화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.113, No.19, 6732-6735, 2009
Isothermal Titration Calorimetry Studies of Neutral Salt Effects on the Thermodynamics of Micelle Formation
Isothermal titration calorimetry, ITC, was used to determine the enthalpy and heat capacity changes that accompany micelle formation of decyldimethylphosphine oxide, APO10, from 15-79 degrees C in the presence of representative neutral salts from the Hofmeister series. The solutions investigated were water, 0.2, 0.5, and 1.0 NaCl, 0.5 M NaF, KCl, KI, guanidinium chloride (GuHCl) and mannitol, and 0.333 M Na2SO4. The heat capacity change at 25 degrees C (but not the cmc) and the parameter that describes the temperature dependence of the heat capacity change, B (cal/(mol K-2)), appear to be correlated. Calculated values of the ion effects on micelle formation from a recent salt ion partitioning model (SPM) of Pegram and Record [J. Phys. Chem. B 2007, 111, 5411-5417] were quantitatively related to the experimental value of the solute free energy increment (SFEI). Use of this model requires a calculation of the solvent accessible area (ASA), which yields values for the extent of hydration of the micelle interior. An alternate method to determine the ASA based on the heat capacity change for micelle formation at 25 degrees C of APO8-12 yielded values for the number of buried carbon atoms (5-12) versus previous estimates (4-8) from analysis of the B parameter.