A general structure-property relationship to predict the enthalpy of vaporisation at ambient temperatures.
The vapour pressure is the most important property of an anthropogenic organic compound in determining its partitioning between the atmosphere and the other environmental media. The enthalpy of vaporisation quantifies the temperature dependence of the vapour pressure and its value around 298 K is needed for environmental modelling. The enthalpy of vaporisation can be determined by different experimental methods, but estimation methods are needed to extend the current database and several approaches are available from the literature. However, these methods have limitations, such as a need for other experimental results as input data, a limited applicability domain, a lack of domain definition, and a lack of predictive validation. Here we have attempted to develop a quantitative structure-property relationship (QSPR) that has general applicability and is thoroughly validated. Enthalpies of vaporisation at 298 K were collected from the literature for 1835 pure compounds. The three-dimensional (3D) structures were optimised and each compound was described by a set of computationally derived descriptors. The compounds were randomly assigned into a calibration set and a prediction set. Partial least squares regression (PLSR) was used to estimate a low-dimensional QSPR model with 12 latent variables. The predictive performance of this model, within the domain of application, was estimated at n=560, q2Ext=0.968 and s=0.028 (log transformed values). The QSPR model was subsequently applied to a database of 100,000+ structures, after a similar 3D optimisation and descriptor generation. Reliable predictions can be reported for compounds within the previously defined applicability domain.
Oberg
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Department of Biology and Environmental Science, University of Kalmar, SE-391 82 Kalmar, Sweden. tomas.oberg@hik.se
D004785:Environmental Pollutants / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D015999:Multivariate Analysis; D009930:Organic Chemicals / Q000737:chemistry; D011312:Pressure; D013329:Structure-Activity Relationship; D013696:Temperature; D013816:Thermodynamics; D014835:Volatilization
D004785:Environmental Pollutants; D009930:Organic Chemicals