Journal of Physical Chemistry B, Vol.116, No.13, 3954-3960, 2012
Phase Transitions of n-Hexadecane in Nanoencapsulated Binary Solutions of n-Hexadecane and 1-Octanol
Binary solutions of n-hexadecane and 1-octanol were encapsulated within poly(tert-butyl methacrylate) nanocapsules and the phase transition behavior of the n-hexadecane studied. A sigmoidal correlation was found between the binary composition of the encapsulated oil and the oil formulation prior to encapsulation. At low 1-octanol fractions in the synthesis, almost no alcohol was encapsulated, but at high 1-octanol fractions, the capsules were enriched in alcohol. The freezing point of the encapsulated n-hexadecane was considerably lower than in the bulk phase. This freezing point was further reduced as the radius of the particle was reduced, which is expected from the Gibbs-Thompson equation. The extracted value at infinite radii was, however, 14 degrees C below the bulk freezing point. The colligative effect of 1-octanol on the freezing point of n-hexadecane, i.e., dT(f)/dx(m) where x(m) is the mass fraction of 1-octanol, was nearly identical to that measured in the bulk system. The specific enthalpy of freezing for the encapsulated system was considerably different from the bulk system. In the bulk system, the freezing enthalpy for n-hexadecane was nearly constant up to 60% mass of 1-octanol. The freezing enthalpy for the encapsulated n-hexadecane showed greater variation with % mass 1-octanol, and had a considerably lower absolute value than the bulk system.