A unified equation for calculating methane vapor pressures in the CH4–H2O system with measured Raman shifts

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C–H symmetric stretching band (υ1) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C–H symmetric stretching band of methane in the vapor phase of CH4–H2O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 °C, and pressures up to 37 MPa. The results show that the CH4 υ1 band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH4-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell.