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Rigidity Symmetry Line for Thermodynamic Fluid Equations-of-State

Journal of Modern Physics 2024年第5期15卷 613-633页

作者： leslie v. woodcock Department of Physics University of Algarve Faro Portugal

We report progress towards a modern scientific description of thermodynamic properties of fluids following the discov.ry (in 2012) of a coexisting critical density hiatus and a supercritical mesophase defined by percolation transitions. The state functions density ρ(p,T), and Gibbs energy G(p,T), of fluids, e.g. CO2, H2O and argon exhibit a symmetry characterised by the rigidity, ω = (dp/dρ)T, between gaseous and liquid states along any isotherm from critical (Tc) to Boyle (TB) temperatures, on either side of the supercritical mesophase. Here, using experimental data for fluid argon, we inv.stigate the low-density cluster physics description of an ideal dilute gas that obeys Dalton’s partial pressure law. Cluster expansions in powers of density relate to a supercritical liquid-phase rigidity symmetry (RS) line (ω = ρrs(T) = RT) to gas phase v.rial coefficients. We show that it is continuous in all deriv.tiv.s, linear within stable fluid phase, and relates analytically to the Boyle-work line (BW) (w = (p/ρ)T = RT), and to percolation lines of gas (PB) and liquid (PA) phases by: ρBW(T) = 2ρPA(T) = 3ρPB(T) = 3ρRS(T)/2 for T TB. These simple relationships arise, because the higher v.rial coefficients (bn, n ≥ 4) cancel due to clustering equilibria, or become negligible at all temperatures (0 T TB) within the gas phase. The Boyle-work line (p/ρBW)T is related exactly at lower densities as T → TB, and accurately for liquid densities, by ρBW(T) = −(b2/b3)T. The RS line, ω(T) = RT, defines a new liquid-density ground-state physical constant (ρRS(0) = (2/3)ρBW(0) for argon). Giv.n the gas-liquid rigidity symmetry, the entire thermodynamic state functions below TB are obtainable from b2(T). A BW

关键词： Liquid-State Theory Cluster Physics Percolation Lines Fluid Thermodynamics Boyle Line Rigidity-Symmetry Line

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Thermodynamics of Criticality: Percolation Loci, Mesophases and a Critical Div.ding Line in Binary-Liquid and Liquid-Gas Equilibria

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Journal of Modern Physics 2016年第8期7卷 760-773页

作者： leslie v. woodcock Department of Physics University of Algarve Faro Portugal

High-temperature and pressure boundaries of the liquid and gas states hav. not been defined thermodynamically. Standard liquid-state physics texts use either critical isotherms or isobars as ad hoc boundaries in phase diagrams. Here we report that percolation transition loci can define liquid and gas states, extending from super-critical temperatures or pressures to “ideal gas” states. Using computational methodology described prev.ously we present results for the thermodynamic states at which clusters of excluded v.lume (v.sub>E) and pockets of av.ilable v.lume (v.sub>A), for a spherical molecule diameter σ, percolate the whole v.lume (v.= v.sub>E + v.sub>A) of the ideal gas. The molecular-reduced temperature (T)/pressure(p) ratios ( ) for the percolation transitions are = 1.495 ± 0.015 and = 1.100 ± 0.015. Further MD computations of percolation loci, for the Widom-Rowlinson (W-R) model of a partially miscible binary liquid (A-B), show the connection between the ideal gas percolation transitions and the 1st-order phase-separation transition. A phase diagram for the penetrable cohesiv. sphere (PCS) model of a one-component liquid-gas is then obtained by analytic transcription of the W-R model thermodynamic properties. The PCS percolation loci extend from a critical coexistence of gas plus liquid to the low-density limit ideal gas. Extended percolation loci for argon, determined from literature equation-of-state measurements exhibit similar phenomena. When percolation loci define phase bounds, the liquid phase spans the whole density range, whereas the gas phase is confined by its percolation boundary within an area of low T and p on the density surface. This is contrary to a general perception and opens a debate on the definitions of gaseous and liquid states.

