Development of an equilibrium headspace gas chromatographic method for the measurement of noncovalent association and partitioning of n-alkylbenzenes at infinite dilution in fulvic acid pseudophase

Abstract

Fulvic acid (FA), the most important water soluble fraction of humic substances in nature, is known to form aggregate pseudophase and complexes with organic and inorganic species. Here, we report a novel equilibrium headspace gas chromatography (eHSGC) and a two-step reaction model to measure n-alkylbenzene–FA association constant (K11) and n-alkylbenzene–pseudophase FAn association constant (Kn1) without solute concentration and response factor. The K11 and Kn1 values were 2–3 orders of magnitude higher than those for sodium dodecylsulfate. Changes in peak area were used to calculate the critical FA-aggregation concentration (cfc), mole fraction based partition coefficients (Kx), activity coefficients of solute inside the aggregate pseudophase (γm∞), and transfer free energies of alkyl CH2 at infinite dilution. The cfc was found to be 10±0.5μM. The Kx values are of the order of 107 in the FA-aggregate pseudophase. The data shows that benzene has the lowest (0.0002) and n-butylbenzene has the highest (0.01) γm∞ values, which are seven orders of magnitude smaller than γw∞ in water. The transfer free energy of association of a CH2 group, −155cal/mol, compared to that of benzene, −9722cal/mol, indicates that the FA-aggregate pseudophase is more polarizable benzene-like and less n-alkane aliphatic-like.