The Physics of the Thermodynamic Entropy

Abstract

The historical idea of entropy as a property of a body has been reviewed and shown to arise from Clausius’s view of heat as motion. This view of heat, being intermediate between the now defunct idea of heat as substance and the modern view that heat represents an exchange of energy, implied that a body contains a definite quantity of heat. Heat, and therefore entropy, was thus considered a property of a body. These ideas led Clausius to develop his famous inequality and the idea that entropy always increases in irreversible, non-cyclic processes. In this paper, the notion of the entropy as a property of a body is examined in detail. A physical meaning is attached to the thermodynamic entropy by showing that a change in the function Q/T can be understood as representing a change in the number of ways that energy can be distributed among the degrees of freedom active in the system at any given temperature. The idea is illustrated with reference to solids and simple liquids. It is shown that the total thermodynamic entropy is, in general, less than the Boltzmann entropy, except for the case of a monatomic classical ideal gas in which the number of degrees of freedom is independent of temperature. Finally, entropy as a state function is discussed. It is argued that this is entirely mathematical in nature and that the entropy of a state represented in p-V space is not equivalent to a physical property of a physical system in the same thermodynamic state.