In thermodynamics, a thermodynamic system is in thermodynamic equilibrium when it is in thermal equilibrium, mechanical equilibrium, radiative equilibrium, and chemical equilibrium. Equilibrium means a state of balance. In a state of thermodynamic equilibrium, there are no net flows of matter or of energy, no phase changes, and no unbalanced potentials (or driving forces), within the system. A system that is in thermodynamic equilibrium experiences no changes when it is isolated from its surroundings.
In non-equilibrium systems there are net flows of matter or energy, or phase changes are occurring; if such changes can be triggered to occur in a system in which they are not already occurring, it is said to be in a metastable equilibrium.
When a body of material starts from a non-equilibrium state of inhomogeneity or chemical non-equilibrium, and is then isolated, it spontaneously evolves towards its own internal state of thermodynamic equilibrium. It is not necessary that all aspects of internal thermodynamic equilibrium be reached simultaneously; some can be established before others.
Classical thermodynamics deals with states of dynamic equilibrium. The state of a system at thermodynamic equilibrium is the one for which some thermodynamic potential is minimized, or for which the entropy (S) is maximized, for specified conditions. One such potential is the Helmholtz free energy (A), for a system with surroundings at controlled constant temperature and volume:
- A = U – TS.
Another potential, the Gibbs free energy (G), is minimized at thermodynamic equilibrium in a system with surroundings at controlled constant temperature and pressure:
- G = U – TS + PV.
where T denotes the absolute thermodynamic temperature, P the pressure, S the entropy, V the volume, and U the internal energy of the system.
Thermodynamic equilibrium is the unique stable stationary state that is approached or eventually reached as the system interacts with its surroundings over a long time. The above-mentioned potentials are mathematically constructed to be the thermodynamic quantities that are minimized under the particular conditions in the specified surroundings.
Conditions for thermodynamic equilibrium 
- For a completely isolated system, S is maximum at thermodynamic equilibrium.
- For a system with controlled constant temperature and volume, A is minimum at thermodynamic equilibrium.
- For a system with controlled constant temperature and pressure, G is minimum at thermodynamic equilibrium.
The various types of equilibriums are achieved as follows:
- Two systems are in thermal equilibrium when their temperatures are the same.
- Two systems are in mechanical equilibrium when their pressures are the same.
- Two systems are in diffusive equilibrium when their chemical potentials are the same.
- All forces are balanced.
Local and global equilibrium 
It is useful to distinguish between global and local thermodynamic equilibrium. In thermodynamics, exchanges within a system and between the system and the outside are controlled by intensive parameters. As an example, temperature controls heat exchanges. Global thermodynamic equilibrium (GTE) means that those intensive parameters are homogeneous throughout the whole system, while local thermodynamic equilibrium (LTE) means that those intensive parameters are varying in space and time, but are varying so slowly that, for any point, one can assume thermodynamic equilibrium in some neighborhood about that point.
If the description of the system requires variations in the intensive parameters that are too large, the very assumptions upon which the definitions of these intensive parameters are based will break down, and the system will be in neither global nor local equilibrium. For example, it takes a certain number of collisions for a particle to equilibrate to its surroundings. If the average distance it has moved during these collisions removes it from the neighborhood it is equilibrating to, it will never equilibrate, and there will be no LTE. Temperature is, by definition, proportional to the average internal energy of an equilibrated neighborhood. Since there is no equilibrated neighborhood, the concept of temperature breaks down, and the temperature becomes undefined.
It is important to note that this local equilibrium may apply only to a certain subset of particles in the system. For example, LTE is usually applied only to massive particles. In a radiating gas, the photons being emitted and absorbed by the gas need not be in thermodynamic equilibrium with each other or with the massive particles of the gas in order for LTE to exist. In some cases, it is not considered necessary for free electrons to be in equilibrium with the much more massive atoms or molecules for LTE to exist.
