Ti-Wei Xue | Searcharxiv

arXiv2021

Equation of state from symmetry

Equation of state (EOS) describes the thermodynamic properties of substances. It has important applications in many fields such as power mechanics, geophysics, astrophysics, and detonation physics. Currently, most EOSs have been constructed using the ideal gas EOS as the base framework. However, this is inappropriate for the substances with high pressures or low temperatures that are far from the ideal gas state. Here we extract a concept of "ideal solid" that is symmetrical with ideal gas and propose its EOS. We verify that the ideal solid EOS represents the thermodynamic properties of the high-pressure and low-temperature limiting state. It indicates that the thermodynamic properties of substances have symmetrical characteristic. Then we develop a universal model by interpolation of the ideal gas and the ideal solid limits. We verify that the universal EOS has high description accuracy in a wide region. The concept of ideal solid and its EOS potentially provides a new direction for the development of the EOS theory.

cond-mat.stat-mech↗

arXiv2020

Reversible Reciprocal Relation of Thermoelectricity

The first Kelvin relation that states the Peltier coefficient should be equal to the product of temperature and Seebeck coefficient is a fundamental principle in thermoelectricity. It has been regarded as an important application and direct experimental verification of Onsager reciprocal relation (ORR) that is a cornerstone of irreversible thermodynamics. However, some critical questions still remain: why Kelvin's proof that omits all irreversibility within a thermoelectric transport process can reach the correct result, how to properly select the generalized-force-flux pairs for deriving the first Kelvin relation from ORR, and whether the first Kelvin relation is restricted by the requirement of linear transport regime. The present work is to answer these questions based on the fundamental thermodynamic principles. Since the thermoelectric effects are reversible, we can redefine the Seebeck and Peltier coefficients using the quantities in reversible processes with no time derivative involved, which are renamed as "reversible Seebeck and Peltier coefficients". The relation between them (called "the reversible reciprocal relation of thermoelectricity") is derived from the Maxwell relations, which can be reduced to the conventional Kelvin relation, when the local equilibrium assumption (LEA) is adopted. In this sense, the validity of the first Kelvin relation is guaranteed by the reversible thermodynamic principles and LEA, without the requirement of linear transport process. Additionally, the generalized force-flux pairs to obtain the first Kelvin relation from ORR can be proper both mathematically and thermodynamically, only when they correspond to the conjugate-variable pairs of which Maxwell relations can yield the reversible reciprocal relation. The present theoretical framework can be further extended to other coupled phenomena.

cond-mat.stat-mech↗