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The modified van der Waals equation of state

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  • Jacques Rault

    (Laboratoire de Physique des Solides, CNRS, Université de Paris-Sud)

Abstract

PVT data of crystallizable materials (CM), minerals, alkali, alkali halides, metals, mineral oxides and hydroxides, rare gas, water, organic compounds and polymers, published in the literature are reanalyzed. It is shown that all these materials under pressure verify the modified van der Waals equation of state (mVW-EOS), discussed recently [J. Rault, Eur. Phys. J. E 40, 82 (2017)]. The characteristic parameters P*V* of this EOS depend only on the nature of the material and not on its state (liquid, glassy, solid of different structure) and whatever are its conductivity and magnetic properties (insulator, conductor, superconductor, paramagnetic, ferromagnetic). This EOS explains the following properties: (a) the fan structure of the isobars V(T), and of the tangents to the isotherms V(P); (b) the superposition principle of the isotherms V(P); (c) the αB rule: the constancy of the thermal pressure coefficient (dP/dT)V = αB, product of the thermal expansion coefficient α and the bulk modulus B; (d) its relation with the Slater conjecture: (dP/dT)V ~ dP/dTm in crystallized materials, Tm being the melting temperature. The characteristic pressure P* (T and V independent) is compared with the various pressures: (i) Pcoh = Ecoh/V, the cohesive energy density; (ii) PLm = Lm/ΔVm, Lm and ΔVm being the enthalpy and volume jumps at the melting, respectively; (iii) PD = ΔHa/DVa, ratio of the activation parameters of the autodiffusion coefficient; (iv) PX = X∕X′, X being the bulk modulus B, shear modulus G, elastic constants Cij, and the yield stress σy of the CM, X′ their pressure derivative (at ambient conditions). All the elastic constants B, G, Cij and the yield stress σy are linear functions of P at low pressure (P

Suggested Citation

  • Jacques Rault, 2019. "The modified van der Waals equation of state," The European Physical Journal B: Condensed Matter and Complex Systems, Springer;EDP Sciences, vol. 92(1), pages 1-32, January.
  • Handle: RePEc:spr:eurphb:v:92:y:2019:i:1:d:10.1140_epjb_e2018-90452-6
    DOI: 10.1140/epjb/e2018-90452-6
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    Keywords

    Solid State and Materials;

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