As an example, LTE will exist in a glass of water that contains a melting ice cube. The temperature inside the glass can be defined at any point, but it is colder near the ice cube than far away from it. If energies of the molecules located near a given point are observed, they will be distributed according to the Maxwell-Boltzmann distribution for a certain temperature. If the energies of the molecules located near another point are observed, they will be distributed according to the Maxwell-Boltzmann distribution for another temperature.
Local thermodynamic equilibrium does not require either local or global stationarity. In other words, each small locality need not have a constant temperature. However, it does require that each small locality change slowly enough to practically sustain its local Maxwell-Boltzmann distribution of molecular velocities. A global non-equilibrium state can be stably stationary only if it is maintained by exchanges between the system and the outside. For example, a globally stably stationary state could be maintained inside the glass of water by continuously adding finely powdered ice into it in order to compensate for the melting, and continuously draining off the meltwater. Transport phenomena are processes that lead a system from local to global thermodynamic equilibrium. Going back to our example, the diffusion of heat will lead our glass of water toward global thermodynamic equilibrium, a state in which the temperature of the glass is completely homogeneous.
Types of equilibrium 
Thermodynamic equilibrium 
Careful and well informed writers about thermodynamics, in their accounts of thermodynamic equilibrium, often enough make provisos or reservations to their statements. Some writers leave such reservations merely implied or more or less unstated.
For example, one widely cited writer, H. B. Callen writes in this context: "In actuality, few systems are in absolute and true equilibrium." He refers to radioactive processes and remarks that they may take "cosmic times to complete, [and] generally can be ignored". He adds "In practice, the criterion for equilibrium is circular. Operationally, a system is in an equilibrium state if its properties are consistently described by thermodynamic theory!"
J.A. Beattie and I. Oppenheim write: "Insistence on a strict interpretation of the definition of equilibrium would rule out the application of thermodynamics to practically all states of real systems."
Another author, cited by Callen as giving a "scholarly and rigorous treatment", and cited by Adkins as having written a "classic text", A.B. Pippard writes in that text: "Given long enough a supercooled vapour will eventually condense, ... . The time involved may be so enormous, however, perhaps 10100 years or more, ... . For most purposes, provided the rapid change is not artificially stimulated, the systems may be regarded as being in equilibrium.
Another author, A. Münster, writes in this context. He observes that thermonuclear processes often occur so slowly that they can be ignored in thermodynamics. He comments: "The concept 'absolute equilibrium' or 'equilibrium with respect to all imaginable processes', has therefore, no physical significance." He therefore states that: "... we can consider an equilibrium only with respect to specified processes and defined experimental conditions." 
According to L. Tisza: "... in the discussion of phenomena near absolute zero. The absolute predictions of the classical theory become particularly vague because the occurrence of frozen-in nonequilibrium states is very common."
The most general kind of thermodynamic equilibrium of a system is through contact with the surroundings that allows simultaneous passages of all chemical substances and all kinds of energy. A system in thermodynamic equilibrium may move with uniform acceleration through space but must not change its shape or size while doing so; thus it is defined by a rigid volume in space. It may lie within external fields of force, determined by external factors of far greater extent than the system itself, so that events within the system cannot in an appreciable amount affect the external fields of force. The system can be in thermodynamic equilibrium only if the external force fields are uniform, and are determining its uniform acceleration, or if it lies in a non-uniform force field but is held stationary there by local forces, such as mechanical pressures, on its surface.
Thermodynamic equilibrium is a primitive notion of the theory of thermodynamics. According to P.M. Morse: "It should be emphasized that the fact that there are thermodynamic states, ... , and the fact that there are thermodynamic variables which are uniquely specified by the equilibrium state ... are not conclusions deduced logically from some philosophical first principles. They are conclusions ineluctably drawn from more than two centuries of experiments." This means that thermodynamic equilibrium is not to be defined solely in terms of other theoretical concepts of thermodynamics. M. Bailyn proposes a fundamental law of thermodynamics that defines and postulates the existence of states of thermodynamic equilibrium.
Textbook definitions of thermodynamic equilibrium are often stated carefully, with some reservation or other.
