Reply to Comment on�"On the relationship between the entropy and enthalpy of interfacial segregation" by P. Lej?ek and S. Hofmann

Abstract

Eur. Phys. J. B 22, 267 (2001) This note aims to resolve some terminological misunderstanding reflected by the comment of Lejcek and Hofmann (L-H). It stems primarily from the difference in two reference systems quite commonly used in the description of interfacial segregation. Our article referred to an ideal solution defined atomistically by equal interactions between all constituents, that exhibits ideal behavior (in accordance with Raoult's law) over all concentrations, no change of internal energy on mixing or demixing, and therefore, the absence of any segregation “driving force”. The use of such ideal solution as a reference system to excess thermodynamical properties, e.g., the “excess free energy of segregation”, is fully consistent with common basic definitions and previous works. The different reference system inherent in the approach used by L-H (in accordance with early segregation theories) is based on the infinitesimally dilute solution approximation (Henry's law region), and is the source of the terminological disagreement regarding the actual meaning of excess properties.