Thermal expansion and stability limits of generalized van der Waals fluids

doi:https://doi.org/10.1021/j100078a034

Title: Thermal expansion and stability limits of generalized van der Waals fluids

Full Record
Other Related Research

Abstract

Generalized van der Waals equations of state can exhibit density anomalies, as characterized by a negative thermal expansion coefficient in some region of the phase diagram, when either the hard core volume, b, or the mean field attractive parameter, a, are made temperature-dependent. If b decreases as the temperature increases, negative thermal expansion occurs at all temperatures. At a given temperature, the liquid becomes anomalous when the pressure is increased; hence the P-T projection of the locus of density maxima has positive slope. The locus of density maxima extends to zero temperature when b is finite at T = 0, and it terminates at a minimum temperature if b diverges at T = 0. If, on the other hand, a increases with temperature while the core volume remains constant, generalized van der Waals fluids exhibit density anomalies that disappear at high pressure. Hence, in this case the locus of density maxima has a negative slope in the P-T plane. The liquid spinodal is re-entrant both when a increases as the temperature increases and when b increases as the temperature decreases, becoming infinite at T = 0. 38 refs., 20 figs., 1 tab.

Authors:

Chakravarthi, A S; Debenedetti, P G; Yeo, S D ^[1]; Sastry, S ^[2]

Princeton Univ., NJ (United States)
Boston Univ., MA (United States)

Publication Date:: 1994-07-07

OSTI Identifier:: 7243350

DOE Contract Number:: FG02-87ER13714

Resource Type:: Journal Article

Journal Name:: Journal of Physical Chemistry; (United States)

Additional Journal Information:: Journal Volume: 98:27; Journal ID: ISSN 0022-3654

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; LIQUIDS; EQUATIONS OF STATE; THERMAL EXPANSION; THERMODYNAMIC PROPERTIES; VAN DER WAALS FORCES; HEAVY WATER; MATHEMATICAL MODELS; SILICA; WATER; CHALCOGENIDES; EQUATIONS; EXPANSION; FLUIDS; HYDROGEN COMPOUNDS; MINERALS; OXIDE MINERALS; OXIDES; OXYGEN COMPOUNDS; PHYSICAL PROPERTIES; SILICON COMPOUNDS; SILICON OXIDES; 360606* - Other Materials- Physical Properties- (1992-); 990200 - Mathematics & Computers; 661300 - Other Aspects of Physical Science- (1992-)

Citation Formats


                    Chakravarthi, A S, Debenedetti, P G, Yeo, S D, and Sastry, S. Thermal expansion and stability limits of generalized van der Waals fluids.  United States: N. p., 1994. 
        Web.  doi:10.1021/j100078a034.

Copy to clipboard


                    Chakravarthi, A S, Debenedetti, P G, Yeo, S D, & Sastry, S. Thermal expansion and stability limits of generalized van der Waals fluids.  United States.  https://doi.org/10.1021/j100078a034

Copy to clipboard


                    Chakravarthi, A S, Debenedetti, P G, Yeo, S D, and Sastry, S. Thu .  
        "Thermal expansion and stability limits of generalized van der Waals fluids".  United States.  https://doi.org/10.1021/j100078a034.

Copy to clipboard


                    
@article{osti_7243350,

  title        = {Thermal expansion and stability limits of generalized van der Waals fluids},

  author       = {Chakravarthi, A S and Debenedetti, P G and Yeo, S D and Sastry, S},

  abstractNote = {Generalized van der Waals equations of state can exhibit density anomalies, as characterized by a negative thermal expansion coefficient in some region of the phase diagram, when either the hard core volume, b, or the mean field attractive parameter, a, are made temperature-dependent. If b decreases as the temperature increases, negative thermal expansion occurs at all temperatures. At a given temperature, the liquid becomes anomalous when the pressure is increased; hence the P-T projection of the locus of density maxima has positive slope. The locus of density maxima extends to zero temperature when b is finite at T = 0, and it terminates at a minimum temperature if b diverges at T = 0. If, on the other hand, a increases with temperature while the core volume remains constant, generalized van der Waals fluids exhibit density anomalies that disappear at high pressure. Hence, in this case the locus of density maxima has a negative slope in the P-T plane. The liquid spinodal is re-entrant both when a increases as the temperature increases and when b increases as the temperature decreases, becoming infinite at T = 0. 38 refs., 20 figs., 1 tab.},

  doi          = {10.1021/j100078a034},

  url          = {https://www.osti.gov/biblio/7243350},
  journal      = {Journal of Physical Chemistry; (United States)},

  issn         = {0022-3654},

  number       = ,

  volume       = 98:27,

  place        = {United States},

  year         = {1994},

  month        = {7}

}

Copy to clipboard

Journal Article:

https://doi.org/10.1021/j100078a034

Other availability

Find in Google Scholar

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Excess free energy and Casimir forces in systems with long-range interactions of van der Waals type: General considerations and exact spherical-model results

