Disequilibrium (thermodynamics)
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Non-equilibrium thermodynamics is a branch of
thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed b ...
that deals with physical systems that are not in
thermodynamic equilibrium Thermodynamic equilibrium is a notion of thermodynamics with axiomatic status referring to an internal state of a single thermodynamic system, or a relation between several thermodynamic systems connected by more or less permeable or impermeable ...
but can be described in terms of macroscopic quantities (non-equilibrium state variables) that represent an extrapolation of the variables used to specify the system in thermodynamic equilibrium. Non-equilibrium thermodynamics is concerned with transport processes and with the rates of
chemical reactions A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an energy change as new products ...
. 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. Many systems and processes can, however, be considered to be in equilibrium locally, thus allowing description by currently known equilibrium thermodynamics. Nevertheless, some natural systems and processes remain beyond the scope of equilibrium thermodynamic methods due to the existence of non variational dynamics, where the concept of free energy is lost. The thermodynamic study of non-equilibrium systems requires more general concepts than are dealt with by
equilibrium thermodynamics {{thermodynamics, cTopic=Branches Equilibrium Thermodynamics is the systematic study of transformations of matter and energy in systems in terms of a concept called thermodynamic equilibrium. The word equilibrium implies a state of balance. Equil ...
. 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, in defining
entropy Entropy is a scientific concept, most commonly associated with states of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the micros ...
at an instant of time in macroscopic terms for systems not in thermodynamic equilibrium. However, it can be done locally, and the macroscopic entropy will then be given by the integral of the locally defined entropy density. It has been found that many systems far outside global equilibrium still obey the concept of local equilibrium.


Scope


Difference between equilibrium and 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. Non-equilibrium thermodynamics, on the other hand, attempting to describe continuous time-courses, needs its
state variables A state variable is one of the set of variables that are used to describe the mathematical "state" of a dynamical system. Intuitively, the state of a system describes enough about the system to determine its future behaviour in the absence of a ...
to have a very close connection with those of equilibrium thermodynamics. This conceptual issue is overcome under the assumption of local equilibrium, which entails that the relationships that hold between macroscopic state variables at equilibrium hold locally, also outside equilibrium. Throughout the past decades, the assumption of local equilibrium has been tested, and found to hold, under increasingly extreme conditions, such as in the shock front of violent explosions, on reacting surfaces, and under extreme thermal gradients. Thus, non-equilibrium thermodynamics provides a consistent framework for modelling not only the initial and final states of a system, but also the evolution of the system in time. Together with the concept of entropy production, this provides a powerful tool in process optimisation, and provides a theoretical foundation for exergy analysis.


Non-equilibrium state variables

The suitable relationship that defines non-equilibrium
thermodynamic state In thermodynamics, a thermodynamic state of a system is its condition at a specific time; that is, fully identified by values of a suitable set of parameters known as state variables, state parameters or thermodynamic variables. Once such a set ...
variables is as follows. When the system is in local 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. 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. When the system is in local 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. In reality, these requirements, although strict, have been shown to be fulfilled even under extreme conditions, such as during phase transitions, at reacting interfaces, and in plasma droplets surrounded by ambient air. There are, however, situations where there are appreciable non-linear effects even at the local scale.


Overview

Some concepts of particular importance for non-equilibrium thermodynamics include time rate of dissipation of energy (Rayleigh 1873, Onsager 1931, alsoGyarmati, I. (1967/1970).Lavenda, B.H. (1978). ''Thermodynamics of Irreversible Processes'', Macmillan, London, .), time rate of entropy production (Onsager 1931), thermodynamic fields,Ziegler, H., (1983). ''An Introduction to Thermomechanics'', North-Holland, Amsterdam, .Balescu, R. (1975). ''Equilibrium and Non-equilibrium Statistical Mechanics'', Wiley-Interscience, New York, , Section 3.2, pages 64-72. dissipative structure, and non-linear dynamical structure. One problem of interest is the thermodynamic study of non-equilibrium
steady state In systems theory, a system or a process is in a steady state if the variables (called state variables) which define the behavior of the system or the process are unchanging in time. In continuous time, this means that for those properties ''p' ...
s, in which
entropy Entropy is a scientific concept, most commonly associated with states of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the micros ...
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'.Lebon, G., Jou, D., Casas-Vázquez, J. (2008). ''Understanding Non-equilibrium Thermodynamics: Foundations, Applications, Frontiers'', Springer-Verlag, Berlin, e-. There are other approaches to non-equilibrium thermodynamics, for example extended irreversible thermodynamics, and generalized thermodynamics, but they are hardly touched on in the present article.


