We have determined
the solubilization and crystallization fields
of KNO3 for simple (Tergitol NP-4 and AOT) and mixed (Tergitol
NP-4 + AOT) microemulsions at 35 °C, depending on water content
and concentration of KNO3. An increase in the content of
AOT in mixed microemulsions leads to widening of the solubilization
field, but the crystallization field narrows up to complete disappearance
(in simple microemulsions of AOT). Fourier transform-infrared spectroscopy,
photon–correlation spectroscopy, and flame photometry were
used to determine the rate of water evaporation (2.6–7.4 μL/min),
hydrodynamic diameter of micelles (4.3–10 nm), and the content
of water and K+ and Na+ ions in the studied
microemulsions at different stages of evaporation crystallization
of KNO3. In simple microemulsions of Tergitol NP-4 crystallization
begins well before that in mixed microemulsions; in mixed microemulsions
the beginning of crystallization requires higher supersaturation (up
to 13 M) compared to simple microemulsions (∼4 M at initial
solubilization capacity of 0.5 vol %). In accordance with the Gibbs–Thomson
(Kelvin) theory, high supersaturations suggest that in mixed micelles
cores of smaller sizes are formed. During crystallization, micelles
with KNO3 solution coexist with KNO3 crystals.
The function of micelles is to supply “building material”
for their growth. Numerical simulation with the help of direct optimization
showed that in mixed micelles at low water contents, Na+ ions are stronger bound with AOT–, owing to which
Na+ ions occur only as impurities in powders.