Issue 39, 2020

Entropy deepens loading chemical potentials of small alcohols by narrow carbon nanotubes

Abstract

Small alcohol confinement within narrow carbon nanotubes has been extensively and systematically studied via rigorous free-energy calculations. Employing molecular dynamics simulations, thermodynamic integration and thermodynamic cycling, the loading process of methanol and ethanol from aqueous solution into (6,6), (7,7) and (8,8) single-walled carbon nanotubes was computed and decomposed into its entropic and energetic terms. For all tubes and alcohols, loading is favoured from infinite dilution in water; for the same alcohol, wider tubes allow for the formation of a collective dipole which is cooperative in terms of electrostatics and reduce the rotational freedom of the loaded particles; narrow tubes only permit the formation of dipole–dipole dimers instead, with a (rotational) entropic gain that compensates for the loss of long-range dipole–dipole interactions. The latter renders deeper loading chemical potentials for narrower tubes when partitioning small alcohols from aqueous solution and it is a clear example of an entropy-energy compensation phenomenon.

Graphical abstract: Entropy deepens loading chemical potentials of small alcohols by narrow carbon nanotubes

Supplementary files

Article information

Article type
Paper
Submitted
26 Jun 2020
Accepted
09 Sep 2020
First published
11 Sep 2020

Phys. Chem. Chem. Phys., 2020,22, 22369-22379

Entropy deepens loading chemical potentials of small alcohols by narrow carbon nanotubes

M. Barria-Urenda and J. A. Garate, Phys. Chem. Chem. Phys., 2020, 22, 22369 DOI: 10.1039/D0CP03426F

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