X-ray diffraction and spectroscopic studies of oleic acid-sodium oleate.

The sodium oleate-oleic acid (1:1) complex (NaHOl(2)) is characterized using X-ray diffraction, FT-IR photoacoustic spectroscopy, FT-Raman spectroscopy, and DSC. The special arrangement of hydrogen-bonded pairs of carboxylic acid and carboxylate groups into unique "head-group" is supported by frequency shifts and partial or total disappearance of characteristic vibrations of carboxylic acid dimer and of carboxylate groups. The well-ordered state of hydrocarbon chains is demonstrated by the existence of sharp Raman bands in the C-C stretching region (1000-1150 cm-1) and other conformationally sensitive modes. The FT-Raman results suggest that the transition at about 32 degrees C involves the cooperative melting of methyl- and carboxyl/carboxylate-sided hydrocarbon chains. From the X-ray diffraction data it is clear that this transition is associated with the disintegration of the hydrogen-bonded carboxylate-carboxylic acid complex, followed by the separate formation of oleic acid and sodium oleate. The packing of hydrocarbon chain in the acid-soap complex is different from the parent oleic acid or sodium oleate. The hydrocarbon chains in the NaHOl(2) form more stable packing (O subcell) in comparison to that of oleic acid. A temperature composition phase diagram is presented.