Per- and polyfluoroalkyl substances (PFAS) are a group
of chemicals
of high environmental concern. However, reliable data for the air/water
partition coefficients (K
aw), which are
required for fate, exposure, and risk analysis, are available for
only a few PFAS. In this study, K
aw values
at 25 °C were determined for 21 neutral PFAS by using the hexadecane/air/water
thermodynamic cycle. Hexadecane/water partition coefficients (K
Hxd/w) were measured with batch partition, shared-headspace,
and/or modified variable phase ratio headspace methods and were divided
by hexadecane/air partition coefficients (K
Hxd/air) to obtain K
aw values over 7 orders
of magnitude (10–4.9 to 102.3). Comparison
to predicted K
aw values by four models
showed that the quantum chemically based COSMOtherm model stood out for accuracy with a root-mean-squared error (RMSE)
of 0.42 log units, as compared to HenryWin, OPERA, and the linear
solvation energy relationship with predicted descriptors (RMSE, 1.28–2.23).
The results indicate the advantage of a theoretical model over empirical
models for a data-poor class like PFAS and the importance of experimentally
filling data gaps in the chemical domain of environmental interest. K
aw values for 222 neutral (or neutral species
of) PFAS were predicted using COSMOtherm as current
best estimates for practical and regulatory use.