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.
Read more about this topic: Thermodynamic Equilibrium
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