In this paper we highlight the advantageous features of both short- and lon
g-chain surfactant systems in determining the most important properties of
three-phase bodies and genuine microemulsions. To this end first the phase
behavior of the simple system H2O-n-dodecane-C4E1 (n-butyl monoglycol ether
) is discussed. From temperature-concentration sections through the phase p
rism at various water-to-oil ratios, a number of isothermal Gibbs triangles
are constructed, which can quantitatively be compared with theories. Furth
ermore, the critical tie-lines of the three-phase body have been precisely
determined. From these measurements it is evident that there is a non-negli
gible monomeric solubility of the surfactant in the excess phases. For long
-chain surfactant systems, the more efficient the surfactant, the larger is
the size of the microstructure of the microemulsion. We report a striking
correlation between the efficiency of a surfactant and its monomeric solubi
lity in the excess phases for 23 systems of the type H2O-n-alkane-CiEj. The
se findings suggest that the monomeric solubility of the surfactant in oil
and water might be the key to describing the main features of these microem
ulsion systems.