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Supercritical fluid gaseous and liquid states: a review of experimental results

dc.contributor.authorKhmelinskii, Igor
dc.contributor.authorWoodcock, Leslie
dc.date.accessioned2020-06-17T13:13:14Z
dc.date.available2020-06-17T13:13:14Z
dc.date.issued2020
dc.description.abstractWe review the experimental evidence, from both historic and modern literature of thermodynamic properties, for the non-existence of a critical-point singularity on Gibbs density surface, for the existence of a critical density hiatus line between 2-phase coexistence, for a supercritical mesophase with the colloidal characteristics of a one-component 2-state phase, and for the percolation loci that bound the existence of gaseous and liquid states. An absence of any critical-point singularity is supported by an overwhelming body of experimental evidence dating back to the original pressure-volume-temperature (p-V-T) equation-of-state measurements of CO2 by Andrews in 1863, and extending to the present NIST-2019 Thermo-physical Properties data bank of more than 200 fluids. Historic heat capacity measurements in the 1960s that gave rise to the concept of “universality” are revisited. The only experimental evidence cited by the original protagonists of the van der Waals hypothesis, and universality theorists, is a misinterpretation of the isochoric heat capacity Cv. We conclude that the body of extensive scientific experimental evidence has never supported the Andrews–van der Waals theory of continuity of liquid and gas, or the existence of a singular critical point with universal scaling properties. All available thermodynamic experimental data, including modern computer experiments, are compatible with a critical divide at Tc, defined by the intersection of two percolation loci at gaseous and liquid phase bounds, and the existence of a colloid-like supercritical mesophase comprising both gaseous and liquid states.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.doi10.3390/e22040437pt_PT
dc.identifier.issn1099-4300
dc.identifier.urihttp://hdl.handle.net/10400.1/14030
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.publisherMDPIpt_PT
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/pt_PT
dc.subjectGas-liquidpt_PT
dc.subjectSupercritical fluidpt_PT
dc.subjectCritical pointpt_PT
dc.subjectSupercriticalmesophasept_PT
dc.subjectUniversality hypothesispt_PT
dc.titleSupercritical fluid gaseous and liquid states: a review of experimental resultspt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.issue4pt_PT
oaire.citation.startPage437pt_PT
oaire.citation.titleEntropypt_PT
oaire.citation.volume22pt_PT
person.familyNameKhmelinskii
person.familyNameWoodcock
person.givenNameIgor
person.givenNameLeslie
person.identifier0000000420541031
person.identifier.ciencia-id0D1A-CB6C-6316
person.identifier.orcid0000-0002-6116-184X
person.identifier.orcid0000-0003-2350-559X
person.identifier.ridC-9587-2011
person.identifier.scopus-author-id6701444934
rcaap.rightsopenAccesspt_PT
rcaap.typearticlept_PT
relation.isAuthorOfPublicationfcb9f09f-2e99-41fb-8c08-7e1acbc65076
relation.isAuthorOfPublicationb550a18f-b4d3-4d68-8b8d-84f3373024aa
relation.isAuthorOfPublication.latestForDiscoveryfcb9f09f-2e99-41fb-8c08-7e1acbc65076

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