The effect of divalent and trivalent salts (CaCl2, CaBr2, MgCl2, MgBr2, LaC
l3, CeCl3, La(NO3)(3), and Ce(NO3)(3)) on the micelle formation in Cs-lecit
hin solutions was investigated using the techniques of static and dynamic l
ight scattering. The critical micelle concentration (cmc), mean hydrodynami
c radius (Rh), gyration radius (R-g), and weight-average molecular weight o
f the micelles were measured as functions of salt identity and concentratio
n, amphiphile concentration, and temperature. It was found that the micelle
s in solutions of magnesium are less likely to form and less stable; their
standard enthalpy is less exothermic as the ionic strength increases. On th
e contrary, the micelles in solutions of calcium and trivalent salts form e
asily, and are more stable; their standard enthalpy is also more exothermic
as the ionic strength increases. Based on our model of the Gibb's free ene
rgy for the salt-added solutions, we obtained the following formula for the
effect of salts on cmc: In(cmc)' = In(cmc) + k(1) I-1/2 + k(2)I, where (cm
c)' and (cmc) are the critical micelle concentrations in salt-added and sal
t-free solutions, respectively, I is the ionic strength, and k(1) and k(2)
are the salt effect parameters. The agreement between the formula and the e
xperimental data for all the systems under study shows that the formula is
more satisfactory than those suggested previously by other authors in descr
ibing the effect of salts on the cmc in the micellar solutions of not only
zwitterionic but also nonionic surfactants. (C) 2001 Academic Press.