Toward Improved Understanding of the Physical Meaning of Entropy in Classical Thermodynamics

The year 2015 marked the 150th anniversary of “entropy” as a concept in classical thermodynamics. Despite its central role in the mathematical formulation of the Second Law and most of classical thermodynamics, its physical meaning continues to be elusive and confusing. This is especially true when we seek a reconstruction of the classical thermodynamics of a system from the statistical behavior of its constituent microscopic particles or vice versa. This paper sketches the classical definition by Clausius and offers a modified mathematical definition that is intended to improve its conceptual meaning. In the modified version, the differential of specific entropy appears as a non-dimensional energy term that captures the invigoration or reduction of microscopic motion upon addition or withdrawal of heat from the system. It is also argued that heat transfer is a better model process to illustrate entropy; the canonical heat engines and refrigerators often used to illustrate this concept are not very relevant to new areas of thermodynamics (e.g., thermodynamics of biological systems). It is emphasized that entropy changes, as invoked in the Second Law, are necessarily related to the non-equilibrium interactions of two or more systems that might have initially been in thermal equilibrium but at different temperatures. The overall direction of entropy increase indicates the direction of naturally occurring heat transfer processes in an isolated system that consists of internally interacting (non-isolated) sub systems. We discuss the implication of the proposed modification on statements of the Second Law, interpretation of entropy in statistical thermodynamics, and the Third Law