The influence of ionic strength on carbonate-based spectroscopic barometry for aqueous fluids: an in-situ Raman study...

The Raman wavenumber of the symmetric stretching vibration of carbonate ion (ν₁-CO₃^2-) was measured in three aqueous solutions containing 2.0 mol·L^-1 Na₂CO₃ and 0.20, 0.42, or 0.92 mol·L^-1 NaCl, respectively, from 122 to 1538 MPa at 22 °C using a moissanite anvil cell. The ν₁ Raman signal linearly shifted to higher wavenumbers with increasing pressure. Most importantly, the slope of ν₁-CO₃^2- Raman frequency shift (∂ν₁/∂P)_I was independent of NaCl concentration. Moreover, elevated ionic strength was found to shift the apparent outline of the carbonate peak toward low wavenumbers, possibly by increasing the proportion of the contact ion pair NaCO₃^-. Further investigations revealed no cross-interaction between the pressure effect and the ionic strength effect on the Raman spectra, possibly because the distribution of different ion-pair species in the carbonate equilibrium was largely pressure-independent. These results suggested that the ionic strength should be incorporated as an additional constraint for measuring the internal pressure of various solution-based systems. Combining the ν₁-CO₃^2- Raman frequency slope with the pressure herein with the values for the temperature or the ionic strength dependencies determined from previous studies, we developed an empirical equation that can be used to estimate the pressure of carbonate-bearing aqueous solutions.