Journal Article Dantchev, Daniel ; Institute of Mechanics, Bulgarian Academy of Sciences, Academic Georgy Bonchev Street Building 4, 1113 Sofia ; Diehl, H W ; ... - Physical Review. E, Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics

We consider systems confined to a d-dimensional slab of macroscopic lateral extension and finite thickness L that undergo a continuous bulk phase transition in the limit L{yields}{infinity} and are describable by an O(n) symmetrical Hamiltonian. Periodic boundary conditions are applied across the slab. We study the effects of long-range pair interactions whose potential decays as bx{sup -(d+{sigma})} as x{yields}{infinity}, with 2<{sigma}<4 and 2<d+{sigma}{<=}6, on the Casimir effect at and near the bulk critical temperature T{sub c,{infinity}}, for 2<d<4. These interactions decay sufficiently fast to leave bulk critical exponents and other universal bulk quantities unchanged--i.e., they are irrelevant in the renormalizationmore »« less
https://doi.org/10.1103/PHYSREVE.73.016131
The Concept of Negative Capacitance in Ionically Conductive Van der Waals Ferroelectrics

Journal Article Neumayer, Sabine M. ; Tao, Lei ; O'Hara, Andrew ; ... - Advanced Energy Materials

Negative capacitance (NC) provides a path to overcome the Boltzmann limit that dictates operating voltages in transistors and, therefore, may open up a path to the challenging proposition of lowering energy consumption and waste heat in nanoelectronic integrated circuits. Typically, NC effects in ferroelectric materials are based on either stabilizing a zero-polarization state or slowing down ferroelectric switching in order to access NC regimes of the free-energy distribution. Here, a fundamentally different mechanism for NC, based on CuInP ₂S ₆, a van der Waals layered ferrielectric, is demonstrated. Using density functional theory and piezo-response force microscopy, it is shown thatmore »« less
https://doi.org/10.1002/aenm.202001726
Antiferromagnetism in the van der Waals layered spin-lozenge semiconductor ${CrTe}_{3}$

Journal Article McGuire, Michael A. ; Garlea, V. Ovidiu ; KC, Santosh ; ... - Physical Review B

We have investigated the crystallographic, magnetic, and transport properties of the van der Waals bonded, layered compound CrTe ₃ on single-crystal and polycrystalline materials. Furthermore, the crystal structure contains layers made up of lozenge-shaped Cr ₄ tetramers. Electrical resistivity measurements show the crystals to be semiconducting, with a temperature dependence consistent with a band gap of 0.3 eV. The magnetic susceptibility exhibits a broad maximum near 300 K characteristic of low dimensional magnetic systems. Weak anomalies are observed in the susceptibility and heat capacity near 55 K, and single-crystal neutron diffraction reveals the onset of long-range antiferromagnetic order at thismore »« less
https://doi.org/10.1103/PhysRevB.95.144421

Full Text Available
Singularity-free interpretation of the thermodynamics of supercooled water

Journal Article Sastry, S ; Debenedetti, P G ; Sciortino, F ; ... - Physical Review. E, Statistical Physics, Plasmas, Fluids, and Related Interdisciplinary Topics

The pronounced increases in isothermal compressibility, isobaric heat capacity, and in the magnitude of the thermal expansion coefficient of liquid water upon supercooling have been interpreted either in terms of a continuous, retracing spinodal curve bounding the superheated, stretched, and supercooled states of liquid water, or in terms of a metastable, low-temperature critical point. Common to these two scenarios is the existence of singularities associated with diverging density fluctuations at low temperature. We show that the increase in compressibility upon lowering the temperature of a liquid that expands on cooling, like water, is not contingent on any singular behavior, butmore »« less
https://doi.org/10.1103/PhysRevE.53.6144
Piezoelectric domain walls in van der Waals antiferroelectric CuInP2Se6

Journal Article Dziaugys, Andrius ; Kelley, Kyle ; Brehm, John A. ; ... - Nature Communications

Polar van der Waals chalcogenophosphates exhibit unique properties, such as negative electrostriction and multi-well ferrielectricity, and enable combining dielectric and 2D electronic materials. Using low temperature piezoresponse force microscopy, we revealed coexistence of piezoelectric and non-piezoelectric phases in CuInP2Se6, forming unusual domain walls with enhanced piezoelectric response. From systematic imaging experiments we have inferred the formation of a partially polarized antiferroelectric state, with inclusions of structurally distinct ferrielectric domains enclosed by the corresponding phase boundaries. The assignment is strongly supported by optical spectroscopies and density-functional-theory calculations. Enhanced piezoresponse at the ferrielectric/antiferroelectric phase boundary and the ability to manipulate this entitymore »« less
https://doi.org/10.1038/s41467-020-17137-0

Full Text Available

Similar Records