Heat Transfer-Based Reconstruction of the Concepts and Laws of Classical Thermodynamics

As an alternative to the mechanistic point of view expressed in Carathe´odory’s axioms, it is shown that the laws and concepts of thermodynamics are covered also by two statements made from a purely heat transfer perspective: Axiom I′—The heat transfer is the same in all zero-work processes that take a system from a given initial state to a given final state. Axiom II′—In the immediate neighborhood of every state of a system there are other states that cannot be reached from the first via a zero-work process. The primary concepts of this formulation are heat transfer, temperature, entropy, and zero-work boundary. Axiom I′ is used to define the property “energy,” and to deduce the secondary (derived) concept of “work transfer.” Axiom II′ is used to define the thermodynamic properties of “volume” and “pressure.” In this new heat transfer-based scheme, the analog of the Kelvin–Planck statement of the second law is: “∮δW < 0 is impossible” for an integral number of cycles executed by a closed system while in communication with no more than one pressure reservoir.