Thermodynamic Relationships for Perfectly Elastic Solids Undergoing Steady-State Heat Flow

Abstract

Available data on insulating, semiconducting, and metallic solids verify our new model that incorporates steady-state heat flow into a macroscopic, thermodynamic description of solids, with agreement being best for isotropic examples. Our model is based on: (1) mass and energy conservation; (2) Fourier’s law; (3) Stefan–Boltzmann’s law; and (4) rigidity, which is a large, yet heretofore neglected, energy reservoir with no counterpart in gases. To account for rigidity while neglecting dissipation, we consider the ideal, limiting case of a perfectly frictionless elastic solid (PFES) which does not generate heat from stress. Its equation-of-state is independent of the energetics, as in the historic model. We show that pressure-volume work (PdV) in a PFES arises from internal interatomic forces, which are linked to Young’s modulus (Ξ) and a constant (n) accounting for cation coordination. Steady-state conditions are adiabatic since heat content (Q) is constant. Because average temperature is also constant and the thermal gradient is fixed in space, conditions are simultaneously isothermal: Under these dual restrictions, thermal transport properties do not enter into our analysis. We find that adiabatic and isothermal bulk moduli (B) are equal. Moreover, Q/V depends on temperature only. Distinguishing deformation from volume changes elucidates how solids thermally expand. These findings lead to simple descriptions of the two specific heats in solids: ∂ln(cP)/∂P = −1/B; cP = nΞ times thermal expansivity divided by density; cP = cVnΞ/B. Implications of our validated formulae are briefly covered.