Enhancement of Structural fluctuation in the region connecting two kinds of critical points in temperature-pressure-composition three-dimensional phase diagram: Raman studies of benzene/CO2 binary systems up to supercritical region.
Pressure dependence of Raman spectra of benzene/CO2 two-component systems was systematically studied at different temperatures and compositions. We estimated the magnitude of inhomogeneous component in Raman bandwidth to get information on the structural fluctuation in the system. It was found that the inhomogeneous bandwidth attains a maximum on an isothermal plane in the temperature-pressure-composition three-dimensional phase diagram when the state point crosses the line connecting the region where the density fluctuation is large (the vicinity of the critical point of neat CO2) and the region where the concentration fluctuation in a binary system is enhanced (the vicinity of the critical solution point). By accumulating such data, we found that the points of large structural fluctuation comprise a sheet that includes the extension line of the gas-liquid equilibrium line in the phase diagram of neat CO2 and the line connecting critical solution points of the two-component system at different temperatures. Interaction between benzene and CO2 molecules in the supercritical region is briefly discussed.
Nakayama
Hideyuki
H
Department of Chemistry, Gakushuin University, 1-5-1 Mejiro, Toshimaku, Tokyo, 171-8588 Japan.
Murai
Miki
M
Tono-oka
Mariko
M
Masuda
Kumiko
K
Ishii
Kikujiro
K
D001554:Benzene / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D011312:Pressure; D012680:Sensitivity and Specificity; D013059:Spectrum Analysis, Raman / Q000295:instrumentation / Q000379:methods*; D013696:Temperature
D002245:Carbon Dioxide; D001554:Benzene