Equation of state for solid benzene valid for temperatures up to 470 K and pressures up to 1800 MPa
File(s)5.0065786.pdf (9.53 MB)
Published version
OA Location
Author(s)
Type
Journal Article
Abstract
The thermodynamic property data for solid phase I of benzene are reviewed and utilized to develop a new fundamental equation of state (EOS) based on Helmholtz energy, following the methodology used for solid phase I of CO2 by Trusler [J. Phys. Chem. Ref. Data 40, 043105 (2011)]. With temperature and molar volume as independent variables, the EOS is able to calculate all thermodynamic properties of solid benzene at temperatures up to 470 K and at pressures up to 1800 MPa. The model is constructed using the quasi-harmonic approximation, incorporating a Debye oscillator distribution for the vibrons, four discrete modes for the librons, and a further 30 distinct modes for the internal vibrations of the benzene molecule. An anharmonic term is used to account for inevitable deviations from the quasi-harmonic model, which are particularly important near the triple point. The new EOS is able to describe the available experimental data to a level comparable with the likely experimental uncertainties. The estimated relative standard uncertainties of the EOS are 0.2% and 1.5% for molar volume on the sublimation curve and in the compressed solid region, respectively; 8%–1% for isobaric heat capacity on the sublimation curve between 4 K and 278 K; 4% for thermal expansivity; 1% for isentropic bulk modulus; 1% for enthalpy of sublimation and melting; and 3% and 4% for the computed sublimation and melting pressures, respectively. The EOS behaves in a physically reasonable manner at temperatures approaching absolute zero and also at very high pressures.
Date Issued
2021-12-01
Date Acceptance
2021-10-08
Citation
Journal of Physical and Chemical Reference Data, 2021, 50 (4), pp.1-25
ISSN
0047-2689
Publisher
American Institute of Physics
Start Page
1
End Page
25
Journal / Book Title
Journal of Physical and Chemical Reference Data
Volume
50
Issue
4
Copyright Statement
© 2021 Author(s). Published by AIP Publishing on behalf of the National Institute of Standards and Technology.
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000719722700001&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry, Physical
Physics, Multidisciplinary
Chemistry
Physics
benzene
equation of state
Helmholtz energy
molar volume
quasi-harmonic approximation
solid
VAN-DER-WAALS
LIQUID-PHASE-EQUILIBRIA
HEAT-CAPACITIES
VAPOR-PRESSURE
CRYSTALLINE BENZENE
THERMODYNAMIC PROPERTIES
RAMAN-SPECTRUM
FREEZE-OUT
CARBON-TETRACHLORIDE
LATTICE-VIBRATIONS
Publication Status
Published
Article Number
ARTN 043104
Date Publish Online
2021-11-15