Ozone Solubility in Aqueous Solutions of Perchlorates and Other Electrolytes: Correction of the Weisenberger-Schumpe Model Parameters for the ClO₄⁻ and O₃

Development and Validation of the Successor to the Weisenberger–Schumpe Solubility Model of Gas in Aqueous Electrolytes: Solubilities of Ar, He, Xe, and O3 in Electrolyte Solutions at 25 °C

“…However for the WS model, although the deviation between the calculated and the experimental Δ K Y–X,1‑1‑2 /Δ K Y–X,1‑1 ratios was minimal (1.5 and 1.51, respectively), the deviation between the calculated and experimental Δ K Y–X,2‑2 /Δ K Y–X,1‑1 ratios (1.0 vs 0.61, respectively) was still significant. Similar observations were made in our work on ozone solubility in solutions of electrolytes of different valence types (e.g., 1-1, 1-1-2, and 2-2), that is, the experimental K S values obtained for these electrolytes could not be simultaneously and accurately described by the WS model. Herein, we tried to determine whether this problem is related to errors in the definition of K S or is a feature of the WS model.…”

“…Xe (99.9999%) was supplied by a medical Xe manufacturer (LLC Akela-N, Moscow, Russia). Some of the employed solutions had been used in previous works, 12,13 while others were prepared using fresh triple distilled water with a resistance of ≥18. •xH 2 O did not exhibit a significant weight loss, whereas a marked weight loss was observed at 200 °C (in which case, the weight stabilized within 38 h).…”

“…The parameters h i and h G,Y were determined using the most reliable set of 43 experimental K S values obtained for electrolytes of 1-1 to 3-3-2-2-2 valence types. Out of these, 38 constants were taken from the present study and our previous works, 12,13 while the other five constants were taken from the works of other authors: K S,Ar = 0.1067 L mol −1 in LiCl, 18 K S,Ar = 0.1437 L mol −1 in NaCl, 18 K S,Ar = 0.0957 L mol −1 in LiCl, 19 K S,Ar = 0.1415 L mol −1 in NaCl, 19 and K S,Ar = 0.1298 L mol −1 in KCl. 19 It should be noted that the K S for ozone in HClO 4 solutions was estimated to be −0.0172 L mol −1 when the initial concentration was in the range 0−1 mol L −1 .…”

“…19 It should be noted that the K S for ozone in HClO 4 solutions was estimated to be −0.0172 L mol −1 when the initial concentration was in the range 0−1 mol L −1 . 12 The ion-and gas-specific parameters for KH and WS models were determined using the linear least-squares fit. 12 The weight coefficients were not considered in the calculations to ensure the uniformity of relative deviations for all the experimental values.…”

“…12 The ion-and gas-specific parameters for KH and WS models were determined using the linear least-squares fit. 12 The weight coefficients were not considered in the calculations to ensure the uniformity of relative deviations for all the experimental values. The values of two parameters were forcibly fixed 20 because of the underdetermination of the systems of normal equations in KH and WS models (eqs 7 and 18).…”