Size distribution of associated clusters in liquid alcohols: Interpretation of simulation results in the frame of SAFT approach

Jiri Janecek 1, * Patrice Paricaud 1, *
* Auteur correspondant
Abstract : The size distribution and topology of associated clusters for primary alcohols is studied using molecular dynamics simulations. Liquid ethanol, propanol, butanol, hexanol, and octanol are simulated at pressure P = 1 bar and temperatures T = 300 K, T = 350 K, and T = 400 K. The fractions of molecules with different sets of hydrogen bonded partners, the size of associated cluster and the site-site distribution functions between atoms participating on hydrogen bonding are extracted from simulated trajectories. For all alcohols longer than ethanol, the length of the alkyl chain has only a marginal effect on the association. Consequently, related properties like coordination numbers of hydroxyl group, size distribution of associates, or fractions of differently coordinated alcohol molecules are independent on the molecular size. Although we employed a force-field without involved polarizability, we observe a positive cooperativity of hydrogen bonding simply as a consequence of steric and electrostatic interactions. The size and topology of associates is analyzed within the frame of 3B model of statistical association fluid theory. Although this approach enables good thermodynamic description of systems containing associating compounds, several insufficiencies appear in the description at molecular level.
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Journal of Chemical Physics, American Institute of Physics, 2013, 139, pp.174502. 〈10.1063/1.4827107〉
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Jiri Janecek, Patrice Paricaud. Size distribution of associated clusters in liquid alcohols: Interpretation of simulation results in the frame of SAFT approach. Journal of Chemical Physics, American Institute of Physics, 2013, 139, pp.174502. 〈10.1063/1.4827107〉. 〈hal-01058097〉

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