Numerical simulation of the solvate structures of acetylsalicylic acid in supercritical carbon dioxide containing polar co-solvents

Abstract

Hydrogen-bonded complexes of acetylsalicylic acid with polar co-solvents in supercritical carbon dioxide, modified by methanol, ethanol, and acetone of 0.03 mole fraction concentration, are studied by numerical methods of classical molecular dynamics simulation and quantum chemical calculations. The structure, energy of formation, and lifetime of hydrogen-bonded complexes are determined, along with their temperature dependences (from 318 to 388 K at constant density of 0.7 g cm−3). It is shown that the hydrogen bonds between acetylsalicylic acid and methanol are most stable at 318 K and are characterized by the highest value of absolute energy. At higher supercritical temperatures, however, the longest lifetime is observed for acetylsalicylic acid–ethanol complexes. These results correlate with the known literature experimental data showing that the maximum solubility of acetylsalicylic acid at density values close to those considered in this work and at temperatures of 318 and 328 K is achieved when using methanol and ethanol as co-solvents, respectively.