Abstract
The oil-water partitioning of a synthetic tetraacid acting as a model compound for indigenous C80-C82 ARN acids has been studied as a function of pH, ionic strength and type of monovalent counterion. Experimental data obtained with ultraviolet-visible and HPLC/UV analyses have been fitted to thermodynamic models based on one, two or four dissociation steps to obtain o/w partition coefficients (K wo ) of the fully protonated acid between chloroform and aqueous solutions, and its apparent acidity constant(s), pK a. As the study is conducted above the CMC of the tetraacid, in general high apparent acidity constants were obtained in the range from 6 to 8 resulting from micellization equilibria. K wo values were obtained in the range from 10−3 to 10−4, and decreasing with increasing salinity. At 50 mM K+, no conclusions could be made regarding the number of distinguishable dissociation steps, while at higher ionic strength (184 mM and 452 mM K+) and at 184 mM Na+ a model with two dissociation steps provided good fits to the experimental data. The first step was found to be given by a pK a ≈ 6.6–6.8 and the second dissociation step at pK a values ≈ 7.8–8.3. The two-step mechanism supports previous results obtained by potentiometric titrations. No significant difference in the o/w behavior was observed when changing the counterion from potassium to sodium. The main partitioning of the tetraacid in the aqueous phase occurred above pH 8, where the fully deprotonated acid was formed.
Acknowledgments
The authors thank the JIP-2 Consortium, consisting of AkzoNobel, Baker Petrolite, BP, Champion Technologies, Chevron, Clariant Oil Services, ConcoPhillips, Shell Global Solutions, Statoil ASA, Talisman Energy, and Total for financial support of the present work.