Quasi-radiationless non-equilibrium thermodynamics of matter in laboratory conditions

According to Wildt (see also Essex.), 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.


Local equilibrium thermodynamics

The terms 'classical irreversible thermodynamics' 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 In mathematics, a volume element provides a means for integrating a function with respect to volume in various coordinate systems such as spherical coordinates and cylindrical coordinates. Thus a volume element is an expression of the form \ma ...
of the system effectively homogeneous, or well-mixed, or without an effective spatial structure. Even within the thought-frame of classical irreversible thermodynamics, care is needed in choosing the independent variables 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 Hysteresis is the dependence of the state of a system on its history. For example, a magnet may have more than one possible magnetic moment in a given magnetic field, depending on how the field changed in the past. Plots of a single component of ...
); 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 assumptionGlansdorff, P., Prigogine, I. (1971). ''Thermodynamic Theory of Structure, Stability, and Fluctuations'', Wiley-Interscience, London, 1971, .Jou, D., Casas-Vázquez, J., Lebon, G. (1993). ''Extended Irreversible Thermodynamics'', Springer, Berlin, , .De Groot, S.R., Mazur, P. (1962). ''Non-equilibrium Thermodynamics'', North-Holland, Amsterdam.Balescu, R. (1975). ''Equilibrium and Non-equilibrium Statistical Mechanics'', John Wiley & Sons, New York, .Mihalas, D., Weibel-Mihalas, B. (1984). ''Foundations of Radiation Hydrodynamics'', Oxford University Press, New York
.
Schloegl, F. (1989). ''Probability and Heat: Fundamentals of Thermostatistics'', Freidr. Vieweg & Sohn, Braunschweig, . (see also Keizer (1987)Keizer, J. (1987). ''Statistical Thermodynamics of Nonequilibrium Processes'', Springer-Verlag, New York, .). 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 spatial variation from infinitesimal volume element to adjacent infinitesimal 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 approach assumes spatial and temporal continuity and even differentiability of locally defined intensive variables such as temperature and internal energy density. While these demands may appear severely constrictive, it has been found that the assumptions of local equilibrium hold for a wide variety of systems, including reacting interfaces, on the surfaces of catalysts, in confined systems such as zeolites, under temperature gradients as large as 10^ K m^, and even in shock fronts moving at up to six times the speed of sound. 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 The kelvin (symbol: K) is the base unit for temperature in the International System of Units (SI). The Kelvin scale is an absolute temperature scale that starts at the lowest possible temperature (absolute zero), taken to be 0 K. By de ...
in the nineteenth century and by
Lars Onsager Lars Onsager (November 27, 1903 – October 5, 1976) was a Norwegian American physical chemist and theoretical physicist. He held the Gibbs Professorship of Theoretical Chemistry at Yale University. He was awarded the Nobel Prize in Chemist ...
in the twentieth. These effects occur at metal junctions, which were originally effectively treated as two-dimensional surfaces, with no spatial volume, and no spatial variation.


Local equilibrium thermodynamics with materials with "memory"

A further extension of local equilibrium thermodynamics is to allow that materials may have "memory", so that their
constitutive equation In physics and engineering, a constitutive equation or constitutive relation is a relation between two or more physical quantities (especially kinetic quantities as related to kinematic quantities) that is specific to a material or substance o ...
s 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

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
flux Flux describes any effect that appears to pass or travel (whether it actually moves or not) through a surface or substance. Flux is a concept in applied mathematics and vector calculus which has many applications in physics. For transport phe ...
es 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.


