Thermal equilibrium

Two physical systems are in thermal equilibrium if no heat flows between them when they are connected by a path permeable to heat. Thermal equilibrium obeys the zeroth law of thermodynamics. A system is said to be in thermal equilibrium with itself if the temperature within the system is spatially and temporally uniform.

Systems in thermodynamic equilibrium are always in thermal equilibrium, but the converse is not always true. If the connection between the systems allows transfer of energy as heat but does not allow transfer of matter or transfer of energy as work, the two systems may reach thermal equilibrium without reaching thermodynamic equilibrium.

The relation of thermal equilibrium is an instance of a contact equilibrium between two bodies, which means that it refers to transfer through a selectively permeable partition, the contact path. For the relation of thermal equilibrium, the contact path is permeable only to heat; it does not permit the passage of matter or work; it is called a diathermal connection. According to Lieb and Yngvason, the essential meaning of the relation of thermal equilibrium includes that it is reflexive and symmetric. It is not included in the essential meaning whether it is or is not transitive. After discussing the semantics of the definition, they postulate a substantial physical axiom, that they call the "zeroth law of thermodynamics", that thermal equilibrium is a transitive relation. They comment that the equivalence classes of systems so established are called isotherms.

Thermal equilibrium of a body in itself refers to the body when it is isolated. The background is that no heat enters or leaves it, and that it is allowed unlimited time to settle under its own intrinsic characteristics. When it is completely settled, so that macroscopic change is no longer detectable, it is in its own thermal equilibrium. It is not implied that it is necessarily in other kinds of internal equilibrium. For example, it is possible that a body might reach internal thermal equilibrium but not be in internal chemical equilibrium; glass is an example.

One may imagine an isolated system, initially not in its own state of internal thermal equilibrium. It could be subjected to a fictive thermodynamic operation of partition into two subsystems separated by nothing, no wall. One could then consider the possibility of transfers of energy as heat between the two subsystems. A long time after the fictive partition operation, the two subsystems will reach a practically stationary state, and so be in the relation of thermal equilibrium with each other. Such an adventure could be conducted in indefinitely many ways, with different fictive partitions. All of them will result in subsystems that could be shown to be in thermal equilibrium with each other, testing subsystems from different partitions. For this reason, an isolated system, initially not its own state of internal thermal equilibrium, but left for a long time, practically always will reach a final state which may be regarded as one of internal thermal equilibrium. Such a final state is one of spatial uniformity or homogeneity of temperature. The existence of such states is a basic postulate of classical thermodynamics. This postulate is sometimes, but not often, called the minus first law of thermodynamics.

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