Abstract
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► Single component naphthenic acids (NAs) have cmc values that vary over a wide range (μM to mM). ► Complex mixtures of NAs display two cmc values over a range of concentration. ► Cmc values correlate to the hydrogen deficiency and molecular weight of NAs. ► Complex mixtures of NAs correspond to a recalcitrant and readily biodegradable fractions. ► Cmc values serve as a metric for establishing relationships between structure and physicochemical properties.
Tensiometry was used to provide estimates of the critical micelle concentration (cmc) values for three sources of naphthenic acids (NAs) and three examples of single component NAs (S1–S3) in aqueous solution at pH 10.5 and 295K. Two commercially available mixtures of NAs and an industrially derived mixture of NAs obtained from Alberta oil sands process water (OSPW) were investigated. The three examples of single component NAs (CnH2n+zO2) were chosen with variable z-series to represent chemical structures with 0–2 rings, as follows: 2-hexyldecanoic acid (z=0; S1), trans-4-pentylcyclohexanecarboxylic acid (z=−2; S2) and dicyclohexylacetic acid (z=−4; S3). The estimated cmc values for S1 (35.6μM), S2 (0.545mM), and S3 (4.71mM) vary over a wide range according to their relative lipophile characteristics of each carboxylate anion. The cmc values for the three complex mixtures of NAs were evaluated. Two disctinct cmc values were observed (second listed in brackets) as follows: Commercial sample 1; 50.9μM (109μM), Commercial sample 2; 22.3μM (52.2μM), and Alberta derived OSPW; 154μM (417μM). These results provide strong support favouring two general classes of NAs in the mixtures investigated with distinct cmc values. We propose that the two groups may be linked to a recalcitrant fraction with a relatively large range of cmc values (52.2–417μM) and a readily biodegradable fraction with a relatively low range of cmc values (22.3–154μM) depending on the source of NAs in a given mixture.