New Fundamental Concepts and Results in Thermodynamics with Chemical Applications

A thermodynamics of open systems has been developed which provides an entirely new theoretical framework based on novel concepts without any recourse to statistical mechanics, The standard chemical potential is replaced by a convective potential itself derived from a new concept referred to as the “thermobaric potential”. Entropy convected by addition of masses into an open system is obtained using only classical concepts without leading to Gibbs’ paradox. A generalized Gibbs-Duhem theorem is derived. Application to chemical systems leads to new expressions for the affinity and an “intrinsic” heat of reaction which excludes the heat of mixing and is more representative of the true chemical energy. These expressions involve only mechanical and calorimetric concepts. They are much more general than the standard formulas which are restricted to temperature variations. The van? Hoff-le Chatelier principle is extended to open systems in terms of the new convective potential.