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It relies on what may be thought of as more or less nearness to thermodynamic equilibrium.

Non-equilibrium thermodynamics is a work in progress, not an established edifice. This article will try to sketch some approaches to it and some concepts important for it. Almost all systems found in nature are not in thermodynamic equilibrium, for they are changing or can be triggered to change over time, and are continuously and discontinuously subject to flux of matter and energy to and from other systems and to chemical reactions. Some systems and processes are, however, in a useful sense, near enough to thermodynamic equilibrium to allow description with useful accuracy by currently known non-equilibrium thermodynamics.

Nevertheless, many natural systems and processes will always remain far beyond the scope of non-equilibrium thermodynamic methods due to the existence of non variational dynamics, where the concept of free energy is lost [1]. The thermodynamic study of non-equilibrium systems requires more general concepts than are dealt with by equilibrium thermodynamics.

One fundamental difference between equilibrium thermodynamics and non-equilibrium thermodynamics lies in the behaviour of inhomogeneous systems, which require for their study knowledge of rates of reaction which are not considered in equilibrium thermodynamics of homogeneous systems. This is discussed below. Another fundamental and very important difference is the difficulty or impossibility, in general, in defining entropy at an instant of time in macroscopic terms for systems not in thermodynamic equilibrium; it can be done, to useful approximation, only in carefully chosen special cases, namely those that are throughout in local thermodynamic equilibrium.

Non-equilibrium thermodynamics

A profound difference separates equilibrium from non-equilibrium thermodynamics. Equilibrium thermodynamics ignores the time-courses of physical processes. In contrast, non-equilibrium thermodynamics attempts to describe their time-courses in continuous detail. Equilibrium thermodynamics restricts its considerations to processes that have initial and final states of thermodynamic equilibrium; the time-courses of processes are deliberately ignored.

Consequently, equilibrium thermodynamics allows processes that pass through states far from thermodynamic equilibrium, that cannot be described even by the variables admitted for non-equilibrium thermodynamics, [4] such as time rates of change of temperature and pressure. A quasi-static process is a conceptual timeless and physically impossible smooth mathematical passage along a continuous path of states of thermodynamic equilibrium.

Non-equilibrium thermodynamics, on the other hand, attempting to describe continuous time-courses, needs its state variables to have a very close connection with those of equilibrium thermodynamics. The suitable relationship that defines non-equilibrium thermodynamic state variables is as follows. On occasions when the system happens to be in states that are sufficiently close to thermodynamic equilibrium, non-equilibrium state variables are such that they can be measured locally with sufficient accuracy by the same techniques as are used to measure thermodynamic state variables, or by corresponding time and space derivatives, including fluxes of matter and energy.

In general, non-equilibrium thermodynamic systems are spatially and temporally non-uniform, but their non-uniformity still has a sufficient degree of smoothness to support the existence of suitable time and space derivatives of non-equilibrium state variables.

Kinetic molecular theory of gases - Physical Processes - MCAT - Khan Academy

Because of the spatial non-uniformity, non-equilibrium state variables that correspond to extensive thermodynamic state variables have to be defined as spatial densities of the corresponding extensive equilibrium state variables. On occasions when the system is sufficiently close to thermodynamic equilibrium, intensive non-equilibrium state variables, for example temperature and pressure, correspond closely with equilibrium state variables.

It is necessary that measuring probes be small enough, and rapidly enough responding, to capture relevant non-uniformity. Further, the non-equilibrium state variables are required to be mathematically functionally related to one another in ways that suitably resemble corresponding relations between equilibrium thermodynamic state variables. This is part of why non-equilibrium thermodynamics is a work in progress. Some concepts of particular importance for non-equilibrium thermodynamics include time rate of dissipation of energy Rayleigh , [9] Onsager , [10] also [8] [11] , time rate of entropy production Onsager , [10] thermodynamic fields, [12] [13] [14] dissipative structure , [15] and non-linear dynamical structure.

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One problem of interest is the thermodynamic study of non-equilibrium steady states , in which entropy production and some flows are non-zero, but there is no time variation of physical variables. One initial approach to non-equilibrium thermodynamics is sometimes called 'classical irreversible thermodynamics'.

According to Wildt [18] see also Essex [19] [20] [21] , current versions of non-equilibrium thermodynamics ignore radiant heat; they can do so because they refer to laboratory quantities of matter under laboratory conditions with temperatures well below those of stars. At laboratory temperatures, in laboratory quantities of matter, thermal radiation is weak and can be practically nearly ignored.

But, for example, atmospheric physics is concerned with large amounts of matter, occupying cubic kilometers, that, taken as a whole, are not within the range of laboratory quantities; then thermal radiation cannot be ignored. The terms 'classical irreversible thermodynamics' [3] and 'local equilibrium thermodynamics' are sometimes used to refer to a version of non-equilibrium thermodynamics that demands certain simplifying assumptions, as follows. The assumptions have the effect of making each very small volume element of the system effectively homogeneous, or well-mixed, or without an effective spatial structure, and without kinetic energy of bulk flow or of diffusive flux.

