title: Association effects in pure methanol via Monte Carlo simulations. II. Thermodynamics.
abstract: A simple methodology [P. Gómez-Álvarez, A. Dopazo-Paz, L. Romani, and D. González-Salgado, J. Chem. Phys. 134, 014512 (2011)] recently developed in the light of the Monte Carlo molecular simulation technique was used in this work to study the association effects on the response functions of methanol over the whole thermodynamic state space. It consists basically on evaluating the first order properties of the fluid (energy and volume) in terms of those for two hypothetical fluids living in the bulk composed by monomers and associated molecules, respectively. In this context, the second order thermodynamic derivatives can be expressed in a perturbative way as the sum of the monomer term (reference term) and the association contribution. Specifically, both contributions to the residual isobaric heat capacity, and to the pressure and temperature derivatives of the volume were determined for the optimized potential for liquid simulation (OPLS) of methanol through NPT Monte Carlo simulations from 250 K to 1000 K along the supercritical isobars 25, 100, 200, 500 MPa, and from 800 K to 350 K at 0.1 MPa. Results showed that both terms are relevant for the residual isobaric heat capacity and that their influence depends considerably on the thermodynamic conditions; however, the volumetric response functions were found mainly affected by the monomer contribution, especially the pressure derivative of the volume.
authors: Department of Applied Physics, University of Vigo, As Lagoas s/n, 32004 Ourense, Spain.
authors: Paula
authors: P
authors: Gómez-Álvarez
authors: Luis
authors: L
authors: Romaní
authors: Diego
authors: D
authors: González-Salgado
mesh_terms: D000432:Methanol / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D009010:Monte Carlo Method; D013816:Thermodynamics
chemical_list: D000432:Methanol