considerably simplify formalized descriptions of problems owing to the transition from their analytical solutions to iterative, stepwise search processes. Analysis of possibilities to simplify the kinetic models and unfolding the methods to implement these possibilities on the basis of

The main idea of the research being described is the refusal to use an equation of trajectory and construction of stepwise methods to analyse processes on the basis of the model of extreme intermediate states (MEIS) that was created by B.M.Kaganovich, S.P.Filippov and E.G.Antsiferov (Antsiferov et al., 1988; Kaganovich, 1991; Kaganovich et al., 1989). The features that make MEIS different from the traditional thermodynamic models are: 1) statement of the problem to be solved (instead of search for a sole point of final equilibrium eq *x* the entire set of thermodynamic attainability t *D y*( ) from the given initial state *y* is considered and the states ext *x* with extreme values of modeled system characteristics of interest to a researcher are found); 2) dual interpretation of the equilibrium notion, i.e. both as a state of rest and as an instant of motion in which the equality of action and counteraction is observed; and 3) dual interpretation of dynamic quantities (work , heat *q* , rate *w* , flow of substance *x* , etc.) both

equilibrium thermodynamic principles constitute the aim of the chapter.

**1. Introduction** 

**Thermodynamics as the Theories** 

 **of Trajectories and States** 

Boris M. Kaganovich, Alexandre V. Keiko, Vitaly A. Shamansky and Maxim S. Zarodnyuk

*Melentiev Energy Systems Institute,* 