For example, A. Münster writes: "An isolated system is in thermodynamic equilibrium when, in the system, no changes of state are occurring at a measurable rate." There are two reservations stated here; the system is isolated; any changes of state are immeasurably slow. He discusses the second proviso by giving an account of a mixture oxygen and hydrogen at room temperature in the absence of a catalyst. Münster points out that a thermodynamic equilibrium state is described by fewer macroscopic variables than is any other state of a given system. This is partly, but not entirely, because all flows within and through the system are zero.
R. Haase's presentation of thermodynamics does not start with a restriction to thermodynamic equilibrium because he intends to allow for non-equilibrium thermodynamics. He considers an arbitrary system with time invariant properties. He tests it for thermodynamic equilibrium by cutting it off from all external influences, except external force fields. If after insulation, nothing changes, he says that the system was in equilibrium.
In a section headed "Thermodynamic equilibrium", H.B. Callen defines equilbrium states in a paragraph. He points out that they "are determined by intrinsic factors" within the system. They are "terminal states", towards which the systems evolve, over time, which may occur with "glacial slowness". This statement does not explicitly say that for thermodynamic equilibrium, the system must be isolated; Callen does not spell out what he means by the words "intrinsic factors".
Another textbook writer, C.J. Adkins, explicitly allows thermodynamic equilibrium to occur in a system which is not isolated. His system is, however, closed with respect to transfer of matter. He writes: "In general, the approach to thermodynamic equilibrium will involve both thermal and work-like interactions with the surroundings." He distinguishes such thermodynamic equilibrium from thermal equilibrium, in which only thermal contact is mediating transfer of energy.
Another textbook author, J.R. Partington, writes: "(i) An equilibrium state is one which is independent of time." But, referring to systems "which are only apparently in equilibrium", he adds : "Such systems are in states of ″false equilibrium.″" Partington's statement does not explicitly state that the equilibrium refers to an isolated system. Like Münster, Partington also refers to the mixture of oxygen and hydrogen. He adds a proviso that "In a true equilibrium state, the smallest change of any external condition which influences the state will produce a small change of state ..." This proviso means that thermodynamic equilibrium must be stable against small perturbations; this requirement is essential for the strict meaning of thermodynamic equilibrium.
A student textbook by F.H. Crawford has a section headed "Thermodynamic Equilibrium". It distinguishes several drivers of flows, and then says: "These are examples of the apparently universal tendency of isolated systems toward a state of complete mechanical, thermal, chemical, and electrical—or, in a single word, thermodynamic—equilibrium."
A monograph on classical thermodynamics by H.A. Buchdahl considers the "equilibrium of a thermodynamic system", without actually writing the phrase "thermodynamic equilibrium". Referring to systems closed to exchange of matter, Buchdahl writes: "If a system is in a terminal condition which is properly static, it will be said to be in equilibrium." Buchdahl's monograph also discusses amorphous glass, for the purposes of thermodynamic description. It states: "More precisely, the glass may be regarded as being in equilibrium so long as experimental tests show that 'slow' transitions are in effect reversible." It is not customary to make this proviso part of the definition of thermodynamic equilibrium, but the converse is usually assumed: that if a body in thermodynamic equilibrium is subject to a sufficiently slow process, that process may be considered to be sufficiently nearly reversible, and the body remains sufficiently nearly in thermodynamic equilibrium during the process.