关键词： Thermodynamics Criticality Percolation Transition Ideal Gas: Liquid State

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Closed v.rial equations for hard parallel cubes andsquares

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Natural Science 2011年第7期3卷 622-632页

作者： leslie v. woodcock 不详

A correlation between maxima in v.rial coefficients (Bn), and “kissing” numbers for hard hyper-spheres up to dimension D = 5, indicates a v.rial equation and close-packing relationship. Known v.rial coefficients up to B7, both for hard parallel cubes and squares, indicate that the limiting differences Bn – Bn-1 behav. similar to spheres and disks, in the respectiv. expan-sions relativ. to maximum close packing. In all cases, the difference Bn – Bn-1 is approaching a negativ. constant with similar functional form in each dimen-sion. This observ.tion enables closed-v.rial equa-tions-of-state for cubes and squares to be obtained. In both the 3D and 2D cases, the v.rial pressures begin to dev.ate from MD thermodynamic pressures at densities well below crystallization. These results consolidate the general conclusion, from prev.ous papers on spheres and disks, that the Mayer cluster expansion cannot represent the thermodynamic fluid phases up to freezing as commonly assumed in statistical theories.

关键词： v.rial Equations Liquid Theory

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Gibbs Density Surface of Water and Steam: 2nd Debate on the Absence of v.n Der Waals’ “Critical Point”

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Natural Science 2014年第6期6卷 411-432页

作者： leslie v. woodcock Department of Physics University of Algarve Faro Portugal

A rev.sed phase diagram for water shows three distinct fluid phases. There is no continuity of liquid and gas, and no “critical point” on Gibbs’ density surface as hypothesized by v.n der Waals. A supercritical colloidal mesophase bounded by percolation transition loci separates supercritical liquid water and gas-phase steam. The water phase is bounded by a percolation transition (PA) of av.ilable v.lume, whereas steam is bounded by the loci of a percolation transition (PB) at a density whereupon a bonded molecular cluster suddenly percolates large distances. At the respectiv. percolation densities, there is no barrier to nucleation of water to steam (PA) or steam to water (PB). Below the critical temperature, the percolation loci become the metastable spinodals in the two-phase coexistence region. A critical div.de is defined by the interception of PA and PB the p-T plane. Critical parameters are obtainable from slopes and intercepts of pressure-density supercritical isotherms within the mesophase. The supercritical mesophase is a fourth equilibrium state besides ice, water and steam. A thermodynamic state function rigidity (dp/dρ)T defines a distinction between liquid and gas, and shows a remarkable symmetry due to an equiv.lence in number density fluctuations, arising from av.ilable v.lume and molecular clusters, in liquid and gas respectiv.ly. Following an earlier debate in these pages [“Fluid phases of argon: A debate on the absence of v.n der Waals’ critical point” Natural Science 5 (2) 194-206 (2013)], we here report further debate on a science of criticality applied to water and steam (APPENDIX 1).

关键词： Water Steam Phase Diagram Critical Line Percolation Loci

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Fluid phases of argon: A debate on the absence of v.n der Waals’ “critical point”

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Natural Science 2013年第2期5卷 194-206页

作者： leslie v. woodcock Manchester Institute of Biotechnology Univ.rsity of Manchester Manchester UK

A phase diagram of argon based upon percolation transition loci determined from literature experimental p-v.isotherms, and simulation v.lues using a Lennard-Jones model shows three fluid phases. The liquid phase spans all temperatures, from a metastable amorphous ground state at 0K, to ultra-high T. There is a supercritical mesophase bounded by percolation transition loci, and a gas phase. Intersection of two percolation loci in the p-T plane thermodynamically defines a critical line between two coexisting gas and liquid critical states at T = Tc, and the single mesophase for T > Tc. A debate on the absence of a v.n der Waals critical point in the Gibbs p-T density surface is appended.

关键词： Critical Point Supercritical Fluids Liquid Phase

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Liquid Pre-Freezing Percolation Transition to Equilibrium Crystal-in-Liquid Mesophase

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Natural Science 2018年第7期10卷 247-262页

作者： leslie v. woodcock Department of Physics University of Algarve Faro Portugal

Pre-freezing anomalies are explained by a percolation transition that delineates the existence of a pure equilibrium liquid state abov. the temperature of 1st-order freezing to the stable crystal phase. The precursor to percolation transitions are hetero-phase fluctuations that giv. 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. Ev.dence from changes in properties that depend upon density and energy fluctuations suggests embryonic nano-crystallites div.rge in size and space at a percolation threshold, whence a colloidal-like equilibrium is stabilized by negativ. surface tension. Below this transition temperature, both crystal and liquid states percolate the phase v.lume 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 deriv.tiv.s the isothermal rigidity [(dp/dρ)T] and isochoric heat capacity [(dU/dT)v. respectiv.ly. The percolation temperature v.ries only slightly with pressure from 51.5°C at 0.1 MPa to around 60°C 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% abov. 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.

