TY - JOUR
T1 - Understanding and Analyzing Freezing-Point Transitions of Confined Fluids within Nanopores
AU - Shimizu, Steven
AU - Agrawal, Kumar Varoon
AU - O'Mahony, Marcus
AU - Drahushuk, Lee W.
AU - Manohar, Neha
AU - Myerson, Allan S.
AU - Strano, Michael S.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/9/22
Y1 - 2015/9/22
N2 - Understanding phase transitions of fluids confined within nanopores is important for a wide variety of technological applications. It is well known that fluids confined in nanopores typically demonstrate freezing-point depressions, δTf, described by the Gibbs-Thomson (GT) equation. Herein, we highlight and correct several thermodynamic inconsistencies in the conventional use of the GT equation, including the fact that the enthalpy of melting, δHm, and the solid-liquid surface energy, SL, are functions of pore diameter, complicating their prediction. We propose a theoretical analysis that employs the Turnbull coefficient, originally derived from metal nucleation theory, and show its consistency as a more reliable quantity for the prediction of δTf. This analysis provides a straightforward method to estimate δTf of nanoconfined organic fluids. As an example, we apply this technique to ibuprofen, an active pharmaceutical ingredient (API), and show that this theory fits well to the experimental δTf of nanoconfined ibuprofen.
AB - Understanding phase transitions of fluids confined within nanopores is important for a wide variety of technological applications. It is well known that fluids confined in nanopores typically demonstrate freezing-point depressions, δTf, described by the Gibbs-Thomson (GT) equation. Herein, we highlight and correct several thermodynamic inconsistencies in the conventional use of the GT equation, including the fact that the enthalpy of melting, δHm, and the solid-liquid surface energy, SL, are functions of pore diameter, complicating their prediction. We propose a theoretical analysis that employs the Turnbull coefficient, originally derived from metal nucleation theory, and show its consistency as a more reliable quantity for the prediction of δTf. This analysis provides a straightforward method to estimate δTf of nanoconfined organic fluids. As an example, we apply this technique to ibuprofen, an active pharmaceutical ingredient (API), and show that this theory fits well to the experimental δTf of nanoconfined ibuprofen.
UR - http://www.scopus.com/inward/record.url?scp=84942155098&partnerID=8YFLogxK
U2 - 10.1021/acs.langmuir.5b02149
DO - 10.1021/acs.langmuir.5b02149
M3 - Article
C2 - 26332689
AN - SCOPUS:84942155098
SN - 0743-7463
VL - 31
SP - 10113
EP - 10118
JO - Langmuir
JF - Langmuir
IS - 37
ER -