Thermodynamics of Protonation and Sodium Binding of Sulfate in Concentrated NaCl and CsCl Solutions Studied by Raman Spectroscopy

Abstract

The protonation constant (pKa) of SO42–(aq) has been determined at ionic strengths 0.5 M ≤I ≤4.0 M in NaCl and CsCl media at 25˚C by using Raman spectroscopy. These data were used to calculate the association constant of the NaSO4–(aq) ion pair in CsCl media. The results are in excellent agreement with previous values obtained by other techniques. The (pKa) was also measured at I = 4 M in both media at temperatures up to 85˚C and the associated enthalpy and entropy changes were calculated. However, reliable thermodynamic data for the ion-pairing reaction could not be obtained at higher temperatures probably because of competition from CsSO4–(aq).