Surfactant-induced surface freezing at the alkane-water interface.

Long-chain alkanes exhibit surface freezing at the alkane-air but not the alkane-water interface. Ellipsometry and surface tensiometry are used to show that a simple cationic surfactant, hexadecyltrimethylammonium bromide (CTAB), can induce surface freezing at the tetradecane-water interface even when present in mole fractions as low as 0.1. The surface-freezing temperature T(s) is a linear function of the interfacial excess of CTAB. The excess surface entropy below T(s), S(sigma)=-0.76+/-0.02 mJ K-1 m(-2), is consistent with a rotator phase. Ellipsometry provides strong evidence for a frozen monolayer in which the chains are oriented near the surface normal.