Open systems thermodynamics

Open Systems Thermodynamic systems in which matter and/or energy may transfer with the surroundings, through the boundaries. 

Consider the arbitrary open thermodynamic system illustrated in Figure 2-32. The foregoing statement of the first law for this open system can be written as... 

Generally, in a system that is energetically and materially isolated from the environment without a change in volume (a closed system), the entropy of the system tends to take on a maximum value, so that any macroscopic structures, except for the arrangement of atoms, cannot survive. On the other hand, in a system exchanging energy and mass with the environment (an open system), it is possible to decrease the entropy more than in a closed system. That is, a macroscopic structure can be maintained. Usually such a system is far from thermodynamic equilibrium, so that it also has nonlinearity. 

Self-organization seems to be counterintuitive, since the order that is generated challenges the paradigm of increasing disorder based on the second law of thermodynamics. In statistical thermodynamics, entropy is the number of possible microstates for a macroscopic state. Since, in an ordered state, the number of possible microstates is smaller than for a more disordered state, it follows that a self-organized system has a lower entropy. However, the two need not contradict each other it is possible to reduce the entropy in a part of a system while it increases in another. A few of the system s macroscopic degrees of freedom can become more ordered at the expense of microscopic disorder. This is valid even for isolated, closed systems. Eurthermore, in an open system, the entropy production can be transferred to the environment, so that here even the overall entropy in the entire system can be reduced. 

The flow of matter and energy through an open system allows the system to self-organize, and to transfer entropy to the environment. This is the basis of the theory of dissipative structures, developed by Ilya Prigogine. He noted that self-organization can only occur far away from thermodynamic equilibrium [17]. 

Dissipative, open systems that allow for the flux of energy and matter may exhibit non-linear and complex behavior. Following the above argumentation, complex systems are usually far from thermodynamic equilibrium but, despite the flux, there may be a stable pattern, which may arise from small perturbations that cause a larger, non-proportional effect. These patterns can be stabilized by positive (amplifying)... 

Regarding the electrode/electrolyte interface, it is important to distinguish between two types of electrochemical systems thermodynamically closed (and in equilibrium) and open systems. While the former can be understood by knowing the equilibrium atomic structure of the interface and the electrochemical potentials of all components, open systems require more information, since the electrochemical potentials within the interface are not necessarily constant. Variations could be caused by electrocatalytic reactions locally changing the concentration of the various species. In this chapter, we will focus on the former situation, i.e., interfaces in equilibrium with a bulk electrode and a multicomponent bulk electrolyte, which are both influenced by temperature and pressures/activities, and constrained by a finite voltage between electrode and electrolyte. 

Figure 3.1 Schematic representations of thermodynamic systems a) isolated system, b) closed system and c) open system...

Only in the last decades has the thermodynamics of open systems been treated intensively and successfully. The thermodynamics of irreversible systems was studied initially by Lars Onsager, and in particular by Ilya Progogine and his Brussels school both studied systems at conditions far from equilibrium. Certain systems have the capacity to remain in a dynamic state far from equilibrium by taking up free energy as a result, the entropy of the environment increases (see Sect. 9.1). 

Whether a reaction is spontaneous or not depends on thermodynamics. The cocktail of chemicals and the variety of chemical reactions possible depend on the local environmental conditions temperature, pressure, phase, composition and electrochemical potential. A unified description of all of these conditions of state is provided by thermodynamics and a property called the Gibbs free energy, G. Allowing for the influx of chemicals into the reaction system defines an open system with a change in the internal energy dt/ given by ... 

A control volume is a volume specified in transacting the solution to a problem typically involving the transfer of matter across the volume s surface. In the study of thermodynamics it is often referred to as an open system, and is essential to the solution of problems in fluid mechanics. Since the conservation laws of physics are defined for (fixed mass) systems, we need a way to transform these expressions to the domain of the control volume. A system has a fixed mass whereas the mass within a control volume can change with time. 

A homogeneous open system consists of a single phase and allows mass transfer across its boundaries. The thermodynamic functions depend not only on temperature and pressure but also on the variables necessary to describe the size of the system and its composition. The Gibbs energy of the system is therefore a function of T, p and the number of moles of the chemical components i, tif. 

In open systems consisting of several components the thermodynamic properties of each component depend on the overall composition in addition to T and p. Chemical thermodynamics in such systems relies on the partial molar properties of the components. The partial molar Gibbs energy at constantp, Tand rij (eq. 1.77) has been given a special name due to its great importance the chemical potential. The corresponding partial molar enthalpy, entropy and volume under the same conditions are defined as... 

The inverse of H determines the geometric compliance matrix (Nalewajski, 1993, 1995, 1997, 1999, 2000, 2002b, 2006a,b Nalewajski and Korchowiec, 1997 Nalewajski et al., 1996, 2008) describing the open system in the Qi,F)-representation. The relevant thermodynamic potential is defined by the total Legendre transform of the system BO potential, which replaces the state-parameters (N, Q) with their energy conjugates (/a, F), respectively ... 

The first law of thermodynamics puts forward the principle of conservation of ener. Written for a general open system (where flow of material in and out of the system can occur) it is... 

In a closed system when temperature and pressure are constant, the sum of chemical potentials of all components is fixed in contrast, in an open system, the chemical potential of all components is influenced by both the thermodynamic parameters of the phases and various parameters outside the system. The main relationship among phases, components, and physical conditions is given by the phase rule. 

In the build mode, a user takes components out from either a thermodynamic open-system inventory shop or a thermodynamic closed-system inventory shop and connects them to form a state or several states, a process or several processes, or a cycle or several cycles. 

Thermodynamic cycles can also be categorized by system as closed-system cycles and open-system cycles. In closed-system cycles, each component of the cycle is considered as a closed system. In open-system cycles, each component of the cycle is considered as an open system. 

Applying the first law and second law of thermodynamics of the open system to each of the four processes of the Carnot vapor cycle yields ... 

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