Cyanide Thermodynamics. III. Enthalpies and Entropies of Ionization of Water and Hydrogen Cyanide

Abstract

The heats (enthalpy changes) associated with the ionization of water and of hydrogen cyanide have been determined by titration calorimetry at 25°C as a function of ionic strength up to 5 M in both NaCl and NaClO₄ media. The enthalpy changes for both reactions exhibit a 'medium effect' with ?H being more positive in NaCl than in NaClO₄ and with the difference becoming more pronounced with increasing ionic strength. This is attributed to the greater solvation of Cl^- cf. CN^- in aqueous solution. The present ?H values are similar to previous published results at high ionic strengths, and are in excellent agreement with the well established literature values at infinite dilution. The present ?H values were combined with literature stability constant data to calculate the corresponding entropies for the ionization of H₂O and HCN as a function of ionic strength.