Critical Behavior of the Dielectric Constant in Asymmetric Fluids

• Published in: The journal of physical chemistry. B 2011-12, Vol.115 (48), p.14000-14007
• Main Authors: Bertrand, C. E, Sengers, J. V, Anisimov, M. A
• Format: Article
• Language: English
• Subjects: Approximation; Asymmetry; Asymptotic properties; Critical temperature; Dielectric constant; Mathematical analysis; Temperature dependence; Thermodynamics
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp2022055

By applying a thermodynamic theory that incorporates the concept of complete scaling, we derive the asymptotic temperature dependence of the critical behavior of the dielectric constant above the critical temperature along the critical isochore and below the critical temperature along the coexistence curve. The amplitudes of the singular terms in the temperature expansions are related to the changes of the critical temperature and the critical chemical potential upon the introduction of an electric field. The results of the thermodynamic theory are then compared with the critical behavior implied by the classical Clausius–Mossotti approximation. The Clausius–Mossotti approximation fails to account for any singular temperature dependence of the dielectric constant above the critical temperature. Below the critical temperature it produces an apparent asymmetric critical behavior with singular terms similar to those implied by the thermodynamic theory, but with significantly different coefficients. We conclude that the Clausius–Mossotti approximation only can account for the observed asymptotic critical behavior of the dielectric constant when the dependence of the critical temperature on the electric field is negligibly small.