Thermodynamic fluid equations-of-state
Autor(a) principal: | |
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Data de Publicação: | 2018 |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10400.1/11342 |
Resumo: | As experimental measurements of thermodynamic properties have improved in accuracy, to five or six figures, over the decades, cubic equations that are widely used for modern thermodynamic fluid property data banks require ever-increasing numbers of terms with more fitted parameters. Functional forms with continuity for Gibbs density surface (p,T) which accommodate a critical-point singularity are fundamentally inappropriate in the vicinity of the critical temperature (T-c) and pressure (p(c)) and in the supercritical density mid-range between gas- and liquid-like states. A mesophase, confined within percolation transition loci that bound the gas- and liquid-state by third-order discontinuities in derivatives of the Gibbs energy, has been identified. There is no critical-point singularity at T-c on Gibbs density surface and no continuity of gas and liquid. When appropriate functional forms are used for each state separately, we find that the mesophase pressure functions are linear. The negative and positive deviations, for both gas and liquid states, on either side of the mesophase, are accurately represented by three or four-term virial expansions. All gaseous states require only known virial coefficients, and physical constants belonging to the fluid, i.e., Boyle temperature (T-B), critical temperature (T-c), critical pressure (p(c)) and coexisting densities of gas ((cG)) and liquid ((cL)) along the critical isotherm. A notable finding for simple fluids is that for all gaseous states below T-B, the contribution of the fourth virial term is negligible within experimental uncertainty. Use may be made of a symmetry between gas and liquid states in the state function rigidity (dp/d)(T) to specify lower-order liquid-state coefficients. Preliminary results for selected isotherms and isochores are presented for the exemplary fluids, CO2, argon, water and SF6, with focus on the supercritical mesophase and critical region. |
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Thermodynamic fluid equations-of-stateGibbs density surfaceCritical-pointTemperature relationTriple-pointArgonPressuresLiquidGasRegionMpaAs experimental measurements of thermodynamic properties have improved in accuracy, to five or six figures, over the decades, cubic equations that are widely used for modern thermodynamic fluid property data banks require ever-increasing numbers of terms with more fitted parameters. Functional forms with continuity for Gibbs density surface (p,T) which accommodate a critical-point singularity are fundamentally inappropriate in the vicinity of the critical temperature (T-c) and pressure (p(c)) and in the supercritical density mid-range between gas- and liquid-like states. A mesophase, confined within percolation transition loci that bound the gas- and liquid-state by third-order discontinuities in derivatives of the Gibbs energy, has been identified. There is no critical-point singularity at T-c on Gibbs density surface and no continuity of gas and liquid. When appropriate functional forms are used for each state separately, we find that the mesophase pressure functions are linear. The negative and positive deviations, for both gas and liquid states, on either side of the mesophase, are accurately represented by three or four-term virial expansions. All gaseous states require only known virial coefficients, and physical constants belonging to the fluid, i.e., Boyle temperature (T-B), critical temperature (T-c), critical pressure (p(c)) and coexisting densities of gas ((cG)) and liquid ((cL)) along the critical isotherm. A notable finding for simple fluids is that for all gaseous states below T-B, the contribution of the fourth virial term is negligible within experimental uncertainty. Use may be made of a symmetry between gas and liquid states in the state function rigidity (dp/d)(T) to specify lower-order liquid-state coefficients. Preliminary results for selected isotherms and isochores are presented for the exemplary fluids, CO2, argon, water and SF6, with focus on the supercritical mesophase and critical region.MDPI AgSapientiaWoodcock, Leslie2018-12-07T14:53:05Z2018-012018-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.1/11342eng1099-430010.3390/e20010022info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-07-24T10:23:08Zoai:sapientia.ualg.pt:10400.1/11342Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:02:51.776474Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Thermodynamic fluid equations-of-state |
title |
Thermodynamic fluid equations-of-state |
spellingShingle |
Thermodynamic fluid equations-of-state Woodcock, Leslie Gibbs density surface Critical-point Temperature relation Triple-point Argon Pressures Liquid Gas Region Mpa |
title_short |
Thermodynamic fluid equations-of-state |
title_full |
Thermodynamic fluid equations-of-state |
title_fullStr |
Thermodynamic fluid equations-of-state |
title_full_unstemmed |
Thermodynamic fluid equations-of-state |
title_sort |
Thermodynamic fluid equations-of-state |
author |
Woodcock, Leslie |
author_facet |
Woodcock, Leslie |
author_role |
author |
dc.contributor.none.fl_str_mv |
Sapientia |
dc.contributor.author.fl_str_mv |
Woodcock, Leslie |
dc.subject.por.fl_str_mv |
Gibbs density surface Critical-point Temperature relation Triple-point Argon Pressures Liquid Gas Region Mpa |
topic |
Gibbs density surface Critical-point Temperature relation Triple-point Argon Pressures Liquid Gas Region Mpa |
description |
As experimental measurements of thermodynamic properties have improved in accuracy, to five or six figures, over the decades, cubic equations that are widely used for modern thermodynamic fluid property data banks require ever-increasing numbers of terms with more fitted parameters. Functional forms with continuity for Gibbs density surface (p,T) which accommodate a critical-point singularity are fundamentally inappropriate in the vicinity of the critical temperature (T-c) and pressure (p(c)) and in the supercritical density mid-range between gas- and liquid-like states. A mesophase, confined within percolation transition loci that bound the gas- and liquid-state by third-order discontinuities in derivatives of the Gibbs energy, has been identified. There is no critical-point singularity at T-c on Gibbs density surface and no continuity of gas and liquid. When appropriate functional forms are used for each state separately, we find that the mesophase pressure functions are linear. The negative and positive deviations, for both gas and liquid states, on either side of the mesophase, are accurately represented by three or four-term virial expansions. All gaseous states require only known virial coefficients, and physical constants belonging to the fluid, i.e., Boyle temperature (T-B), critical temperature (T-c), critical pressure (p(c)) and coexisting densities of gas ((cG)) and liquid ((cL)) along the critical isotherm. A notable finding for simple fluids is that for all gaseous states below T-B, the contribution of the fourth virial term is negligible within experimental uncertainty. Use may be made of a symmetry between gas and liquid states in the state function rigidity (dp/d)(T) to specify lower-order liquid-state coefficients. Preliminary results for selected isotherms and isochores are presented for the exemplary fluids, CO2, argon, water and SF6, with focus on the supercritical mesophase and critical region. |
publishDate |
2018 |
dc.date.none.fl_str_mv |
2018-12-07T14:53:05Z 2018-01 2018-01-01T00:00:00Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10400.1/11342 |
url |
http://hdl.handle.net/10400.1/11342 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
1099-4300 10.3390/e20010022 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
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application/pdf |
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MDPI Ag |
publisher.none.fl_str_mv |
MDPI Ag |
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reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
repository.mail.fl_str_mv |
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1799133262571896832 |