关键词： Liquid State Percolation Phase Transition Pre-Freezing Mesophase

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Nature of the Supercritical Mesophase

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Natural Science 2014年第10期6卷 797-807页

作者： Hamza J. Magnier Robin A. Curtis leslie v. woodcock Department of Physics University of Algarve Faro Portugal Manchester Institute of Biotechnology University of Manchester Manchester UK

It has been reported that at temperatures abov. the critical there is no “continuity of liquid and gas”, as originally hypothesized by v.n der Waals [1]. Rather, both gas and liquid phases, with characteristic properties as such, extend to supercritical temperatures [2]-[4]. Each phase is bounded by the locus of a percolation transition, i.e. a higher-order thermodynamic phase change associated with percolation of gas clusters in a large v.id, or liquid interstitial v.cancies in a large cluster. Between these two-phase bounds, it is reported there exists a mesophase that resembles an otherwise homogeneous dispersion of gas micro-bubbles in liquid (foam) and a dispersion of liquid micro-droplets in gas (mist). Such a colloidal-like state of a pure one-component fluid represents a hitherto unchartered equilibrium state of matter besides pure solid, liquid or gas. Here we prov.de compelling ev.dence, from molecular dynamics (MD) simulations, for the existence of this supercritical mesophase and its colloidal nature. We report preliminary results of computer simulations for a model fluid using a simplistic representation of atoms or molecules, i.e. a hard-core repulsion with an attraction so short that the atoms are referred to as “adhesiv. spheres”. Molecular clusters, and hence percolation transitions, are unambiguously defined. Graphics of color-coded clusters show colloidal characteristics of the supercritical mesophase. We append this Letter to Natural Science with a debate on the scientific merits of its content courtesy of correspondence with Nature (Appendix).

关键词： Supercritical Mesophase Adhesiv.-Sphere Criticality Liquid-Gas

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Storylines of family medicine Ⅷ:clinical approaches

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Family Medicine and Community Health 2024年第S3期12卷 70-78页

作者： William B v.ntres leslie A Stone Lauren E Gibson-Oliv.r Elizabeth Kyle Meehan Mari A Ricker Dav.d Loxterkamp Stacy A Ogbeide Frank v.deGruy Megan R Mahoney Stev.n Lin Clare MacRae Stewart W Mercer Family and Prev.ntiv. Medicine University of Arkansas for Medical Sciences College of MedicineLittle RockArkansasUSA Family and Community Medicine The University of Arizona College of Medicine-TucsonTucsonArizonaUSA Bucksport Regional Health Center BucksportMaineUSA Family and Community Medicine UT Health San Antonio Long School of MedicineSan AntonioTexasUSA Eugene S.Farley Jr.Health Policy CenterUniversity of Colorado Anschutz Medical Campus School of MedicineAuroraColoradoUSA Family and Community Medicine University of California San Francisco School of MedicineSan FranciscoCaliforniaUSA Div.sion of Primary Care and Population Health Stanford MedicinePalo AltoCaliforniaUSA Usher Institute Edinburgh Medical SchoolUniversity of EdinburghEdinburghUK

Storylines of Family Medicine is a 12-part series of thematically linked mini-essays with accompanying illustrations that explore the many dimensions of family medicine as interpreted by indiv.dual family physicians and medical educators in the USA and elsewhere around the ***‘Ⅷ:clinical approaches’,authors address the following themes:‘Ev.luation,diagnosis and managementⅠ—toward a working diagnosis’,‘Ev.luation,diagnosis and managementⅡ—process steps’,‘Interweav.ng integrativ. medicine and family medicine’,‘Halfway—the art of clinical judgment’,‘Seamless integration in family medicine—team-based care’,‘Technology—uncov.ring stories from noise’and‘Caring for patients with multiple long-term conditions’.May readers recognise in these essays the uniqueness of a family medicine approach to care.

关键词： uniqueness dimensions illustration

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Storylines of family medicine Ⅱ:foundational building blocks—context,community and health

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Family Medicine and Community Health 2024年第S3期12卷 12-22页

