Direct pH Measurement of NaCl-Bearing Fluid with an in Situ Sensor at 400°C and 40 Megapascals

The pH of concentrated NaCl-HCl fluids (0.57 mole of NaCl per kilogram of water) has been measured at supercritical conditions of water with a yttria-stabilized zirconia sensor in a titanium flow reactor. At 400°C and 40 megapascals, the in situ pH of the fluids, ranging from 3.3 to 6.2, differs greatly from its original value of 1.9 to 7.6 at ambient conditions. The measurements agree well with theoretical predictions, showing strong associations of HCl° and NaOH° complexes in high-temperature fluids. The pH sensor provides a powerful tool to investigate unambiguously the distribution of species in aqueous fluids at elevated temperatures and pressures.