Publication
Thermodynamics of gas–liquid colloidal equilibrium states: hetero-phase fluctuations
| dc.contributor.author | Woodcock, Leslie | |
| dc.date.accessioned | 2020-02-18T18:03:31Z | |
| dc.date.available | 2020-02-18T18:03:31Z | |
| dc.date.issued | 2019 | |
| dc.description.abstract | Following on from two previous JETC (Joint European Thermodynamics Conference) presentations, we present a preliminary report of further advances towards the thermodynamic description of critical behavior and a supercritical gas-liquid coexistence with a supercritical fluid mesophase defined by percolation loci. The experimental data along supercritical constant temperature isotherms (T >= T-c) are consistent with the existence of a two-state mesophase, with constant change in pressure with density, rigidity, (dp/d rho) (T), and linear thermodynamic state-functions of density. The supercritical mesophase is bounded by 3rd-order phase transitions at percolation thresholds. Here we present the evidence that these percolation transitions of both gaseous and liquid states along any isotherm are preceded by pre-percolation hetero-phase fluctuations that can explain the thermodynamic properties in the mesophase and its vicinity. Hetero-phase fluctuations give rise to one-component colloidal-dispersion states; a single Gibbs phase retaining 2 degrees of freedom in which both gas and liquid states with different densities percolate the phase volume. In order to describe the thermodynamic properties of two-state critical and supercritical coexistence, we introduce the concept of a hypothetical homo-phase of both gas and liquid, defined as extrapolated equilibrium states in the pre-percolation vicinity, with the hetero-phase fractions subtracted. We observe that there can be no difference in chemical potential between homo-phase liquid and gaseous states along the critical isotherm in mid-critical isochoric experiments when the meniscus disappears at T = T-c. For T > T-c, thermodynamic states comprise equal mole fractions of the homo-phase gas and liquid, both percolating the total phase volume, at the same temperature, pressure, and with a uniform chemical potential, stabilised by a positive finite interfacial surface tension. | pt_PT |
| dc.description.version | info:eu-repo/semantics/publishedVersion | pt_PT |
| dc.identifier.doi | 10.3390/e21121189 | pt_PT |
| dc.identifier.issn | 1099-4300 | |
| dc.identifier.uri | http://hdl.handle.net/10400.1/13528 | |
| dc.language.iso | eng | pt_PT |
| dc.peerreviewed | yes | pt_PT |
| dc.publisher | MDPI | pt_PT |
| dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | pt_PT |
| dc.subject | Hetero-phase fluctuation | pt_PT |
| dc.subject | Percolation transition | pt_PT |
| dc.subject | Supercritical mesophase | pt_PT |
| dc.subject | Liquid state | pt_PT |
| dc.subject | Argon | pt_PT |
| dc.title | Thermodynamics of gas–liquid colloidal equilibrium states: hetero-phase fluctuations | pt_PT |
| dc.type | journal article | |
| dspace.entity.type | Publication | |
| oaire.citation.issue | 12 | pt_PT |
| oaire.citation.startPage | 1189 | pt_PT |
| oaire.citation.title | Entropy | pt_PT |
| oaire.citation.volume | 21 | pt_PT |
| person.familyName | Woodcock | |
| person.givenName | Leslie | |
| person.identifier.orcid | 0000-0003-2350-559X | |
| rcaap.rights | openAccess | pt_PT |
| rcaap.type | article | pt_PT |
| relation.isAuthorOfPublication | b550a18f-b4d3-4d68-8b8d-84f3373024aa | |
| relation.isAuthorOfPublication.latestForDiscovery | b550a18f-b4d3-4d68-8b8d-84f3373024aa |