作者： William B v.ntres leslie A Stone Rupal Shah Tamala Carter Geoffrey M Gusoff Winston Liaw Bich-May Nguyen Joanna v.Rachelson Mary Alice Scott Teresa L Schiff-Elfalan Seiji Yamada Robert C Like Kathleen Zoppi A Peter Catinella Richard M Frankel Shailendra Prasad Family and Prev.ntiv. Medicine University of Arkansas for Medical Sciences College of MedicineLittle RockArkansasUSA Bridge Lane Group Practice LondonUK Penn Center for Community Health Workers University of PennsylvaniaPhiladelphiaPennsylvaniaUSA National Clinician Scholars Program UCLA David Geffen School of MedicineLos AngelesCaliforniaUSA Health Systems and Population Health Sciences University of Houston Tilman J Fertitta Family College of MedicineHoustonTexasUSA Southern New Mexico Family Medicine Residency Program Las CrucesNew MexicoUSA New Mexico Primary Care Training Program Silver CityNew MexicoUSA Anthropology New Mexico State UniversityLas CrucesNew MexicoUSA Family Medicine and Community Health University of Hawai'i at Manoa John A Burns School of MedicineHonoluluHawaiiUSA Family Medicine and Community Health Rutgers Robert Wood Johnson Medical SchoolNew BrunswickNew JerseyUSA Family Medicine Indiana University School of MedicineIndianapolisIndianaUSA Family Medicine–Transmountain Texas Tech University Health Sciences CenterEl PasoTexasUSA Medicine Indiana University School of MedicineIndianapolisIndianaUSA Family Medicine and Community Health University of Minnesota Medical School-Twin Cities CampusMinneapolisMinnesotaUSA

Storylines of Family Medicine is a 12-part series of thematically linked mini-essays with accompanying illustrations that explore the many dimensions of family medicine,as interpreted by indiv.dual family physicians and medical educators in the USA and elsewhere around the ***‘Ⅱ:foundational building blocks—context,community and health’,authors address the following themes:‘Context—grounding family medicine in time,place and being’,‘Recentring community’,‘Community-oriented primary care’,‘Embeddedness in practice’,‘The meaning of health’,‘Disease,illness and sickness—core concepts’,‘The biopsychosocial model’,‘The biopsychosocial approach’and‘Family medicine as social medicine.’May readers grasp new implications for medical education and practice in these essays.

关键词： thematic illustration dimensions

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Recent v.ntures in Interdisciplinary Arctic Research:The ARCPATH Project

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Adv.nces in Atmospheric Sciences 2024年第8期41卷 1559-1568页

作者： Astrid E.J.OGILv.E leslie A.KING Noel KEENLYSIDE François COUNILLON Brynhildur DAv.ÐSDÓTTIR Níels EINARSSON Sergey GULEv.Ke FAN Torben KOENIGK James R.MCGOODWIN Marianne H.RASMUSSON Shuting YANG Institute of Arctic and Alpine Research(INSTAAR) University of ColoradoBoulder CO 80303USA Stefansson Arctic Institute AkureyriÍS-600Iceland Royal Roads Univ.rsity BC V9B 5Y2Canada Univ.rsity of Bergen Bergen N-5007Norway Nansen Env.ronmental and Remote Sensing Centre Bergen N-5007Norway Univ.rsity of Iceland Reykjavík 102Iceland Shirshov.Institute of Oceanology Moscow 117218Russia Moscow State Univ.rsity Moscow 11991Russia Chinese Academy of Sciences Beijing 100045China Swedish Meteorological and Hydrological Institute SE-60176 NorrköpingSweden Danish Meteorological Institute CopenhagenØ2100Denmark Obukhov.Institute of Atmospheric Physics RAS119017MoscowRussia

This paper celebrates Professor Yongqi GAO's significant achiev.ment in the field of interdisciplinary studies within the context of his final research project Arctic Climate Predictions: Pathways to Resilient Sustainable Societies-ARCPATH(https://***/en/projects/finished-projects/arcpath). The disciplines represented in the project are related to climatology, anthropology, marine biology, economics, and the broad spectrum of social-ecological studies. Team members were drawn from the Nordic countries, Russia, China, the United States, and Canada. The project was transdisciplinary as well as interdisciplinary as it included collaboration with local knowledge holders. ARCPATH made significant contributions to Arctic research through an improv.d understanding of the mechanisms that driv. climate v.riability in the Arctic. In tandem with this research, a combination of historical inv.stigations and social, economic, and marine biological fieldwork was carried out for the project study areas of Iceland, Greenland, Norway, and the surrounding seas, with a focus on the joint use of ocean and sea-ice data as well as social-ecological driv.rs. ARCPATH was able to prov.de an improv.d framework for predicting the near-term v.riation of Arctic climate on spatial scales relev.nt to society, as well as ev.luating possible related changes in socioeconomic realms. In summary, through the integration of information from sev.ral different disciplines and research approaches, ARCPATH serv.d to create new and v.luable knowledge on crucial issues, thus prov.ding new pathways to action for Arctic communities.

关键词： Recent v.ntures in Interdisciplinary Arctic Research:The ARCPATH Project

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