Geometric Universality and Thermodynamic Microstructure of Real Fluids in a Unified Entropic Framework

Abstract

We introduce a unified entropic framework for real fluids that encompasses the van der Waals, Berthelot, Redlich Kwong, and Peng Robinson equations of state within a common thermodynamic description. The corresponding microscopic interactions are then explored using Geometrothermodynamics, GTD, through the scalar curvature $mathcal{R}$ of the equilibrium manifold. We show that curvature singularities accurately reproduce macroscopic critical phenomena, while vanishing curvature $\mathcal{R}=0$ identifies specific thermodynamic states where attractive and repulsive intermolecular forces effectively balance. Furthermore, we introduce a set of dimensionless critical-amplitude ratios $Q^i_{j}$, which reveal universal geometric features of the critical regime. Although individual critical amplitudes exhibit a logarithmic dependence on the system size, these invariant ratios organize different molecular species according to the strength of criticality and encode universal scaling features, suggesting their potential as robust classification parameters. Finally, employing Bayesian inference and Markov Chain Monte Carlo, MCMC methods, we statistically reconstruct the zero-curvature curves. The posterior distributions support the consistency of the geometric scaling behavior, demonstrating that the GTD manifold encodes non-trivial information about the underlying thermodynamical models.