Characterization of Long Linear and Branched Alkanes and Alcohols for Temperatures up to 573.15 K by Surface Light Scattering and Molecular Dynamics Simulations

Klein T, Lenahan F, Kerscher M, Rausch MH, Economou IG, Koller TM, Fröba AP (2020)

Publication Language: English

Publication Type: Journal article, Original article

Publication year: 2020

Journal

Journal of Physical Chemistry B American Chemical Society

Book Volume: 124

Pages Range: 4146-4163

Journal Issue: 20

DOI: 10.1021/acs.jpcb.0c01740

Abstract

This work contributes to the characterization of long linear and branched alkanes and alcohols via the determination of their thermophysical properties up to temperatures of 573.15 K. For this, experimental techniques including surface light scattering (SLS) and molecular dynamics (MD) simulations were used under equilibrium conditions to analyze the influences of chain length, branching, and hydroxylation on liquid density, liquid viscosity, and surface tension. For probing these effects, 12 pure model systems given by the linear alkanes n-dodecane, n-hexadecane, n-octacosane, n-triacontane, and n-tetracontane, the linear alcohols 1-dodecanol, 1-hexadecanol, and 1,12-dodecanediol, the branched alkanes 2,2,4,4,6,8,8-heptamethylnonane (HMN) and 2,6,10,15,19,23-hexamethyltetracosane (squalane), and the branched alcohols 2-butyl-1-octanol and 2-hexyl-1-decanol were investigated at or close to saturation conditions at temperatures between 298.15 and 573.15 K. Based on the experimental results for the liquid densities, liquid viscosities, and surface tensions with average expanded uncertainties (k = 2) of 0.061, 2.1, and 2.6%, respectively, the performance of the three commonly employed force fields (FFs) TraPPE, MARTINI, and L-OPLS was assessed in MD simulations. To improve the simulation results for the best-performing all-atom L-OPLS FF at larger temperatures, a modified version was suggested. This incorporates a temperature dependence for the energy parameters of the Lennard-Jones potential obtained by calibrating only against the experimental liquid density data of n-dodecane. By transferring this approach to all other systems studied, the modified L-OPLS FF shows now a distinctly better representation of the equilibrium and transport properties of the long alkanes and alcohols, especially at high temperatures.

Authors with CRIS profile

Tobias Klein Institute of Advanced Optical Technologies - Thermophysical Properties (AOT-TP) Frances Lenahan Institute of Advanced Optical Technologies - Thermophysical Properties (AOT-TP) Manuel Kerscher Institute of Advanced Optical Technologies - Thermophysical Properties (AOT-TP) Michael Rausch Institute of Advanced Optical Technologies - Thermophysical Properties (AOT-TP) Thomas Manfred Koller Institute of Advanced Optical Technologies - Thermophysical Properties (AOT-TP) Andreas Paul Fröba Institute of Advanced Optical Technologies - Thermophysical Properties (AOT-TP)

Additional Organisation(s)

Erlangen Graduate School in Advanced Optical Technologies (SAOT)

Related research project(s)

Thermophysical Properties of Long-Chained Hydrocarbons, Alcohols, and their Mixtures with Dissolved Gases Nov. 1, 2018 - March 31, 2022

Involved external institutions

National Centre for Scientific Research (NCSR) "Demokritos" GR Greece (GR)

How to cite

APA:

Klein, T., Lenahan, F., Kerscher, M., Rausch, M.H., Economou, I.G., Koller, T.M., & Fröba, A.P. (2020). Characterization of Long Linear and Branched Alkanes and Alcohols for Temperatures up to 573.15 K by Surface Light Scattering and Molecular Dynamics Simulations. Journal of Physical Chemistry B, 124(20), 4146-4163. https://doi.org/10.1021/acs.jpcb.0c01740

MLA:

Klein, Tobias, et al. "Characterization of Long Linear and Branched Alkanes and Alcohols for Temperatures up to 573.15 K by Surface Light Scattering and Molecular Dynamics Simulations." Journal of Physical Chemistry B 124.20 (2020): 4146-4163.

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