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Zeroth law of thermodynamics


The zeroth law of thermodynamics states that if two thermodynamic systems are each in thermal equilibrium with a third, then they are in thermal equilibrium with each other. Accordingly, thermal equilibrium between systems is a transitive relation.

Two systems are said to be in the relation of thermal equilibrium if they are linked by a wall permeable only to heat and they do not change over time. As a convenience of language, systems are sometimes also said to be in a relation of thermal equilibrium if they are not linked so as to be able to transfer heat to each other, but would not do so if they were connected by a wall permeable only to heat.

The physical meaning of the law was expressed by Maxwell in the words: "All heat is of the same kind". For this reason, another statement of the law is "All diathermal walls are equivalent".

The law is important for the mathematical formulation of thermodynamics, which needs the assertion that the relation of thermal equilibrium is an equivalence relation. This information is needed for a mathematical definition of temperature that will agree with the physical existence of valid thermometers.

A thermodynamic system is by definition in its own state of internal thermodynamic equilibrium, that is to say, there is no change in its observable state (i.e. macrostate) over time and no flows occur in it. One precise statement of the zeroth law is that the relation of thermal equilibrium is an equivalence relation on pairs of thermodynamic systems. In other words, the set of all systems each in its own state of internal thermodynamic equilibrium may be divided into subsets in which every system belongs to one and only one subset, and is in thermal equilibrium with every other member of that subset, and is not in thermal equilibrium with a member of any other subset. This means that a unique "tag" can be assigned to every system, and if the "tags" of two systems are the same, they are in thermal equilibrium with each other, and if different, they are not. This property is used to justify the use of empirical temperature as a tagging system. Empirical temperature provides further relations of thermally equilibrated systems, such as order and continuity with regard to "hotness" or "coldness", but these are not implied by the standard statement of the zeroth law.


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