Theory of excluded volume equation of state: Higher approximations and new generation of equations of state for entire density range

2004 ◽  
Vol 121 (4) ◽  
pp. 1873-1877 ◽  
Author(s):  
Anatoly I. Rusanov

It is argued that since statistical mechanics has developed in two ways, the dynamical approach of Boltzmann and the equilibrium approach of Gibbs, both should be valuable in rubber elasticity. It is shown that this is indeed the case, and the generality of these approaches allows one to study the problem in greater depth than hitherto. In particular, damping terms in the elastic behaviour of rubber can be calculated, and also the effect of entanglements and excluded volume on the equation of state. It is noticeable that although the calculated equations of state are quite complex, they do not fit into a simple pattern of invariants. The future for these developments is briefly discussed.


Minerals ◽  
2019 ◽  
Vol 9 (10) ◽  
pp. 636 ◽  
Author(s):  
Frank Stacey

None of the 40+ equations that have been proposed to describe material properties at the pressures of the Earth’s core and mantle have escaped serious criticism. In this paper, some basic algebraic and thermodynamic constraints are reviewed, with the conclusion that the next step should be a re-examination of the relationship between the dependence of the bulk modulus, K, on pressure, P, that is K ′ ≡ d K / d P , and the normalized (dimensionless) pressure, P / K . A linear relationship between 1 / K ′ and P / K terminating at the infinite pressure asymptote, at which these quantities become equal, has been used for analysing properties at extreme pressure, but may be inadequate for calculations requiring precise derivatives of an equation of state. A new analysis indicates that d ( 1 / K ′ ) / d ( P / K ) increases with compression (or P / K ), but there are, at present, no reliable equations representing this. Relationships between higher derivatives of K and the thermodynamic Grüneisen parameter offer the prospect of a resolution of the problem and hence a new generation of fundamentally-based equations of state. Although an earlier conclusion that a completely general ‘universal’ equation is not possible, in principle, is confirmed in this study, the fundamental relationships present strong constraints for the forms of other proposed equations.


Author(s):  
Natalia Andrulionis ◽  
Natalia Andrulionis ◽  
Ivan Zavialov ◽  
Ivan Zavialov ◽  
Elena Kovaleva ◽  
...  

This article presents a new method of laboratory density determination and construction equations of state for marine waters with various ionic compositions and salinities was developed. The validation of the method was performed using the Ocean Standard Seawater and the UNESCO thermodynamic equation of state (EOS-80). Density measurements of water samples from the Aral Sea, the Black Sea and the Issyk-Kul Lake were performed using a high-precision laboratory density meter. The obtained results were compared with the density values calculated for the considered water samples by the EOS-80 equation. It was shown that difference in ionic composition between Standard Seawater and the considered water bodies results in significant inaccuracies in determination of water density using the EOS-80 equation. Basing on the laboratory measurements of density under various salinity and temperature values we constructed a new equation of state for the Aral Sea and the Black Sea water samples and estimated errors for their coefficients.


1984 ◽  
Vol 49 (5) ◽  
pp. 1116-1121
Author(s):  
Josef P. Novák ◽  
Jaroslav Matouš ◽  
Petr Pick ◽  
Jiří Pick

Published data on the solubility of water in compressed gases were employed for calculating the interaction coefficients kij in the Redlich-Kwong-Soave equations of state for binary systems of water with argon, nitrogen, CO2, N2O, CH4, C2H6, or C2H4. With these coefficients, the estimate of the solubility of water in these gases has been improved by more than one order.


2021 ◽  
Vol 23 (3) ◽  
Author(s):  
Peter Korn

AbstractWe consider the hydrostatic Boussinesq equations of global ocean dynamics, also known as the “primitive equations”, coupled to advection–diffusion equations for temperature and salt. The system of equations is closed by an equation of state that expresses density as a function of temperature, salinity and pressure. The equation of state TEOS-10, the official description of seawater and ice properties in marine science of the Intergovernmental Oceanographic Commission, is the most accurate equations of state with respect to ocean observation and rests on the firm theoretical foundation of the Gibbs formalism of thermodynamics. We study several specifications of the TEOS-10 equation of state that comply with the assumption underlying the primitive equations. These equations of state take the form of high-order polynomials or rational functions of temperature, salinity and pressure. The ocean primitive equations with a nonlinear equation of state describe richer dynamical phenomena than the system with a linear equation of state. We prove well-posedness for the ocean primitive equations with nonlinear thermodynamics in the Sobolev space $${{\mathcal {H}}^{1}}$$ H 1 . The proof rests upon the fundamental work of Cao and Titi (Ann. Math. 166:245–267, 2007) and also on the results of Kukavica and Ziane (Nonlinearity 20:2739–2753, 2007). Alternative and older nonlinear equations of state are also considered. Our results narrow the gap between the mathematical analysis of the ocean primitive equations and the equations underlying numerical ocean models used in ocean and climate science.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
J. Lütgert ◽  
J. Vorberger ◽  
N. J. Hartley ◽  
K. Voigt ◽  
M. Rödel ◽  
...  

AbstractWe present structure and equation of state (EOS) measurements of biaxially orientated polyethylene terephthalate (PET, $$({\hbox {C}}_{10} {\hbox {H}}_8 {\hbox {O}}_4)_n$$ ( C 10 H 8 O 4 ) n , also called mylar) shock-compressed to ($$155 \pm 20$$ 155 ± 20 ) GPa and ($$6000 \pm 1000$$ 6000 ± 1000 ) K using in situ X-ray diffraction, Doppler velocimetry, and optical pyrometry. Comparing to density functional theory molecular dynamics (DFT-MD) simulations, we find a highly correlated liquid at conditions differing from predictions by some equations of state tables, which underlines the influence of complex chemical interactions in this regime. EOS calculations from ab initio DFT-MD simulations and shock Hugoniot measurements of density, pressure and temperature confirm the discrepancy to these tables and present an experimentally benchmarked correction to the description of PET as an exemplary material to represent the mixture of light elements at planetary interior conditions.


Entropy ◽  
2021 ◽  
Vol 23 (7) ◽  
pp. 846
Author(s):  
Donya Ohadi ◽  
David S. Corti ◽  
Mark J. Uline

Modifications to the traditional Onsager theory for modeling isotropic–nematic phase transitions in hard prolate spheroidal systems are presented. Pure component systems are used to identify the need to update the Lee–Parsons resummation term. The Lee–Parsons resummation term uses the Carnahan–Starling equation of state to approximate higher-order virial coefficients beyond the second virial coefficient employed in Onsager’s original theoretical approach. As more exact ways of calculating the excluded volume of two hard prolate spheroids of a given orientation are used, the division of the excluded volume by eight, which is an empirical correction used in the original Lee–Parsons resummation term, must be replaced by six to yield a better match between the theoretical and simulation results. These modifications are also extended to binary mixtures of hard prolate spheroids using the Boublík–Mansoori–Carnahan–Starling–Leland (BMCSL) equation of state.


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