Basic concepts

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 In fluid dynamics, Couette flow is the flow of a viscosity, viscous fluid in the space between two surfaces, one of which is moving tangentially relative to the other. The relative motion of the surfaces imposes a shear stress on the fluid and ind ...
, a fluid enclosed between two flat walls moving in opposite directions and defining non-equilibrium conditions at the walls.
Laser A laser is a device that emits light through a process of optical amplification based on the stimulated emission of electromagnetic radiation. The word ''laser'' originated as an acronym for light amplification by stimulated emission of radi ...
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 Complex fluids are mixtures that have a coexistence between two phases: solid–liquid ( suspensions or solutions of macromolecules such as polymers), solid–gas (granular), liquid–gas (foams) or liquid–liquid (emulsions). They exhibit unusu ...
, 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. 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. The system's properties are then most conveniently described using the thermodynamic potential
Helmholtz free energy In thermodynamics, the Helmholtz free energy (or Helmholtz energy) is a thermodynamic potential that measures the useful work obtainable from a closed thermodynamic system at a constant temperature ( isothermal). The change in the Helmholtz ene ...
(''A'' = ''U'' - ''TS''), a
Legendre transformation In mathematics, the Legendre transformation (or Legendre transform), first introduced by Adrien-Marie Legendre in 1787 when studying the minimal surface problem, is an involutive transformation on real-valued functions that are convex on a rea ...
of the energy. If, next to fluctuations of the energy, the macroscopic dimensions (volume) of the system are left fluctuating, we use the
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol is a thermodynamic potential that can be used to calculate the maximum amount of Work (thermodynamics), work, other than Work (thermodynamics)#Pressure–v ...
(''G'' = ''U'' + ''PV'' - ''TS''), where the system's properties are determined both by the temperature and by the pressure. 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.), often called thermodynamic forces. 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 Entropy is a scientific concept, most commonly associated with states of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the micros ...
in equilibrium thermodynamics. That is why in such cases a more generalized Legendre transformation should be considered. This is the extended Massieu potential. By definition, the
entropy Entropy is a scientific concept, most commonly associated with states of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the micros ...
(''S'') is a function of the collection of extensive quantities E_i. Each extensive quantity has a conjugate intensive variable I_i (a restricted definition of intensive variable is used here by comparison to the definition given in this link) so that: : I_i = \frac. We then define the extended
Massieu function In thermodynamics, the Massieu function (sometimes called Massieu–Gibbs function, Massieu potential, or Gibbs function, or characteristic (state) function in its original terminology), symbol ( Psi), is defined by the following relation: ...
as follows: : \ k_ M = S - \sum_i( I_i E_i), where \ k_ is the
Boltzmann constant The Boltzmann constant ( or ) is the proportionality factor that relates the average relative thermal energy of particles in a ideal gas, gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin (K) and the ...
, whence : \ k_ \, dM = \sum_i (E_i \, dI_i). The independent variables are the intensities. Intensities are global values, valid for the system as a whole. When boundaries impose to the system different local conditions, (e.g. temperature differences), there are intensive variables representing the average value and others representing gradients or higher moments. 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.


Stationary states, fluctuations, and stability

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 1998, page 323). The stable stationary state has a local maximum of entropy and is locally the most reproducible state of the system. There are theorems about the irreversible dissipation of fluctuations. Here 'local' means local with respect to the abstract space of thermodynamic coordinates of state of the system. If the stationary state is unstable, then any fluctuation will almost surely trigger the virtually explosive departure of the system from the unstable stationary state. This can be accompanied by increased export of entropy.


Local thermodynamic equilibrium

The scope of present-day non-equilibrium thermodynamics does not cover all physical processes. A condition for the validity of many studies in non-equilibrium thermodynamics of matter is that they deal with what is known as ''local thermodynamic equilibrium''.


