Thermodynamical Properties Of Temporal Self-organization Structure In Nonideal Chemical Reaction System

Dissipative structure theory has indicated that under certain conditions an open system far from equilibrium through exchanging energy and matter with the external world will be instable and probably become an order structure in time, space and function from unstable state. The question how to explore certain thermodynamical function to describe the dissipative system, in other words, for an established dissipative structure the study of the change of some important thermodynamical functions such as entropy production and entropy flow during the formation of structure, is a new one in the thermodynamical research of dissipative structure. In addition, the construction of the classical dissipative structure was based on the ideal system, which led to the limitation of application in practical system. The fact that new branch may appear and new dissipative structure may be formed in nonideal dissipative system has been discovered. According to the above two points, the thesis has analyzed and studied the thermodynamical properties of the temporal self-organization structure in nonideal chemical reaction system and developed the theory of dissipative structure.Such kind of nonideal pure dissipative system without convective effect is our object of research in this thesis. To begin with, we consider the nonideality of this system and discuss the temporal general expression of thermodynamical function change between a state of the temporalself-organization structure in such kind of system and referred steady state of the corresponding thermodynmical branch. The periodic average values of the change of entropy, entropy production and entropy flow have been deduced. Meanwhile, compared with the thermodynamical properties of corresponding ideal system, the excess non-equilibrium thermodynamical function has been defined, which reflects the effect of nonideality on the entire dissipative system.Two simple kinds of nonideal models including Amagat gas mixture and regular solution have been analyzed thoroughly in the second part. On the basis of the definition of Amagat gas mixture and regular solution, their nonideal characters have been explored. Having made some hypothesis, we have demonstrated corresponding activity coefficient expression of each species in two kinds of nonideal systems when using molar concentrations.Chapter 3 and chapter 4 deal with the thermodynamical properties of the temporal self-organization structure formed in several systems of typical nonideal chemical reaction model under constant temperature and homogeneous phase. We have separately discussed thermodynamical properties of conservative oscillation and limit cycle oscillation in Lotka model and Brusselator model of Amagat gas mixture and regular solution. Moreover, through numerical simulation and numerical integration, we have analyzed their dynamical behavior and calculated periodic average values of entropy change, mean molar entropy change, entropy production change, entropy flow change, mean entropy production change and mean entropy flow change due to unit change of total rate. Meanwhile, we have drawn function spectrum of energy dissipation and entropy flow.I . Evolving rules of some important thermodynamic functions such as entropy, entropy production and entropy flow during the formation of the limit cycle oscillation and the conservative oscillation show that these functions can't characterize features of dissipative structures.(1). As to the conservative oscillation of Amagat gas mixture, the periodic average values of entropy change and mean molar entropy change keep risingIt is concluded that evolving rules of some thermodynamic functions such as entropy, entropy production and entropy flow are concerned with structure, nonideal model and nonideality. So they can't characterize features of dissipative structures.II. Evolving rules of dissipative distribution function and entropy flow distribution function show that these functions can characterize features of dissipative structures.(1). Under the dif...