TY - JOUR
T1 - Liquid-vapor isotopic fractionation factors of diatomic fluids
T2 - A direct comparison between molecular simulation and experiment
AU - Chialvo, Ariel A.
AU - Horita, Juske
N1 - Funding Information:
This research was sponsored by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences under Contract No. DE-AC05-00OR22725 with Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC. The authors express gratitude to Dr. Jadran Vrabec (Institut für Technische Thermodynamik und Thermische Verfahrenstechnick, Stuttgart) for the courtesy of providing the tabulation of the VLE data of their quadrupolar parametrization used in this paper, as well as to Dr. Thomas Driesner (Isotope Geochemistry and Mineral Resources, ETH Zürich) and Dr. V. B. Polyakov (Institute of Experimental Mineralogy, Russian Academy of Sciences, Chernogolovka) for insightful discussions.
PY - 2006
Y1 - 2006
N2 - Liquid-vapor fractionation factors of molecular fluids are studied by molecular-based simulation, Gibbs ensemble Monte Carlo, and isothermal-isochoric molecular dynamics of realistic models for N 2, O 2, and CO. The temperature dependence of the fractionation factors for 15N 14N/ 14N 2, 15N 2/ 14N 2, 18O 16O/ 16O 2, 18O 2/ 16O/ 16O 2, 13C 16O/ 12C 16O, and 12C 18O/ 12C 16O along the vapor-liquid coexistence curves as predicted by simulation is compared with the existing experimental data to assess the accuracy of ℏ 2-order Kirkwood-Wigner free energy expansion for specific model parametrizations. Predictions of the fractionation factors for other isotopologue pairs, including 18O 17O/ 16O 2, 16O 17O/ 16O 2, and 17O 2/ 16O 2, as well as tests of some approximations behind the microscopic interpretation of the fractionation factors are also given.
AB - Liquid-vapor fractionation factors of molecular fluids are studied by molecular-based simulation, Gibbs ensemble Monte Carlo, and isothermal-isochoric molecular dynamics of realistic models for N 2, O 2, and CO. The temperature dependence of the fractionation factors for 15N 14N/ 14N 2, 15N 2/ 14N 2, 18O 16O/ 16O 2, 18O 2/ 16O/ 16O 2, 13C 16O/ 12C 16O, and 12C 18O/ 12C 16O along the vapor-liquid coexistence curves as predicted by simulation is compared with the existing experimental data to assess the accuracy of ℏ 2-order Kirkwood-Wigner free energy expansion for specific model parametrizations. Predictions of the fractionation factors for other isotopologue pairs, including 18O 17O/ 16O 2, 16O 17O/ 16O 2, and 17O 2/ 16O 2, as well as tests of some approximations behind the microscopic interpretation of the fractionation factors are also given.
UR - http://www.scopus.com/inward/record.url?scp=33746321282&partnerID=8YFLogxK
U2 - 10.1063/1.2215611
DO - 10.1063/1.2215611
M3 - Article
AN - SCOPUS:33746321282
VL - 125
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
SN - 0021-9606
IS - 3
M1 - 034510
ER -