An approach for the calculation of vaporization enthalpies of aromatic and heteroaromatic compounds at 298.15 K applicable to supercooled liquids

• Published in: Journal of molecular liquids Vol. 319; p. 114330
• Main Authors: Solomonov, Boris N., Yagofarov, Mikhail I.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-12-2020
• ISSN: 0167-7322; 1873-3166
• DOI: 10.1016/j.molliq.2020.114330

An approach for the calculation of the vaporization enthalpies of aromatic and heteroaromatic compounds at T = 298.15 K with accuracy competitive with experiment was proposed. The vaporization enthalpies may be calculated from the solution enthalpies of liquid and solvation enthalpies in benzene. The solution enthalpies of liquids were shown to be constant within a given type of aromatic compounds. For a set of 67 liquid and 41 solid aromatic and heteroaromatic compounds not capable of intermolecular hydrogen bonding, it was experimentally demonstrated that the solution enthalpies of liquids or supercooled liquids in benzene were equal to 1 ± 1 kJ·mol−1. The way to consider intermolecular hydrogen bonding, e.g., in phenol, aniline, pyrrole derivatives, was also proposed. The methods for solvation enthalpy calculation were proposed previously.
The calculated and literature vaporization enthalpies values of 415 aromatic and heteroaromatic compounds were compared. Average absolute deviation amounted to 1.3 kJ·mol−1. The proposed approach is especially valuable for calculation of the vaporization enthalpies of low-volatile compounds, including those solid at T = 298.15 K.
•Approach for calculation of vaporization enthalpies of aromatic compounds at 298.15 K was proposed.•Solution enthalpies of non-hydrogen-bonded aromatic liquids in benzene were shown to be 1 ± 1 kJ·mol−1.•Ways to estimate solution enthalpies of hydrogen-bonded aromatic liquids in benzene were proposed.•For calculation of solvation enthalpy in benzene group additivity scheme may be used.•For 415 compounds accuracy of the approach was shown to be competitive with experiment.