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Thermodynamic equilibrium


Thermodynamic equilibrium is an axiomatic concept of thermodynamics. It is an internal state of a single thermodynamic system, or a relation between several thermodynamic systems connected by more or less permeable or impermeable walls. In thermodynamic equilibrium there are no net macroscopic flows of matter or of energy, either within a system or between systems. In a system in its own state of internal thermodynamic equilibrium, no macroscopic change occurs. Systems in mutual thermodynamic equilibrium are simultaneously in mutual thermal, mechanical, chemical, and radiative equilibria. Systems can be in one kind of mutual equilibrium, though not in others. In thermodynamic equilibrium, all kinds of equilibrium hold at once and indefinitely, until disturbed by a thermodynamic operation. In a macroscopic equilibrium, almost or perfectly exactly balanced microscopic exchanges occur; this is the physical explanation of the notion of macroscopic equilibrium.

A thermodynamic system in its own state of internal thermodynamic equilibrium has a spatially uniform temperature. Its intensive properties, other than temperature, may be driven to spatial inhomogeneity by an unchanging long range force field imposed on it by its surroundings.

In non-equilibrium systems, by contrast, there are net flows of matter or energy. 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.

Though it is not a widely named law, it is an axiom of thermodynamics that there exist states of thermodynamic equilibrium. The second law of thermodynamics states that when a body of material starts from an equilibrium state, in which portions of it are held at different states by more or less permeable or impermeable partitions, and a thermodynamic operation removes or makes the partitions more permeable and it is isolated, then it spontaneously reaches its own new state of internal thermodynamic equilibrium, and this is accompanied by an increase in the sum of the entropies of the portions.


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