Open AccessOn the mechanism of some first‐order enantiotropic solid‐state phase transitions: from Simon through Ubbelohde to Mnyukh
Author(s) -
Herbstein Frank H.
Publication year - 2006
Publication title -
acta crystallographica section b
Language(s) - English
Resource type - Journals
eISSN - 1600-5740
pISSN - 0108-7681
DOI - 10.1107/s0108768106008640
Subject(s) - phase transition , nucleation , phase (matter) , ferroelectricity , order (exchange) , crystal (programming language) , condensed matter physics , materials science , crystallography , thermodynamics , chemistry , physics , quantum mechanics , optoelectronics , finance , computer science , dielectric , economics , programming language
The first (so‐called) lambda transition in solids was found in the specific heat measurements for NH 4 Cl at 242 K by F. Simon in 1922 [Simon (1922). Ann. Phys. 68 , 241–280]. Analogous phenomena found in many other solids gave rise to doubts (expressed most clearly by A. R. Ubbelohde some 50 years ago) about the applicability of classical thermodynamics to some phase transitions [Ubbelohde (1956). Brit. J. Appl. Phys. 7 , 313–321]. However, Y. Mnyukh's studies of enantiotropic phase transitions in eight organic crystals showed that all proceed by a nucleation‐and‐growth mechanism [summarized in Mnyukh (2001), Fundamentals of Solid State Phase Transitions, Ferromagnetism and Ferroelectricity . 1st Books]. Nucleation is localized at defects in the parent phase; growth can be epitaxic and oriented if parent and daughter phases have closely similar structures, or random (not oriented) if there are substantial structural differences. This conclusion is supported by a critical review of Mnyukh's eight examples and other results published in the interim. It seems that Ubbelohde's invocation of `hybrid crystals' and `smeared transitions' can mostly be accounted for by lack of equilibrium in the phase‐transition studies cited by him. However, the intermediate phase in 4,4′‐dichlorobenzophenone appears to have structural resemblances to Ubbelohde's' `hybrid crystal'.