A spectral displacement study of cyclodextrin/naphthenic acids inclusion complexes

Abstract

The spectral displacement technique has been used to obtain 1:1 β-cyclodextrin (β-CD)/carboxylate anion equilibrium binding constants (K2) for some complex mixtures of naphthenic acids (NAs) and some examples of single-component NAs in aqueous solution. Three specific examples of single-component NAs were chosen with variable Z values as follows: 2-hexyldecanoic acid (Z = 0; S1), trans-4-pentylcyclohexanecarboxylic acid (Z = –2; S2), and dicyclohexylacetic acid (Z = –4; S3). The estimated K2 values for S1, S2, and S3 are as follows: 1.42 × 103 M–1, 52.2 × 104 M–1, and 13.1 × 104 M–1, respectively. The corresponding K2 values are 2.34 × 104 M–1 and 1.27 × 104 M–1 for commercial (Fluka) and industrial (Syncrude) sourced NAs, respectively. The magnitude of K2 for 1:1 complexes formed between β-CD and S1, S2, or S3 did not correlate with the degree of hydrogen deficiency (Z-series) but there was a correlation with the size of the guest molecules (n) examined in this study. The correlation between complex stability and the relative size of the lipophilic fragments of the guest molecule are related to the importance of the hydrophobic effect for inclusion of such carboxylic acid guest molecules within β-CD.