The thermodynamics of pressurized methanol: A simple hydrogen-bonded liquid as a touchstone for experiment and computer simulations

YD Fomin and LN Dzhavadov and EN Tsiok and VN Ryzhov and VV Brazhkin, JOURNAL OF CHEMICAL PHYSICS, 157 (2022).

DOI: 10.1063/5.0116083

Methanol as a basic liquid and the simplest alcohol is widely used in industry and scientific experiments. However, there are still no reliable data on the thermodynamic properties of methanol at high pressure. Here, we present an experimental and computational study of the thermodynamic properties of liquid methanol under high pressure up to 15 kbar, which significantly exceeds previously reported pressures. A temperature response to a small adiabatic change in pressure has been measured using a piston-cylinder apparatus. We have compared our experimental results with the literature data for lower pressures and NIST approximations. We find that all existing experimental data do not agree with each other and with our experiments. The NIST approximations are mainly based on low pressure data and appear to be unreliable in the high pressure region, giving even qualitatively wrong results. OPLS and COMPASS force field models have been used in the method of molecular dynamics. The agreement of molecular simulation with our experimental data is definitely unsatisfactory, which means that the most common computational models of methanol are not sufficiently good. We hope that these experimental data and approximations will help in developing better computational models. Published under an exclusive license by AIP Publishing.

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