Novel methods for predicting gas-particle partitioning during the formation of secondary organic aerosol

Several methods have been presented in the literature to predict an organic chemical's equilibrium partitioning between the water insoluble organic matter (WIOM) component of aerosol and the gas phase, Ki, WIOM as a function of temperature. They include (i) polyparameter linear free energy relationships calibrated with empirical aerosol sorption data, as well as (ii) the solvation models implemented in SPARC and (iii) the quantum-chemical software Cosmotherm, which predict solvation equilibria from molecular structure alone. We demonstrate that these methods can be used to predict Ki, WIOM for large numbers of individual molecules implicated in secondary organic aerosol (SOA) formation, including those with multiple functional groups. Although very different in their theoretical foundations, these methods give remarkably consistent results for the products of the reaction of normal alkanes with OH, i.e. their partition coefficients Ki, WIOM generally agree within one order of magnitude over a range of more than ten orders of magnitude. This level of agreement is much better than that achieved by different vapour pressure estimation methods that are more commonly used in the SOA community. Also, in contrast to the agreement between vapour pressure estimates, that between the Ki, WIOM estimates does not deteriorate with increasing number of functional groups. Furthermore, these partitioning coefficients Ki, WIOM are found to predict the SOA mass yield in chamber experiments of the oxidation of normal alkanes as good or better than a vapour pressure based method. If a Ki, WIOM prediction method was based on one or more surrogate molecules representing the solvation properties of the mixed OM phase of SOA, the choice of those molecule(s) was found to have a relatively minor effect on the predicted Ki, WIOM, as long as the molecule(s) are not very polar. This suggests that a single surrogate molecule, such as 1-octanol or a hypothetical SOA structure proposed by Kalberer et al. (2004), may often be sufficient to represent the WIOM component of the SOA phase, greatly simplifying the prediction. The presented methods could substitute for vapour pressure based methods in studies such as the explicit modeling of SOA formation from single precursor molecules in chamber experiments or the assignment of SOA-forming molecules to volatility basis sets.