Ponderable matter

''Local thermodynamic equilibrium of matter'' (see also Keizer (1987) means that conceptually, for study and analysis, the system can be spatially and temporally divided into 'cells' or 'micro-phases' of small (infinitesimal) size, in which classical thermodynamical equilibrium conditions for matter are fulfilled to good approximation. These conditions are unfulfilled, for example, in very rarefied gases, in which molecular collisions are infrequent; and in the boundary layers of a star, where radiation is passing energy to space; and for interacting fermions at very low temperature, where dissipative processes become ineffective. When these 'cells' are defined, one admits that matter and energy may pass freely between contiguous 'cells', slowly enough to leave the 'cells' in their respective individual local thermodynamic equilibria with respect to intensive variables. One can think here of two 'relaxation times' separated by order of magnitude. Zubarev D. N.,(1974).
Nonequilibrium Statistical Thermodynamics
', translated from the Russian by P.J. Shepherd, New York, Consultants Bureau. ; .
The longer relaxation time is of the order of magnitude of times taken for the macroscopic dynamical structure of the system to change. The shorter is of the order of magnitude of times taken for a single 'cell' to reach local thermodynamic equilibrium. If these two relaxation times are not well separated, then the classical non-equilibrium thermodynamical concept of local thermodynamic equilibrium loses its meaning and other approaches have to be proposed, see for instance Extended irreversible thermodynamics. For example, in the atmosphere, the speed of sound is much greater than the wind speed; this favours the idea of local thermodynamic equilibrium of matter for atmospheric heat transfer studies at altitudes below about 60 km where sound propagates, but not above 100 km, where, because of the paucity of intermolecular collisions, sound does not propagate.


Milne's definition in terms of radiative equilibrium

Edward A. Milne, thinking about stars, gave a definition of 'local thermodynamic equilibrium' in terms of the
thermal radiation Thermal radiation is electromagnetic radiation emitted by the thermal motion of particles in matter. All matter with a temperature greater than absolute zero emits thermal radiation. The emission of energy arises from a combination of electro ...
of the
matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of atoms, which are made up of interacting subatomic pa ...
in each small local 'cell'. He defined 'local thermodynamic equilibrium' in a 'cell' by requiring that it macroscopically absorb and spontaneously emit radiation as if it were in radiative equilibrium in a cavity at the
temperature Temperature is a physical quantity that quantitatively expresses the attribute of hotness or coldness. Temperature is measurement, measured with a thermometer. It reflects the average kinetic energy of the vibrating and colliding atoms making ...
of the matter of the 'cell'. Then it strictly obeys Kirchhoff's law of equality of radiative emissivity and absorptivity, with a black body source function. The key to local thermodynamic equilibrium here is that the rate of collisions of ponderable matter particles such as molecules should far exceed the rates of creation and annihilation of photons.


Entropy in evolving systems

It is pointed out by W.T. Grandy Jr, that entropy, though it may be defined for a non-equilibrium system is—when strictly considered—only a macroscopic quantity that refers to the whole system, and is not a dynamical variable and in general does not act as a local potential that describes local physical forces. Under special circumstances, however, one can metaphorically think as if the thermal variables behaved like local physical forces. The approximation that constitutes classical irreversible thermodynamics is built on this metaphoric thinking. This point of view shares many points in common with the concept and the use of entropy in continuum thermomechanics, which evolved completely independently of statistical mechanics and maximum-entropy principles.


