Reversible work of formation of an embryo of a new phase within a uniform macroscopic mother phase

被引:66
作者
Debenedetti, PG [1 ]
Reiss, H
机构
[1] Princeton Univ, Dept Chem Engn, Princeton, NJ 08544 USA
[2] Princeton Univ, Princeton Mat Inst, Princeton, NJ 08544 USA
[3] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
关键词
D O I
10.1063/1.475938
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A thermodynamically consistent formalism is derived fur calculating the reversible work needed to form a small amount of a new phase (embryo) within a uniform macroscopic mother phase. The treatment gees beyond the classic work of Gibbs, who solved the problem for the particular case in which the embryo is in equilibrium with the mother phase, constituting a so-called critical nucleus. The formalism results in a new expression for the reversible work of embryo formation, the extrema conditions for which yield the correct conditions of equilibrium between the critical nucleus and the mother phase, as well as Gibbs' result for the reversible work needed to form the critical nucleus. The new expression for the work of embryo formation differs from the one commonly used in the nucleation literature, In order to extend the Gibbsian formalism to noncritical nuclei, it is necessary to introduce a constraint that prevents the free transfer of matter between the embryo and the mother phase. The present approach is valid in the limit in which curvature contributions to the interfacial energy can be neglected. (C) 1998 American Institute of Physics. [S0021-9606(98)50513-2].
引用
收藏
页码:5498 / 5505
页数:8
相关论文
共 20 条
[1]  
Becker R, 1935, ANN PHYS-BERLIN, V24, P719
[2]   Constraints, metastability, and inherent structures in liquids [J].
Corti, DS ;
Debenedetti, PG ;
Sastry, S ;
Stillinger, FH .
PHYSICAL REVIEW E, 1997, 55 (05) :5522-5534
[3]  
Debenedetti P. G, 1996, METASTABLE LIQUIDS C
[4]   SELF-NUCLEATION IN SULFURIC ACID-WATER SYSTEM [J].
DOYLE, GJ .
JOURNAL OF CHEMICAL PHYSICS, 1961, 35 (03) :795-&
[5]   ONE-DIMENSIONAL RIGOROUS HOLE THEORY OF FLUIDS - INTERNALLY CONSTRAINED ENSEMBLES [J].
ELKOSHI, Z ;
REISS, H ;
HAMMERICH, AD .
JOURNAL OF STATISTICAL PHYSICS, 1985, 41 (3-4) :685-708
[6]  
Farkas L, 1927, Z PHYS CHEM-STOCH VE, V125, P236
[7]  
Gibbs J.W., 1878, Trans. Connecticut Acad. Arts Sci., V16, P343
[8]  
Gibbs J.W., 1876, Am.J. Sci, V3, P108, DOI DOI 10.2475/AJS.S3-16.96.441
[9]  
Gibbs J. W., 1961, SCI PAPERS JW GIBBS, V1
[10]   HOMOGENEOUS NUCLEATION OF VAPOR CONDENSATION .2. KINETIC ASPECTS [J].
MCDONALD, JE .
AMERICAN JOURNAL OF PHYSICS, 1963, 31 (01) :31-&