Raman spectroscopic characterization of gas mixtures .2. Quantitative composition and pressure determination of the CO2-CH4 system

Raman spectral parameters were determined for the nu(1) band of CH4 and the nu(1) and 2 nu(2) bands (Fermi diad) of CO2 in pure CO2 and CO2-CH4 mixtures at pressures up to 700 bars and room temperature, Peak position, area, height, and width were investigated as functions of pressure and composition, The peak positions of the CH4 and CO2 bands shift to lower relative wavenumbers as fluid pressure is increased, The peak position of the lower-wavenumber member of the Fermi diad for CO2 is sensitive to fluid composition, whereas the peak positions of the CH4 band and the upper Fermi diad member for CO2 are relatively insensitive in the CO2-CH4 system, The magnitude of the shifts in each of the three peak positions (as a function of pressure) is sufficient to be useful as a monitor of fluid pressure, The relative molar proportions in a CO2-CH4 mixture may be determined from the peak areas: the ratio of the peak areas of the CH4 band and the CO2 upper Fermi diad member is very sensitive to composition, whereas above about 100 bars, it is Insensitive to pressure, Likewise, the peak height ratio is very sensitive to composition but also to fluid pressure, The individual peak widths of CO2 and CH4, as well as the ratios of the widths of the CH4 peak to the CO2 peaks are a sensitive function of pressure and, to a lesser extent, composition, Thus, upon determination of fluid composition, the peak width ratios may be used as a monitor of fluid pressure, The application of these spectral parameters to a suite of natural CO2-CH4 inclusions has yielded internally-consistent, quantitative determinations of the fluid composition and density.