Irreversible process defined

In words when a system undergoes a change, the increase in entropy of the system is equal to or greater than the heat absorbed in the process divided by the temperature. On the other hand, the equality, which provides a definition of entropy increment, applies to any reversible process, whereas the inequality refers to a spontaneous (or irreversible) process, defined as one which proceeds without intervention from the outside. Example 1 illustrates the reversible and irreversible reactions. 

Most textbooks in chemical thermodynamics place the main focus on the equilibrium of chemical reactions. In this textbook, however, the affinity of irreversible processes, defined by the second law of thermodynamics, has been treated as the main subject. The concept of affinity is applicable in general not only to the processes of chemical reactions but also to all kinds of irreversible processes. 

Spontaneous processes are particular examples of irreversible processes defined in Section 12.1. In stark contrast with reversible processes, they do not proceed through a sequence of equilibrium states, and their direction cannot be reversed by an infinitesimal change in the direction of some externally applied... 

In an irreversible process the temperature and pressure of the system (and other properties such as the chemical potentials to be defined later) are not necessarily definable at some intemiediate time between the equilibrium initial state and the equilibrium final state they may vary greatly from one point to another. One can usually define T and p for each small volume element. (These volume elements must not be too small e.g. for gases, it is impossible to define T, p, S, etc for volume elements smaller than the cube of the mean free... 

The processes that occur at a finite rate, with finite differences of temperature and pressure between parts of a system or between a system and its surroundings, are irreversible processes. It has been shown that the entropy of an isolated system increases in every natural (i.e., irreversible) process. It may be noted that this statement is restricted to isolated systems and that entropy in this case refers to the total entropy of the system. When natural processes occur in an isolated system, the entropy of some portions of the system may decrease and that of other portions may increase. The total increment, however, is always greater than the total decrement. The entropy of a nonisolated system may either increase or decrease, depending on whether heat is added to it or removed from it and whether irreversible processes occur within it. Considered all in all, it is necessary to define clearly the system under consideration when increases and decreases in entropy are discussed. 

The irreversible processes described must not occur even on open circuit. In a reversible cell, a definite equilibrium must be established and this may be defined in terms of the intensive variables in a similar way to the description of phase and chemical equilibria of electroneutral components. 

The usual emphasis on equilibrium thermodynamics is somewhat inappropriate in view of the fact that all chemical and biological processes are rate-dependent and far from equilibrium. The theory of non-equilibrium or irreversible processes is based on Onsager s reciprocity theorem. Formulation of the theory requires the introduction of concepts and parameters related to dynamically variable systems. In particular, parameters that describe a mechanism that drives the process and another parameter that follows the response of the systems. The driving parameter will be referred to as an affinity and the response as a flux. Such quantities may be defined on the premise that all action ceases once equilibrium is established. 

The sum is equal to zero for reversible processes, where the system is always under equilibrium conditions, and larger than zero for irreversible processes. The entropy change of the surroundings is defined as... 

To continue the present topic, we would like to underline that often irreversible redox processes do not cause the appearance of new, well-defined redox waves such as to induce an accurate examination of the underlying chemical complications. Nevertheless, not always irreversible redox changes lead to complete destruction of the metal complex under examination. Analysis of the products arising from irreversible processes can sometimes reveal interesting chemical pathways. 

Concerning statement 1,1 believe that one should first define what exactly is meant by approximation. In La Fin des Certitudes (p. 29), Prigogine rightly attacks the rather widely present view according to which statistical mechanics requires a (brute) coarse graining (i.e., a grouping of the microscopic states into cells, considered as the basic units of the theory). This process is, indeed, an arbitrary approximation that cannot be accepted as a basis of the fundamental explanation of the very real macroscopic irreversible processes. 

In the development of the second law and the definition of the entropy function, we use the phenomenological approach as we did for the first law. First, the concept of reversible and irreversible processes is developed. The Carnot cycle is used as an example of a reversible heat engine, and the results obtained from the study of the Carnot cycle are generalized and shown to be the same for all reversible heat engines. The relations obtained permit the definition of a thermodynamic temperature scale. Finally, the entropy function is defined and its properties are discussed. 

Having defined the entropy function, we must next determine some of its properties, particularly its change in reversible and irreversible processes taking place in isolated systems. (In each case a simple process is considered first, then a generalization.)... 

In an advancing irreversible process such as a mechanical movement of a body, dissipation of energy for instance from a mechanical form to a thermal form (frictional heat) takes place. The second law of thermodynamics defines the energy dissipation due to irreversible processes in terms of the creation of entropy Slrr or the creation of uncompensated heat Qirr. 

The mixing of substances is an irreversible process that takes place creating entropy in the system. The entropy thus created is defined as the entropy of mixing SM. Suppose two different ideal gases with different volumes Vl and V2 are mixed isothermally at a constant pressure p to make a single mixture system with a volume V, + V2 as shown in Fig. 3. 10. The overall entropy S1 of both individual systems before the mixing is obtained from Eq. 3.47 as shown in Eq. 3.49 ... 

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