%0 Journal Article
%T Liquid Pre-Freezing Percolation Transition to Equilibrium Crystal-in-Liquid Mesophase
%A Leslie V. Woodcock
%J Natural Science
%P 247-262
%@ 2150-4105
%D 2018
%I Scientific Research Publishing
%R 10.4236/ns.2018.107026
%X <strong>Pre-freezing anomalies are explained by a percolation transition that delineates the existence of a pure equilibrium liquid state above the temperature of 1st-order freezing to the stable crystal phase. The precursor to percolation transitions are hetero-phase fluctuations that give rise to molecular clusters of an otherwise unstable state in the stable host phase. In-keeping with the Ostwald¡¯s step rule, clusters of a crystalline state, closest in stability to the liquid, are the predominant structures in pre-freezing hetero-phase fluctuations. Evidence from changes in properties that depend upon density and energy fluctuations suggests embryonic nano-crystallite</strong><strong>s diverge in size and space at a percolation threshold, whence a colloidal-like equilibrium is stabilized by negative surface tension. Below this transition temperature, both crystal and liquid states percolate the phase volume in an equilibrium state of dispersed coexistence. We obtain a preliminary estimate of the prefreezing percolation line for water determined from higher-order discontinuities in Gibbs energy that derivatives the isothermal rigidity [(dp/d¦Ñ)T] and isochoric heat capacity [(dU/dT)v] respectively. The percolation temperature varies only slightly with pressure from 51.5¡ãC at 0.1 MPa to around 60¡ãC at 100 MPa. We conjecture that the predominant dispersed crystal structure is a tetrahedral ice, which is the closest of the higher-density ices (II to XV) to liquid water in configurational energy. Inspection of thermodynamic and transport properties of liquid argon also indicate the existence of a similar prefreezing percolation transition at ambient pressures (0.1 MPa) around 90 K, ~6% above the triple point (84 K). These findings account for many anomalous properties of equilibrium and supercooled liquids generally, and also explain Kauzmann¡¯s ¡°paradox¡± at a ¡°glass¡± transition.</strong>
%K Liquid State
%K Percolation
%K Phase Transition
%K Pre-Freezing Mesophase
%U http://www.scirp.org/journal/PaperInformation.aspx?PaperID=86094