A. Münster carefully extends his definition of thermodynamic equilibrium for isolated systems by introducing a concept of contact equilibrium. This specifies particular processes that are allowed when considering thermodynamic equilibrium for non-isolated systems, with special concern for open systems, which may gain or lose matter from or to their surroundings. A contact equilibrium is between the system of interest and a system in the surroundings, brought into contact with the system of interest, the contact being through a special kind of wall; for the rest, the whole joint system is isolated. Walls of this special kind were also considered by C. Carathéodory, and are mentioned by other writers also. They are selectively permeable. They may be permeable only to mechanical work, or only to heat, or only to some particular chemical substance. Each contact equilibrium defines an intensive parameter; for example, a wall permeable only to heat defines an empirical temperature. A contact equilibrium can exist for each chemical constituent of the system of interest. In a contact equilibrium, despite the possible exchange through the selectively permeable wall, the system of interest is changeless, as if it were in isolated thermodynamic equilibrium. This scheme follows the general rule that "... we can consider an equilibrium only with respect to specified processes and defined experimental conditions."  Thermodynamic equilibrium for an open system means that, with respect to every relevant kind of selectively permeable wall, contact equilibrium exists when the respective intensive parameters of the system and surroundings are equal. This definition does not consider the most general kind of thermodynamic equilibrium, which is through unselective contacts. This definition does not simply state that no current of matter or energy exists in the interior or at the boundaries; but it is compatible with the following definition, which does so state.
M. Zemansky also distinguishes mechanical, chemical, and thermal equilibrium. He then writes: "When the conditions for all three types of equilibrium are satisfied, the system is said to be in a state of thermodynamic equilibrium".
P.M. Morse writes that thermodynamics is concerned with "states of thermodynamic equilibrium". He also uses the phrase "thermal equilibrium" while discussing transfer of energy as heat between a body and a heat reservoir in its surroundings, though not explicitly defining a special term 'thermal equilibrium'.
J.R. Waldram writes of "a definite thermodynamic state". He defines the term "thermal equilibrium" for a system "when its observables have ceased to change over time". But shortly below that definition he writes of a piece of glass that has not yet reached its "full thermodynamic equilibrium state".
Considering equilibrium states, M. Bailyn writes: "Each intensive variable has its own type of equilibrium." He then defines thermal equilibrium, mechanical equilibrium, and material equilibrium. Accordingly, he writes: "If all the intensive variables become uniform, thermodynamic equilibrium is said to exist." He is not here considering the presence of an external force field.
J.G. Kirkwood and I. Oppenheim define thermodynamic equilibrium as follows: "A system is in a state of thermodynamic equilibrium if, during the time period allotted for experimentation, (a) its intensive properties are independent of time and (b) no current of matter or energy exists in its interior or at its boundaries with the surroundings." It is evident that they are not restricting the definition to isolated or to closed systems. They do not discuss the possibility of changes that occur with "glacial slowness", and proceed beyond the time period allotted for experimentation. They note that for two systems in contact, there exists a small subclass of intensive properties such that if all those of that small subclass are respectively equal, then all respective intensive properties are equal. States of thermodynamic equilibrium may be defined by this subclass, provided some other conditions are satisfied.
Characteristics of a state of thermodynamic equilibrium 
Uniform temperature 
According to E.A. Guggenheim, "The most important conception of thermodynamics is temperature." Planck introduces his treatise with a brief account of heat and temperature and thermal equilibrium, and then announces: "In the following we shall deal chiefly with homogeneous, isotropic bodies of any form, possessing throughout their substance the same temperature and density, and subject to a uniform pressure acting everywhere perpendicular to the surface." As did Carathéodory, Planck was setting aside surface effects and external fields and anisotropic crystals. Though referring to temperature, Planck did not there explicitly refer to the concept of thermodynamic equilibrium. In contrast, Carathéodory's scheme of presentation of classical thermodynamics for closed systems postulates the concept of an "equilibrium state" following Gibbs (Gibbs speaks routinely of a "thermodynamic state"), though not explicitly using the phrase 'thermodynamic equilibrium', nor explicitly postulating the existence of a temperature to define it.
The temperature within a system in thermodynamic equilibrium is uniform in space as well as in time. This is so in all cases, including those of non-uniform external force fields. In order that a system may be in its own internal state of thermodynamic equilibrium, it is of course necessary, but not sufficient, that it be in its own internal state of thermal equilibrium; it is possible for a system to reach internal mechanical equilibrium before it reaches internal thermal equilibrium.
