TY - JOUR

T1 - Structure of tert-butyl alcohol in carbon tetrachloride solution. Molecular dynamics simulation study

AU - Anikeenko, Alexey V.

AU - Medvedev, Nikolai N.

N1 - This work was supported by the Russian Science Foundation , grant No. 22-23-00620.

PY - 2024/1/1

Y1 - 2024/1/1

N2 - The structure of tert-butyl alcohol (TBA) solution in carbon tetrachloride (CCl4) is studied over the entire concentration range using molecular dynamics simulation (MD). It is shown that at low alcohol concentrations (within 5% molar fraction), separate small associates of TBA appear as a result of hydrogen bonding between alcohol molecules, and cyclic structures of four TBA molecules appear among these associates. With increasing concentration, the formation of hydrogen-bonded associates quickly reaches its limit corresponding to 1.7 bonds per molecule as in pure TBA. At high alcohol concentrations, both linear and cyclic associates of TBA molecules are observed with a noticeable fraction of cyclic tetramers. Using the Voronoi method, aggregates of the nearest TBA molecules are considered. The number and size of such aggregates grows rapidly with concentration due to the presence of “nuclei” formed by hydrogen bonding. At an alcohol mole fraction of 15%, a percolation cluster of TBA molecules begins to form in the solution. On the contrary, in the local environment of CCl4 molecules no significant structural rearrangements occur, only a gradual replacement of the molecules is observed upon addition of alcohol. However at low content of CCl4 in alcohol, we can see some tendency to clustering of CCl4 molecules, which may indicate on a slight solvophobic effect in this solution.

AB - The structure of tert-butyl alcohol (TBA) solution in carbon tetrachloride (CCl4) is studied over the entire concentration range using molecular dynamics simulation (MD). It is shown that at low alcohol concentrations (within 5% molar fraction), separate small associates of TBA appear as a result of hydrogen bonding between alcohol molecules, and cyclic structures of four TBA molecules appear among these associates. With increasing concentration, the formation of hydrogen-bonded associates quickly reaches its limit corresponding to 1.7 bonds per molecule as in pure TBA. At high alcohol concentrations, both linear and cyclic associates of TBA molecules are observed with a noticeable fraction of cyclic tetramers. Using the Voronoi method, aggregates of the nearest TBA molecules are considered. The number and size of such aggregates grows rapidly with concentration due to the presence of “nuclei” formed by hydrogen bonding. At an alcohol mole fraction of 15%, a percolation cluster of TBA molecules begins to form in the solution. On the contrary, in the local environment of CCl4 molecules no significant structural rearrangements occur, only a gradual replacement of the molecules is observed upon addition of alcohol. However at low content of CCl4 in alcohol, we can see some tendency to clustering of CCl4 molecules, which may indicate on a slight solvophobic effect in this solution.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85177990808&origin=inward&txGid=35e1ee810b76a83d8831df44691179c4

UR - https://www.mendeley.com/catalogue/d96eaa62-7240-3a1c-8f2f-1663b28aff54/

U2 - 10.1016/j.molliq.2023.123573

DO - 10.1016/j.molliq.2023.123573

M3 - Article

VL - 393

JO - Journal of Molecular Liquids

JF - Journal of Molecular Liquids

SN - 0167-7322

M1 - 123573

ER -