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Ion-induced multiply reentrant liquid-liquid transitions and the nature of criticality in ethanol-water mixture

Bagchi, Debjani and Kumar, Anil and Menon, Reghu (2006) Ion-induced multiply reentrant liquid-liquid transitions and the nature of criticality in ethanol-water mixture. In: Journal Of Chemical Physics, 125 (3). 034511 -1-034511-10.

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We report a quite unusual feature of four liquid-liquid reentrant transitions in ethanol (E)+water (W)+ammonium sulfate mixture by meticulous tuning of the ammonium sulfate concentration in a narrow range, as a function of temperature, at atmospheric pressure. Detailed exploration of the intricate phase behavior in terms of E/W sections shows that the range of triple reentrance shrinks with increasing E/W. The behavior of osmotic susceptibility is investigated by light scattering, near the critical point, in the one-phase region by varying the temperature at fixed concentration of the components, in a particular E/W section. The critical exponent of susceptibility (gamma) and correlation length (nu) are observed to have Fisher renormalized Ising values [Phys. Rev. 176, 237 (1968)], with gamma(r)=1.41 and nu(r)=0.718. The effective susceptibility exponent, gamma(eff), exhibits a sharp, nonmonotonic crossover from Ising to mean-field critical behavior, which is completed outside the critical regime. The amplitude of the correlation length, xi(o)(=21.2 +/- 0.4 angstrom), deduced from light scattering experiment, is an order of magnitude larger than the typical values in usual aqueous electrolyte systems. This value of xi(o) is further verified from small-angle x-ray scattering (SAXS) experiments and found to be consistent. SAXS experiments on the critical sample reveal the presence of long-ranged intermolecular correlations, leading to supramolecular structuring, at a temperature far away from the critical point. These results convincingly demonstrate that the finite length scale arising due to the structuring competes with the diverging correlation length of critical concentration fluctuations, which influences the nonasymptotic critical behavior in this aqueous electrolyte system. The sulphate ions play a dominant role in both structuring and the complex phase behavior.

Item Type: Journal Article
Publication: Journal Of Chemical Physics
Publisher: American Institute Of Physics
Additional Information: Copyright of this article belongs to American Institute Of Physics.
Department/Centre: Division of Physical & Mathematical Sciences > Physics
Date Deposited: 31 Mar 2009 04:40
Last Modified: 19 Sep 2010 04:57
URI: http://eprints.iisc.ac.in/id/eprint/17635

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