Number of real variables needed for specification 
In his exposition of his scheme of closed system equilibrium thermodynamics, C. Carathéodory initially postulates that experiment reveals that a definite number of real variables define the states that are the points of the manifold of equilibria. In the opinion of Prigogine and Defay (1945): "It is a matter of experience that when we have specified a certain number of macroscopic properties of a system, then all the other properties are fixed." This opinion of Prigogine and Defay is in precise agreement with this postulate of Carathéodory. As noted above, according to A. Münster, the number of variables needed to define a thermodynamic equilibrium is the least for any state of a given isolated system. As noted above, J.G. Kirkwood and I. Oppenheim point out that a state of thermodynamic equilibrium may be defined by a special subclass of intensive variables, with a definite number of members in that subclass.
If the thermodynamic equilibrium lies in an external force field, it is only the temperature that can in general be expected to be spatially uniform. Intensive variables other than temperature will in general be non-uniform if the external force field is non-zero. In such a case, in general, additional variables are needed to describe the spatial non-uniformity.
Stability against small perturbations 
As noted above, J.R. Partington points out that a state of thermodynamic equilibrium is stable against small perturbations. Without this condition, in general, experiments intended to study systems in thermodynamic equilibrium are in severe difficulties.
Approach to thermodynamic equilibrium within an isolated system 
When a body of material starts from a non-equilibrium state of inhomogeneity or chemical non-equilibrium, and is then isolated, it spontaneously evolves towards its own internal state of thermodynamic equilibrium. It is not necessary that all aspects of internal thermodynamic equilibrium be reached simultaneously; some can be established before others. For example, in many cases of such evolution, internal mechanical equilibrium is established much more rapidly than the other aspects of the eventual thermodynamic equilibrium. Another example is that, in many cases of such evolution, thermal equilibrium is reached much more rapidly than chemical equilibrium.
Thermal equilibrium 
Thermal equilibrium is achieved when two systems in thermal contact with each other cease to have a net exchange of energy. It follows that if two systems are in thermal equilibrium, then their temperatures are the same.
Thermal equilibrium occurs when a system's macroscopic thermal observables have ceased to change with time. For example, an ideal gas whose distribution function has stabilised to a specific Maxwell-Boltzmann distribution would be in thermal equilibrium. This outcome allows a single temperature and pressure to be attributed to the whole system. For an isolated body, it is quite possible for mechanical equilibrium to be reached before thermal equilibrium is reached, but eventually, all aspects of equilibrium, including thermal equilibrium, are necessary for thermodynamic equilibrium.
An explicit distinction between 'thermal equilibrium' and 'thermodynamic equilibrium' is made by B. C. Eu. He considers two systems in thermal contact, one a thermometer, the other a system in which there are occurring several irreversible processes, entailing non-zero fluxes; the two systems are separated by a wall permeable only to heat. He considers the case in which, over the time scale of interest, it happens that both the thermometer reading and the irreversible processes are steady. Then there is thermal equilibrium without thermodynamic equilibrium. Eu proposes consequently that the zeroth law of thermodynamics can be considered to apply even when thermodynamic equilibrium is not present; also he proposes that if changes are occurring so fast that a steady temperature cannot be defined, then "it is no longer possible to describe the process by means of a thermodynamic formalism. In other words, thermodynamics has no meaning for such a process." This illustrates the importance for thermodynamics of the concept of temperature.
A system's internal state of thermodynamic equilibrium should be distinguished from a "stationary state" in which thermodynamic parameters are unchanging in time but the system is not isolated, so that there are, into and out of the system, non-zero macroscopic fluxes which are constant in time.
Non-equilibrium thermodynamics is a branch of thermodynamics that deals with systems that are not in thermodynamic equilibrium. Most systems found in nature are not in thermodynamic equilibrium because 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. The thermodynamic study of non-equilibrium systems requires more general concepts than are dealt with by equilibrium thermodynamics. Many natural systems still today remain beyond the scope of currently known macroscopic thermodynamic methods.
