BACKGROUND: Introducing an adduct into an extractant system is an effective method of improving extraction performance. The effect of additives upon extraction is very important, especially in the case of interfacial behaviour. In most work published in the literature, there is little data on the interfacial behaviour of extractants and modifiers. As the mass transfer must pass through an interface, the influence of isooctanol on the interfacial activity and mass transfer of ytterbium(III) using 2-ethylhexylphosphonic acid mono-2-ethlhexyl ester has been investigated. RESULTS: With increasing amounts of isooctanol, the interfacial tension and surface excess (Gamma(max)) of the 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester(HEHEHP)-isooctanol system decreased, and the area of the absorbed HEHEHP molecule (Amin) increased. The interfacial activity of the HEHEHP-isooctanol system varied significantly depending on ionic strength and temperature and the mass transfer flux decreased with increasing isooctanol content. CONCLUSION: Isooctanol has a strong influence on the interfacial activity of the HEHEHP system. The influence of isooctanol on the mass transfer rate of ytterbium extraction has been discussed qualitatively. (C) 2008 Society of Chemical Industry