Gaseous solubilities of carbon dioxide (1), hydrogen sulfide (2), and their binary mixture (x(2) ≈ 0.2, 0.5, 0.8) have been measured in the ionic liquid 1-octyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide ([C(8)mim][Tf(2)N]) at temperatures ranging from (303.15 to 353.15) K and at pressures under 2 MPa. The observed PTx solubility data were used to obtain Henry's law constants and correlated by three models: (1) the simple Krichevsky-Kasarnovsky (KK) equation, (2) a model comprised of the extended Henry's law and the Pitzer's virial expansion for the excess Gibbs free energy, and (3) the generic Redlich-Kwong (RK) cubic equation of state proposed for gas-ionic liquid systems. The correlations from the three models show quite good consistency with the experimental data for IL/CO(2) and IL/H(2)S binary mixtures within experimental uncertainties. For IL/CO(2)/H(2)S ternary mixtures, the RK model shows the best correlation with the experimental data. The comparison showed that the solubility of H(2)S is about two times as great as that of CO(2) in the ionic liquid studied in this work. It was further found, by comparison of the experimental data of this study with those of previous reports, that the solubility of H(2)S in [C(n)mim][Tf(2)N] ILs increases as the number of carbon atoms in the alkyl substituent of methylimidazolium cation, n, increases. In addition, quantum chemical calculations at DFT/B3LYP level of theory using 6-311+G(d) and 6-311++G(2d,2p) basis sets were performed on the isolated systems studied in this work to provide explanations from a molecular point of view for the observed experimental trends.
Tarnishing layers grown on copper exposed to air contaminated by traces of sulfur dioxide and/or hydrogen sulfide were detected by a coulometric and characterized by a chemical method. Depending on the nature of the corrosive gas, or on the use of a gas mixture, it was found that sulfate, sulfide, oxides or a mixed oxide-sulfide compound could be formed in these conditions. The same tarnishing products were found, either in hydrogen sulfide or in a sulfur dioxide + hydrogen sulfide mixture, and the same linear growth law of the copper (I) sulfide was also found, within the limits of the duration of the corrosion test, in the two gaseous environments.Die auf Kupfer in mit Spuren von Schwefeldioxid undioder Schwefelwasserstoff verunreinigter Luft entstandenen Anlaufschichten wurden mit coulornetrischen Methoden nachgewiesen und mit einer chemischen Methode identifiziert. Aufgrund der Ergebnisse entstehen je nach dem einwirkenden aggressiven Gas bzw. Gasgemisch Sulfate, Sulfide, Oxide oder Gemische von Oxiden und Sulfiden. Sowohl in Schwefelwasserstoff als auch in dessen Gemischen mit Schwefeldioxid treten die gleichen Produkte in den Anlaufschichten auf, und fur die Bildung von Cu(1)sulfidschichten gilt (im Rahmen der benutzten Versuchsdauer) in beiden Medien das gleiche lineare Zeitgesetz.
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