Low Surface Coverage Interactions of Sulfur Dioxide on Selected Transition Metal Catalysts from 273 to 423 °K

Abstract

Calorimetric beats of adsorption for sulfur dioxide at low surface coverages from 0.004 to 0.600 μmol m−2 on a number of supported transition metal catalysts have been measured between 273 and 423 °K mainly by an adiabatic technique. The catalysts included Fe2O3, Mn2O3, V2O5, MnSO4, and "NiS" ail supported on silica gel.Sulfur dioxide adsorption/desorption isotherms, nitrogen adsorption data, and chemical and infrared analyses were also determined to provide further ancillary information.Heats of adsorption at 423 °K for adsorbed amounts of 0.004 μmol m−2 varied with the adsorbent from nearly 39.0 for Mn2O3 on silica gel to 23.0 kcal mol−1 for the silica gel support medium. With increase in surface coverage to 0.600 μmol m−2 the heat values begin to steady at 6 to 7, 7 to 8, and 8 to 9 kcal mol−1 at 423, 373, and 323 °K, respectively, and less discrimination is observed among the various materials. Preadsorption of small amounts of sulfur dioxide on the supported oxides followed by oxygen admission caused sharp initial falls of as much as 7 to 8 kcal mol−1 in the heat values whereas preadsorption of oxygen followed by sulfur dioxide gave only slight heat increases of around 1 kcal mol−1.It is proposed that sulfur dioxide is chemisorbed on all surfaces with the strongest interactions occurring at the lowest coverages. Sulfates are formed on the oxides as confirmed by chemical analysis, and it is postulated that multiple hydrogen bond formation occurs on silica gel through the interaction of sulfur dioxide oxygen atoms with surface hydroxy groups.