Entropy in non-equilibrium

To describe deviation of the thermodynamic system from equilibrium, in addition to constitutive variables x_1, x_2, ..., x_n that are used to fix the equilibrium state, as was described above, a set of variables \xi_1, \xi_2,\ldots that are called ''internal variables'' have been introduced. The equilibrium state is considered to be stable and the main property of the internal variables, as measures of non-equilibrium of the system, is their tending to disappear; the local law of disappearing can be written as relaxation equation for each internal variable where \tau_i= \tau_i(T, x_1, x_2, \ldots, x_n) is a relaxation time of a corresponding variables. It is convenient to consider the initial value \xi_i^0 are equal to zero. The above equation is valid for small deviations from equilibrium; The dynamics of internal variables in general case is considered by Pokrovskii.Pokrovskii V.N. (2013) A derivation of the main relations of non-equilibrium thermodynamics. Hindawi Publishing Corporation: ISRN Thermodynamics, vol. 2013, article ID 906136, 9 p. https://dx.doi.org/10.1155/2013/906136. Entropy of the system in non-equilibrium is a function of the total set of variables The essential contribution to the thermodynamics of the non-equilibrium systems was brought by the
Nobel Prize The Nobel Prizes ( ; ; ) are awards administered by the Nobel Foundation and granted in accordance with the principle of "for the greatest benefit to humankind". The prizes were first awarded in 1901, marking the fifth anniversary of Alfred N ...
winner Ilya
Prigogine Prigozhin or Prigogine () is a masculine East Slavic surname originating from the adjective ''prigozhii'', meaning ''useful'', ''suitable'', ''nice''; its feminine counterpart is Prigozhina. The surname may refer to the following notable people: ...
, when he and his collaborators investigated the systems of chemically reacting substances. The stationary states of such systems exists due to exchange both particles and energy with the environment. In section 8 of the third chapter of his book, Prigogine has specified three contributions to the variation of entropy of the considered system at the given volume and constant temperature T . The increment of
entropy Entropy is a scientific concept, most commonly associated with states of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the micros ...
S can be calculated according to the formula The first term on the right hand side of the equation presents a stream of thermal energy into the system; the last term—a part of a stream of energy h_\alpha coming into the system with the stream of particles of substances \Delta N_\alpha that can be positive or negative, \eta_\alpha= h_\alpha- \mu_\alpha, where \mu_\alpha is
chemical potential In thermodynamics, the chemical potential of a Chemical specie, species is the energy that can be absorbed or released due to a change of the particle number of the given species, e.g. in a chemical reaction or phase transition. The chemical potent ...
of substance \alpha. The middle term in (1) depicts
energy dissipation In thermodynamics, dissipation is the result of an irreversible process that affects a thermodynamic system. In a dissipative process, energy (internal, bulk flow kinetic, or system potential) transforms from an initial form to a final form, whe ...
(
entropy production Entropy production (or generation) is the amount of entropy which is produced during heat process to evaluate the efficiency of the process. Short history Entropy is produced in irreversible processes. The importance of avoiding irreversible p ...
) due to the relaxation of internal variables \xi_j. In the case of chemically reacting substances, which was investigated by Prigogine, the internal variables appear to be measures of incompleteness of chemical reactions, that is measures of how much the considered system with chemical reactions is out of equilibrium. The theory can be generalised, to consider any deviation from the equilibrium state as an internal variable, so that we consider the set of internal variables \xi_j in equation (1) to consist of the quantities defining not only degrees of completeness of all chemical reactions occurring in the system, but also the structure of the system, gradients of temperature, difference of concentrations of substances and so on.