General references 
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- C. Michael Hogan, Leda C. Patmore and Harry Seidman (1973) Statistical Prediction of Dynamic Thermal Equilibrium Temperatures using Standard Meteorological Data Bases, Second Edition (EPA-660/2-73-003 2006) United States Environmental Protection Agency Office of Research and Development, Washington DC 
- F. Mandl (1988) Statistical Physics, Second Edition, John Wiley & Sons
- H.R. Griem, 2005
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- Callen, H.B. (1960/1985), p. 13.
- Adkins, C.J. (1968/1983), p. 7.
- Partington, J.R. (1949), p. 161.
- Crawford, F.H. (1963), p. 5.
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- Buchdahl, H.A. (1966), p. 111.
- Adkins, C.J. (1968/1983), p. 8.
- Münster, A. (1970), p. 53.
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Cited bibliography 
- Adkins, C.J. (1968/1983). Equilibrium Thermodynamics, third edition, McGraw-Hill, London, ISBN 0-521-25445-0.
- Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-88318-797-3.
- Beattie, J.A., Oppenheim, I. (1979). Principles of Thermodynamics, Elsevier Scientific Publishing, Amsterdam, ISBN 0-444-41806-7.
- Boltzmann, L. (1896/1964). Lectures on Gas Theory, translated by S.G. Brush, University of California Press, Berkeley.
- Buchdahl, H.A. (1966). The Concepts of Classical Thermodynamics, Cambridge University Press, Cambridge UK.
- Callen, H.B. (1960/1985). Thermodynamics and an Introduction to Thermostatistics, (1st edition 1960) 2nd edition 1985, Wiley, New York, ISBN 0-471-86256-8.
- Carathéodory, C. (1909). Untersuchungen über die Grundlagen der Thermodynamik, Mathematische Annalen, 67: 355–386. A translation may be found here. Also a mostly reliable translation is to be found at Kestin, J. (1976). The Second Law of Thermodynamics, Dowden, Hutchinson & Ross, Stroudsburg PA.
- Chapman, S., Cowling, T.G. (1939/1970). The Mathematical Theory of Non-uniform gases. An Account of the Kinetic Theory of Viscosity, Thermal Conduction and Diffusion in Gases, third edition 1970, Cambridge University Press, London.
- Crawford, F.H. (1963). Heat, Thermodynamics, and Statistical Physics, Rupert Hart-Davis, London, Harcourt, Brace & World, Inc.
- de Groot, S.R., Mazur, P. (1962). Non-equilibrium Thermodynamics, North-Holland, Amsterdam. Reprinted (1984), Dover Publications Inc., New York, ISBN 0486647412.
- Denbigh, K.G. (1951). Thermodynamic of the Steady State, Methuen, London.
- Eu, B.C. (2002). Generalized Thermodynamics. The Thermodynamics of Irreversible Processes and Generalized Hydrodynamics, Kluwer Academic Publishers, Dordrecht, ISBN 1-4020-0788-4.
- Fitts, D.D. (1962). Nonequilibrium thermodynamics. A Phenomenological Theory of Irreversible Processes in Fluid Systems, McGraw-Hill, New York.
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- Griem, H.R. (2005). Principles of Plasma Spectroscopy (Cambridge Monographs on Plasma Physics), Cambridge University Press, New York ISBN 0-521-61941-6.
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- Zemansky, M. (1937/1968). Heat and Thermodynamics. An Intermediate Textbook, fifth edition 1967, McGraw–Hill Book Company, New York.
- Breakdown of Local Thermodynamic Equilibrium George W. Collins, The Fundamentals of Stellar Astrophysics, Chapter 15
- Thermodynamic Equilibrium, Local and otherwise lecture by Michael Richmond
- Non-Local Thermodynamic Equilibrium in Cloudy Planetary Atmospheres Paper by R. E. Samueison quantifying the effects due to non-LTE in an atmosphere
- Local Thermodynamic Equilibrium
- Xchanger Inc, webpage Calculator for thermodynamic equilibrium of pneumatic conveying air and conveyed product.