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Determination of the temperature dependence of the equilibrium constants K n  ,n−1  for the reactions A  − B n  = A  − B n−1  + B where A −  equals Cl −  and O 2  −  and B is HOH, CH 3 OH, or CH 3 CN leads to the corresponding ΔH 0  n−1 , ΔG 0  n−1,n , and ΔS 0  n−1,n  values. The experimental technique is based on mass spectrometric detection of ions escaping from a high pressure ion source. At n = 1, Cl −  is solvated most strongly by methanol, then CH 3 CN and HOH. At higher n a cross over is observed with water becoming the best solvent. These results are in agreement with the positive transfer enthalpies and free energies for Cl −  from the liquid solvents HOH → CH 3 OH and HOH → CH 3 CN reported in the literature.O 2  −  is solvated more strongly than Cl −  appearing thus as an ion of "size" intermediate between Cl −  and F −  Again CH 3 OH gives the highest interaction for n = 1, however for n &gt; 1 water gives stronger interactions.

Solvation of Cl− and O2− with H2O, CH3OH, and CH3CN in the gas phase

Solvation of Cl⁻ and O₂⁻ with H₂O, CH₃OH, and CH₃CN in the gas phase