Nonequilibrium thermodynamics, chemical

The current density j is, according to linear nonequilibrium thermodynamics, proportional to the gradient of a chemical potential difference... 

A generalized model of transport allowing for component interactions is provided by nonequilibrium thermodynamics where the flux of component i through the membrane /, [gmol/(cm -s)] is written as a first-order perturbation of the chemical potential dp,/dx [cal/(gmohcm)] ... 

An important result of nonequilibrium thermodynamics (Boudard, 1976) is that the ratio of the forward and reverse rates of a chemical reaction varies with the reaction s free energy change according to... 

TNG.67.1. Prigogine, Nonequilibrium Thermodynamics and Chemical Evolution An Overview,... 

NONEQUILIBRIUM THERMODYNAMICS A PRIMER UNIMOLECULAR CHEMICAL KINETICS MOLECULARITY ORDER OF REACTION ELEMENTARY REACTIONS Unimolecular forward/bimolecular reverse, CHEMICAL KINETICS Unimolecular isomerization,... 

Nonequilibrium thermodynamics—with applications to physical, chemical, and biological systems—has received much attention in recent years. 

We review in Section II the basic results of nonequilibrium thermodynamic stability theory and recall the thermodynamic and kinetic conditions necessary to the occurrence of cooperative coherent behaviors in chemical systems. We briefly indicate some known experimental systems that meet these requirements and in which dissipative structures... 

Miroslav Grmela, Multiscale Equilibrium and Nonequilibrium Thermodynamics in Chemical Engineering... 

In Chap. 3 (Sect. 3.6), we discussed limitations of the FREZCHEM model that were broadly grouped under Pitzer-equation parameterization and mathematical modeling. There exists another limitation related to equilibrium principles. The foundations of the FREZCHEM model rest on chemical thermodynamic equilibrium principles (Chap. 2). Thermodynamic equilibrium refers to a state of absolute rest from which a system has no tendency to depart. These stable states are what the FREZCHEM model predicts. But in the real world, unstable (also known as disequilibrium or metastable) states may persist indefinitely. Life depends on disequilibrium processes (Gaidos et al. 1999 Schulze-Makuch and Irwin 2004). As we point out in Chap. 6, if the Universe were ever to reach a state of chemical thermodynamic equilibrium, entropic death would terminate life. These nonequilibrium states are related to reaction kinetics that may be fast or slow or driven by either or both abiotic and biotic factors. Below are four examples of nonequilibrium thermodynamics and how we can cope, in some cases, with these unstable chemistries using existing equilibrium models. 

Steinicke and Linke [17] refer to several microscopic and macroscopic states of mechanically stressed solids. Short time effects can be described by stochastic means or nonequilibrium thermodynamics. Long-lasting effects can be measured by calorimetry. The chemical potential and activity of the stressed solid can be measured depending on the induced defects. These defects include ... 

Other early attempts at quantification from first principles included use of the Dobretsov equation for surface ionization through nonequilibrium thermodynamics [87], use of quantum mechanical models [88,89], and others, including surface bond breaking and dissociative [90] or chemical ionization [91]. None of these led to successful quantification schemes. An evaluation of several of these methods was made by Rudat and Morrison [92]. 

We can specially show that the main principles of nonequilibrium thermodynamics (the Onsager relations, the Prigogine theorem, symmetry principle) and other theories of motion (for example, theory of dynamic systems, synergetics, thermodynamic analysis of chemical kinetics) are observed in the MEIS-based equilibrium modeling. In order to do that, we will derive these statements from the principles of equilibrium thermodynamics. 

Development of the "flow" MEIS with the form reminding the models of nonequilibrium thermodynamics seems to be a very promising direction in equilibrium modeling of physical and chemical systems. Application of these models opens prospects for simpler analysis and solution of many complex problems related to the calculations of processes considered to be irreversible in principle. Certainly the flows in MEIS are interpreted statically as the coordinates of states. Thermodynamic interpretations are naturally extended to the kinetic coefficients that relate these flows with forces. Correctness of such interpretations is confirmed by the application of MP, being the theory of equilibrium states, as the terms for MEIS description. 

Nonequilibrium thermodynamics was chosen as a main object for comparison, though an essential part of conclusions drawn below is useful in MEIS comparison with the models of chemical kinetics, synergetics, theory of dynamic systems and other models, model engineering and theories of motions. Comparison is made from two standpoints (1) a scope of areas of effective applications and (2) simplicity and fruitfulness of computing experiments. 

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