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Even within the thought-frame of classical irreversible thermodynamics, care [11] is needed in choosing the independent variables [22] for systems. In some writings, it is assumed that the intensive variables of equilibrium thermodynamics are sufficient as the independent variables for the task such variables are considered to have no 'memory', and do not show hysteresis ; in particular, local flow intensive variables are not admitted as independent variables; local flows are considered as dependent on quasi-static local intensive variables. Also it is assumed that the local entropy density is the same function of the other local intensive variables as in equilibrium; this is called the local thermodynamic equilibrium assumption [8] [11] [15] [16] [23] [24] [25] [26] see also Keizer [27].

Radiation is ignored because it is transfer of energy between regions, which can be remote from one another. In the classical irreversible thermodynamic approach, there is allowed very small spatial variation, from very small volume element to adjacent very small volume element, but it is assumed that the global entropy of the system can be found by simple spatial integration of the local entropy density; this means that spatial structure cannot contribute as it properly should to the global entropy assessment for the system. This approach assumes spatial and temporal continuity and even differentiability of locally defined intensive variables such as temperature and internal energy density.

All of these are very stringent demands. Consequently, this approach can deal with only a very limited range of phenomena. This approach is nevertheless valuable because it can deal well with some macroscopically observable phenomena.

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Non-equilibrium thermodynamics - Wikipedia

In other writings, local flow variables are considered; these might be considered as classical by analogy with the time-invariant long-term time-averages of flows produced by endlessly repeated cyclic processes; examples with flows are in the thermoelectric phenomena known as the Seebeck and the Peltier effects, considered by Kelvin in the nineteenth century and by Lars Onsager in the twentieth.

A further extension of local equilibrium thermodynamics is to allow that materials may have "memory", so that their constitutive equations depend not only on present values but also on past values of local equilibrium variables. Thus time comes into the picture more deeply than for time-dependent local equilibrium thermodynamics with memoryless materials, but fluxes are not independent variables of state. Extended irreversible thermodynamics is a branch of non-equilibrium thermodynamics that goes outside the restriction to the local equilibrium hypothesis. The space of state variables is enlarged by including the fluxes of mass, momentum and energy and eventually higher order fluxes.

The formalism is well-suited for describing high-frequency processes and small-length scales materials. There are many examples of stationary non-equilibrium systems, some very simple, like a system confined between two thermostats at different temperatures or the ordinary Couette flow , a fluid enclosed between two flat walls moving in opposite directions and defining non-equilibrium conditions at the walls. Laser action is also a non-equilibrium process, but it depends on departure from local thermodynamic equilibrium and is thus beyond the scope of classical irreversible thermodynamics; here a strong temperature difference is maintained between two molecular degrees of freedom with molecular laser, vibrational and rotational molecular motion , the requirement for two component 'temperatures' in the one small region of space, precluding local thermodynamic equilibrium, which demands that only one temperature be needed.

Damping of acoustic perturbations or shock waves are non-stationary non-equilibrium processes. Driven complex fluids , turbulent systems and glasses are other examples of non-equilibrium systems. The mechanics of macroscopic systems depends on a number of extensive quantities. It should be stressed that all systems are permanently interacting with their surroundings, thereby causing unavoidable fluctuations of extensive quantities.


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Equilibrium conditions of thermodynamic systems are related to the maximum property of the entropy. If the only extensive quantity that is allowed to fluctuate is the internal energy, all the other ones being kept strictly constant, the temperature of the system is measurable and meaningful. Non-equilibrium systems are much more complex and they may undergo fluctuations of more extensive quantities.

The boundary conditions impose on them particular intensive variables, like temperature gradients or distorted collective motions shear motions, vortices, etc. If free energies are very useful in equilibrium thermodynamics, it must be stressed that there is no general law defining stationary non-equilibrium properties of the energy as is the second law of thermodynamics for the entropy in equilibrium thermodynamics.

That is why in such cases a more generalized Legendre transformation should be considered. This is the extended Massieu potential.

Introduction

We then define the extended Massieu function as follows:. Intensities are global values, valid for the system as a whole. When boundaries impose to the system different local conditions, e. The latter are the thermodynamic forces driving fluxes of extensive properties through the system. It may be shown that the Legendre transformation changes the maximum condition of the entropy valid at equilibrium in a minimum condition of the extended Massieu function for stationary states, no matter whether at equilibrium or not.

In thermodynamics one is often interested in a stationary state of a process, allowing that the stationary state include the occurrence of unpredictable and experimentally unreproducible fluctuations in the state of the system. The fluctuations are due to the system's internal sub-processes and to exchange of matter or energy with the system's surroundings that create the constraints that define the process. If the stationary state of the process is stable, then the unreproducible fluctuations involve local transient decreases of entropy.

The reproducible response of the system is then to increase the entropy back to its maximum by irreversible processes: the fluctuation cannot be reproduced with a significant level of probability. Fluctuations about stable stationary states are extremely small except near critical points Kondepudi and Prigogine , page There are theorems about the irreversible dissipation of fluctuations.

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