Henry's law constant of hydrocarbons in air-water system: The cavity ovality effect on the non-electrostatic contribution term of solvation free energy

• Published in: SAR and QSAR in environmental research Vol. 16; no. 5; pp. 461 - 482
• Main Authors: Modarresi, H., Modarress, H., Dearden, J. C.
• Format: Journal Article
• Language: English
• Published: England Taylor & Francis Group 01.10.2005
• Subjects: Air; Cavity ovality; Henry's law constant; Hydrocarbons - chemistry; Neural Networks (Computer); QSPR; Quantitative Structure-Activity Relationship; Solvation free energy; Solvent-accessible surface area; Solvents - chemistry; Static Electricity; Surface Properties; Thermodynamics; Water
• ISSN: 1062-936X; 1029-046X
• DOI: 10.1080/10659360500319869

In this study, a quantitative structure-property relationship (QSPR) model for the prediction of Henry's law constants of aliphatic hydrocarbons in air-water system has been developed, based on a data-set of 189 compounds. The well-known linear thermodynamic relation between the logarithm of Henry's law constant and solvation free energy has been used for developing the model. It is emphasised that the solvent-accessible surface area (SASA) descriptor is not adequate for predicting the solvation free energy of a wide range of aliphatic hydrocarbons; there are many compounds that have the same solvent-accessible surface area with different solvation free energy. Therefore, we have introduced cavity ovality as a good descriptor of molecular cavity shape factor. The root mean square error (RMSE) of the QSPR regression model based on SASA improves from 0.40 to 0.22 by introducing the cavity ovality descriptor. The QSPR linear ovality model has good statistical parameters (r 2  = 0.90). To emphasise the significant effect of the new descriptor, a non-linear neural network model with only two nodes in the hidden layer was developed, and also yielded a RMSE of 0.22.