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 nor of energy within a system or between systems. In a system that is 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, while 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, perfectly or almost perfectly balanced microscopic exchanges occur; this is the physical explanation of the notion of macroscopic equilibrium.
A thermodynamic system in a 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 systems that are at a state of non-equilibrium there are, by contrast, net flows of matter or energy. If such changes can be triggered to occur in a system in which they are not already occurring, the system is said to be in a meta-stable equilibrium.
Though 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 an isolated 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, 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.
Overview
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 (in the absence of an applied voltage), or for which the entropy (S) is maximized, for specified conditions. One such potential is the Helmholtz free energy (A), for a closed system at constant volume and temperature (controlled by a heat bath):
Another potential, the Gibbs free energy (G), is minimized at thermodynamic equilibrium in a closed system at constant temperature and pressure, both controlled by the surroundings:
where T denotes the absolute thermodynamic temperature, P the pressure, S the entropy, V the volume, and U the internal energy of the system. In other words, is a necessary condition for chemical equilibrium under these conditions (in the absence of an applied voltage).
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 a completely isolated system, S is maximum at thermodynamic equilibrium. For a closed system at controlled constant temperature and volume, A is minimum at thermodynamic equilibrium. For a closed system at controlled constant temperature and pressure without an applied voltage, 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 and there is no significant external driving force.