Flows and forces

The fundamental relation of classical equilibrium thermodynamics W. Greiner, L. Neise, and H. Stöcker (1997), ''Thermodynamics and Statistical Mechanics (Classical Theoretical Physics)'' ,Springer-Verlag, New York, P85, 91, 101,108,116, . : dS=\fracdU+\fracdV-\sum_^s\fracdN_i expresses the change in
entropy Entropy is a scientific concept, most commonly associated with states of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the micros ...
dS of a system as a function of the intensive quantities
temperature Temperature is a physical quantity that quantitatively expresses the attribute of hotness or coldness. Temperature is measurement, measured with a thermometer. It reflects the average kinetic energy of the vibrating and colliding atoms making ...
T,
pressure Pressure (symbol: ''p'' or ''P'') is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure (also spelled ''gage'' pressure)The preferred spelling varies by country and eve ...
p and i^
chemical potential In thermodynamics, the chemical potential of a Chemical specie, species is the energy that can be absorbed or released due to a change of the particle number of the given species, e.g. in a chemical reaction or phase transition. The chemical potent ...
\mu_i and of the differentials of the extensive quantities
energy Energy () is the physical quantity, quantitative physical property, property that is transferred to a physical body, body or to a physical system, recognizable in the performance of Work (thermodynamics), work and in the form of heat and l ...
U,
volume Volume is a measure of regions in three-dimensional space. It is often quantified numerically using SI derived units (such as the cubic metre and litre) or by various imperial or US customary units (such as the gallon, quart, cubic inch) ...
V and i^
particle number In thermodynamics, the particle number (symbol ) of a thermodynamic system is the number of constituent particles in that system. The particle number is a fundamental thermodynamic property which is conjugate to the chemical potential. Unlike m ...
N_i. Following Onsager (1931,I), let us extend our considerations to thermodynamically non-equilibrium systems. As a basis, we need locally defined versions of the extensive macroscopic quantities U, V and N_i and of the intensive macroscopic quantities T, p and \mu_i. For classical non-equilibrium studies, we will consider some new locally defined intensive macroscopic variables. We can, under suitable conditions, derive these new variables by locally defining the gradients and flux densities of the basic locally defined macroscopic quantities. Such locally defined gradients of intensive macroscopic variables are called 'thermodynamic forces'. They 'drive' flux densities, perhaps misleadingly often called 'fluxes', which are dual to the forces. These quantities are defined in the article on
Onsager reciprocal relations In thermodynamics, the Onsager reciprocal relations express the equality of certain ratios between flows and forces in thermodynamic systems out of equilibrium, but where a notion of local equilibrium exists. "Reciprocal relations" occur betw ...
. Establishing the relation between such forces and flux densities is a problem in statistical mechanics. Flux densities (J_i) may be coupled. The article on Onsager reciprocal relations considers the stable near-steady thermodynamically non-equilibrium regime, which has dynamics linear in the forces and flux densities. In stationary conditions, such forces and associated flux densities are by definition time invariant, as also are the system's locally defined entropy and rate of entropy production. Notably, according to
Ilya Prigogine Viscount Ilya Romanovich Prigogine (; ; 28 May 2003) was a Belgian physical chemist of Russian-Jewish origin, noted for his work on dissipative structures, complex systems, and irreversibility. Prigogine's work most notably earned him the 19 ...
and others, when an open system is in conditions that allow it to reach a stable stationary thermodynamically non-equilibrium state, it organizes itself so as to minimize total entropy production defined locally. This is considered further below. One wants to take the analysis to the further stage of describing the behaviour of surface and volume integrals of non-stationary local quantities; these integrals are macroscopic fluxes and production rates. In general the dynamics of these integrals are not adequately described by linear equations, though in special cases they can be so described.


Onsager reciprocal relations

Following Section III of Rayleigh (1873), Onsager (1931, I) showed that in the regime where both the flows (J_i) are small and the thermodynamic forces (F_i) vary slowly, the rate of creation of entropy (\sigma) is linearly related to the flows: : \sigma = \sum_i J_i\frac and the flows are related to the gradient of the forces, parametrized by a
matrix Matrix (: matrices or matrixes) or MATRIX may refer to: Science and mathematics * Matrix (mathematics), a rectangular array of numbers, symbols or expressions * Matrix (logic), part of a formula in prenex normal form * Matrix (biology), the m ...
of coefficients conventionally denoted L: : J_i = \sum_ L_ \frac from which it follows that: : \sigma = \sum_ L_ \frac\frac The
second law of thermodynamics The second law of thermodynamics is a physical law based on Universal (metaphysics), universal empirical observation concerning heat and Energy transformation, energy interconversions. A simple statement of the law is that heat always flows spont ...
requires that the matrix L be
positive definite In mathematics, positive definiteness is a property of any object to which a bilinear form In mathematics, a bilinear form is a bilinear map on a vector space (the elements of which are called '' vectors'') over a field ''K'' (the elements of w ...
.
Statistical mechanics In physics, statistical mechanics is a mathematical framework that applies statistical methods and probability theory to large assemblies of microscopic entities. Sometimes called statistical physics or statistical thermodynamics, its applicati ...
considerations involving microscopic reversibility of dynamics imply that the matrix L is
symmetric Symmetry () in everyday life refers to a sense of harmonious and beautiful proportion and balance. In mathematics, the term has a more precise definition and is usually used to refer to an object that is invariant under some transformations ...
. This fact is called the ''Onsager reciprocal relations''. The generalization of the above equations for the rate of creation of entropy was given by Pokrovskii.


