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J Phys Chem B. 2013 May 9;117(18):5675-82. doi: 10.1021/jp401510m. Epub 2013 Apr 29.

Experimental measurement of speeds of sound in dense supercritical carbon monoxide and development of a high-pressure, high-temperature equation of state.

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  • 1Chemical Science Directorate, Lawrence Livermore National Laboratory, Livermore, California 94550, United States. zaug1@llnl.gov

Abstract

We report the adiabatic sound speeds for supercritical fluid carbon monoxide along two isotherms, from 0.17 to 2.13 GPa at 297 K and from 0.31 to 3.2 GPa at 600 K. The carbon monoxide was confined in a resistively heated diamond-anvil cell, and the sound speed measurements were conducted in situ using a recently reported variant of the photoacoustic light scattering effect. The measured sound speeds were then used to parametrize a single site dipolar exponential-6 intermolecular potential for carbon monoxide. PρT thermodynamic states, sound speeds, and shock Hugoniots were calculated using the newly parametrized intermolecular potential and compared to previously reported experimental results. Additionally, we generated an analytical equation of state for carbon monoxide by fitting to a grid of calculated PρT states over a range of 0.1-10 GPa and 150-2000 K. A 2% mean variation was found between computed high-pressure solid-phase densities and measured data-a surprising result for a spherical interaction potential. We further computed a rotationally dependent fluid to β-solid phase boundary; results signal the relative magnitude of short-range rotational disorder under conditions that span existing phase boundary measurements.

PMID:
23586650
[PubMed - indexed for MEDLINE]
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