An apparent critical point in binary mixtures of nitrotoluene with alkanes: Experimental and simulation study

Issue title: Atomic and molecular nonlinear optics: Theory, Experiment and Computation A homage to the pioneering work of Stanisław Kielich (1925-1993)

Guest editors: G. Maroulis, T. Bancewicz, B. Champagne and A.D. Buckingham

Article type: Research Article

Authors: Ratajczak, Blazej^a | Sliwinska-Bartkowiak, Malgorzata^{a; *} | Koziol, Tomasz^a | Coasne, Benoit^b | Gubbins, Keith E.^c

Affiliations: [a] Faculty of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland | [b] Department of Chemical Physics, University of Montpellier, Mont.2, France | [c] Department of Chemical & Biomolecular Eng., North Carolina State University, Raleigh, NC, USA

Correspondence: [*] Corresponding author. E-mail: [email protected].

Abstract: We report an experimental and simulation study of binary mixtures of o- and m-nitrotoluene with decane and hexadecane. Mixtures of o-nitrotoluene with alkanes form a classical critical mixtures, but m-nitrotoluene / n – alkane mixtures show an apparent critical point, which lies in a metastable, experimentally inaccessible state, below the melting point, affecting physical and chemical properties of this systems in the stable liquid phase. The presence of the apparent critical point in this mixture has been experimentally observed by Nonlinear Dielectric Effect (NDE) measurements as an anomalous increase in the NDE values typical of critical concentrations. The phase diagram of this mixture shows evidence that the system freezes in the homogenous phase and its melting point is higher than its critical temperature [1-3]. For such a system, we performed Monte Carlo simulations aimed at analysing the kind of phase transitions observed, and the conditions of their occurrence in a nonpolar/dipolar mixture. We perform studies for classical critical systems of o-nitrotoluene with decane and hexadecane The enthalpy, configurational energy and radial distribution function have been estimated by the MC simulation method in the NPT system. Immiscibility conditions according to Schoen and Hoheisel [4] approach are also discussed.

Keywords: Metastable mixtures, MC simulations, near critical point, nonlinear dielectric effect

DOI: 10.3233/JCM-2010-0327

Journal: Journal of Computational Methods in Sciences and Engineering, vol. 10, no. 3-6, pp. 575-586, 2010