Speculated extremal principles for non-equilibrium processes

Until recently, prospects for useful extremal principles in this area have seemed clouded. Nicolis (1999) concludes that one model of atmospheric dynamics has an attractor which is not a regime of maximum or minimum dissipation; she says this seems to rule out the existence of a global organizing principle, and comments that this is to some extent disappointing; she also points to the difficulty of finding a thermodynamically consistent form of entropy production. Another top expert offers an extensive discussion of the possibilities for principles of extrema of entropy production and of dissipation of energy: Chapter 12 of Grandy (2008)Grandy, W.T., Jr (2008). is very cautious, and finds difficulty in defining the 'rate of internal entropy production' in many cases, and finds that sometimes for the prediction of the course of a process, an extremum of the quantity called the rate of dissipation of energy may be more useful than that of the rate of entropy production; this quantity appeared in Onsager's 1931 origination of this subject. Other writers have also felt that prospects for general global extremal principles are clouded. Such writers include Glansdorff and Prigogine (1971), Lebon, Jou and Casas-Vásquez (2008), and Šilhavý (1997). There is good experimental evidence that heat convection does not obey extremal principles for time rate of entropy production. Theoretical analysis shows that chemical reactions do not obey extremal principles for the second differential of time rate of entropy production. The development of a general extremal principle seems infeasible in the current state of knowledge.


Applications

Non-equilibrium thermodynamics has been successfully applied to describe biological processes such as
protein folding Protein folding is the physical process by which a protein, after Protein biosynthesis, synthesis by a ribosome as a linear chain of Amino acid, amino acids, changes from an unstable random coil into a more ordered protein tertiary structure, t ...
/unfolding and transport through membranes. It is also used to give a description of the dynamics of
nanoparticle A nanoparticle or ultrafine particle is a particle of matter 1 to 100 nanometres (nm) in diameter. The term is sometimes used for larger particles, up to 500 nm, or fibers and tubes that are less than 100 nm in only two directions. At ...
s, which can be out of equilibrium in systems where catalysis and electrochemical conversion is involved. Also, ideas from non-equilibrium thermodynamics and the informatic theory of entropy have been adapted to describe general economic systems.


See also

*
Time crystal In condensed matter physics, a time crystal is a quantum system of particles whose lowest-energy state is one in which the particles are in repetitive motion. The system cannot lose energy to the environment and come to rest because it is alread ...
*
Dissipative system A dissipative system is a thermodynamically open system which is operating out of, and often far from, thermodynamic equilibrium in an environment with which it exchanges energy and matter. A tornado may be thought of as a dissipative system. Di ...
*
Entropy production Entropy production (or generation) is the amount of entropy which is produced during heat process to evaluate the efficiency of the process. Short history Entropy is produced in irreversible processes. The importance of avoiding irreversible p ...
*
Extremal principles in non-equilibrium thermodynamics Energy dissipation and entropy production extremal principles are ideas developed within non-equilibrium thermodynamics that attempt to predict the likely steady states and dynamical structures that a physical system might show. The search for extr ...
*
Self-organization Self-organization, also called spontaneous order in the social sciences, is a process where some form of overall order and disorder, order arises from local interactions between parts of an initially disordered system. The process can be spont ...
* Autocatalytic reactions and order creation * Self-organizing criticality * Bogoliubov-Born-Green-Kirkwood-Yvon hierarchy of equations *
Boltzmann equation The Boltzmann equation or Boltzmann transport equation (BTE) describes the statistical behaviour of a thermodynamic system not in a state of equilibrium; it was devised by Ludwig Boltzmann in 1872.Encyclopaedia of Physics (2nd Edition), R. G ...
*
Vlasov equation In plasma physics, the Vlasov equation is a differential equation describing time evolution of the distribution function of collisionless plasma consisting of charged particles with long-range interaction, such as the Coulomb interaction. The e ...
*
Maxwell's demon Maxwell's demon is a thought experiment that appears to disprove the second law of thermodynamics. It was proposed by the physicist James Clerk Maxwell in 1867. In his first letter, Maxwell referred to the entity as a "finite being" or a "being ...
*
Information entropy In information theory, the entropy of a random variable quantifies the average level of uncertainty or information associated with the variable's potential states or possible outcomes. This measures the expected amount of information needed ...
*
Spontaneous symmetry breaking Spontaneous symmetry breaking is a spontaneous process of symmetry breaking, by which a physical system in a symmetric state spontaneously ends up in an asymmetric state. In particular, it can describe systems where the equations of motion o ...
* Frenesy *
Autopoiesis The term autopoiesis (), one of several current theories of life, refers to a system capable of producing and maintaining itself by creating its own parts. The term was introduced in the 1972 publication '' Autopoiesis and Cognition: The Realizat ...
*
Maximum power principle In mathematical analysis, the maximum and minimum of a function are, respectively, the greatest and least value taken by the function. Known generically as extremum, they may be defined either within a given range (the ''local'' or ''relative ...


