Understanding and predicting the diffusivity of organic compounds in polydimethylsiloxane material for passive sampler applications using a simple quantitative structure–property relationship model

<jats:title>Abstract</jats:title><jats:sec><jats:label /><jats:p>The diffusivity of 145 compounds in polydimethylsiloxane (PDMS) material was determined in the laboratory using a film stacking technique. The results were pooled with available literature data, providing a final data set of 198 compounds with diffusivity (<jats:italic>D</jats:italic><jats:sub>PDMS</jats:sub>) spanning over approximately 5 log units. The principal variables controlling the diffusivity of penetrants were investigated by comparing <jats:italic>D</jats:italic><jats:sub>PDMS</jats:sub> within and between different homologous series. The dipole moment, molecular size, and flexibility of penetrants appear to be the most prevalent factors controlling a compound's diffusivity. A nonlinear quantitative structure–property relationship is proposed using as predicting variables the molecular volume, the number of rotatable bonds, the topological polar surface area, and the number of O and N atoms. The final relationship has a correlation coefficient of <jats:italic>R</jats:italic><jats:sup>2</jats:sup> = 0.81 and a mean absolute error of 0.26 m<jats:sup>2</jats:sup> s<jats:sup>−1</jats:sup> (log unit), approaching the average error for the experimentally determined values (0.12 m<jats:sup>2</jats:sup> s<jats:sup>−1</jats:sup>). The model, based on a heuristic approach, is ready for use by analytical chemists with no specific background in theoretical chemistry (notably for passive sampler development). <jats:italic>Environ Toxicol Chem</jats:italic> 2018;37:1291–1300. © 2018 SETAC</jats:p></jats:sec>