A Guide to Entropy and the Second Law of Thermodynamics

Abstract

This article is a short version of a longer article to appear in Physics Reports (cond-mat/9708200). The essential postulates of classical thermodynamics are formulated, from which the second law is deduced as the principle of increase of entropy in irreversible adiabatic processes that take one equilibrium state to another. The entropy constructed here is defined only for equilibrium states and no attempt is made to define it otherwise. Statistical mechanics does not enter these considerations. One of the main concepts that makes everything work is the comparison principle (which, in essence, states that any two states of the same chemical composition can be connected by an adiabatic process) and we show that it can be derived from some assumptions about the pressure and thermal equilibrium. Temperature is derived from entropy, but at the start not even the concept of `hotness' is assumed. Our formulation offers a certain clarity and rigor that goes beyond most textbook discussions of the second law.