References


Sources

* Callen, H.B. (1960/1985). ''Thermodynamics and an Introduction to Thermostatistics'', (1st edition 1960) 2nd edition 1985, Wiley, New York, . * Eu, B.C. (2002). ''Generalized Thermodynamics. The Thermodynamics of Irreversible Processes and Generalized Hydrodynamics'', Kluwer Academic Publishers, Dordrecht, . * Glansdorff, P., Prigogine, I. (1971). ''Thermodynamic Theory of Structure, Stability, and Fluctuations'', Wiley-Interscience, London, 1971, . * Grandy, W.T. Jr (2008). ''Entropy and the Time Evolution of Macroscopic Systems''. Oxford University Press. . * Gyarmati, I. (1967/1970). ''Non-equilibrium Thermodynamics. Field Theory and Variational Principles'', translated from the Hungarian (1967) by E. Gyarmati and W.F. Heinz, Springer, Berlin. * Lieb, E.H., Yngvason, J. (1999). 'The physics and mathematics of the second law of thermodynamics', ''Physics Reports'', 310: 1–96
See also this.


Further reading

* Ziegler, Hans (1977): ''An introduction to Thermomechanics''. North Holland, Amsterdam. . Second edition (1983) . * Kleidon, A., Lorenz, R.D., editors (2005). ''Non-equilibrium Thermodynamics and the Production of Entropy'', Springer, Berlin. . * Prigogine, I. (1955/1961/1967). ''Introduction to Thermodynamics of Irreversible Processes''. 3rd edition, Wiley Interscience, New York. * Zubarev D. N. (1974):
Nonequilibrium Statistical Thermodynamics
'. New York, Consultants Bureau. ; . * Keizer, J. (1987). ''Statistical Thermodynamics of Nonequilibrium Processes'', Springer-Verlag, New York, . * Zubarev D. N., Morozov V., Ropke G. (1996): ''Statistical Mechanics of Nonequilibrium Processes: Basic Concepts, Kinetic Theory''. John Wiley & Sons. . * Zubarev D. N., Morozov V., Ropke G. (1997): ''Statistical Mechanics of Nonequilibrium Processes: Relaxation and Hydrodynamic Processes''. John Wiley & Sons. . * Tuck, Adrian F. (2008). ''Atmospheric turbulence : a molecular dynamics perspective''. Oxford University Press. . * Grandy, W.T. Jr (2008). ''Entropy and the Time Evolution of Macroscopic Systems''. Oxford University Press. . * Kondepudi, D., Prigogine, I. (1998). ''Modern Thermodynamics: From Heat Engines to Dissipative Structures''. John Wiley & Sons, Chichester. . * de Groot S.R., Mazur P. (1984). ''Non-Equilibrium Thermodynamics'' (Dover). * Ramiro Augusto Salazar La Rotta. (2011). ''The Non-Equilibrium Thermodynamics, Perpetual''


External links


Stephan Herminghaus' Dynamics of Complex Fluids Department at the Max Planck Institute for Dynamics and Self Organization


- 1992- book by Xavier de Hemptinne.
Nonequilibrium Thermodynamics of Small Systems
- PhysicsToday.org
Into the Cool
- 2005 book by Dorion Sagan and Eric D. Schneider, on nonequilibrium thermodynamics and
evolutionary theory Evolution is the change in the heritable characteristics of biological populations over successive generations. It occurs when evolutionary processes such as natural selection and genetic drift act on genetic variation, resulting in certai ...
. *
Thermodynamics "beyond" local equilibrium
{{DEFAULTSORT:Non-Equilibrium Thermodynamics Branches of thermodynamics