In Situ ATR-FTIR Spectroscopic Study of Adsorption of Perchlorate, Sulfate, and Thiosulfate Ions onto Chromium(III) Oxide Hydroxide Thin Films

A thin chromium oxide hydroxide colloid film has been used as a model of the passive stainless steel surface for studies of anion adsorption from aqueous solutions. The adsorption of perchlorate, sulfate, and thiosulfate ions has been investigated by in situ attenuated total reflection infrared (ATR-IR) spectroscopy. Surface charge was monitored from the surface excess concentrations of tetramethylammonium ions and of perchlorate ions using the infrared spectroscopic STIRS technique. The colloid film showed a high positive charge at low pH and a low negative charge at high pH. The adsorption of sulfate was only observed for a positive surface charge. The infrared spectrum of adsorbed sulfate was significantly altered by the interfacial electric field, but there was no evidence of sulfate coordination to surface Cr(III) ions. Thiosulfate gave adsorption behavior analogous to sulfate. Adsorption isotherms for sulfate and for thiosulfate were determined from infrared spectral data, and Langmuir binding constants of (2.3 ± 0.4) × 105 and (1.4 ± 0.4) × 105 M-1 were obtained for the respective adsorbates. The lack of chemical binding of sulfate and of thiosulfate to the chromium oxide hydroxide surface may be part of the basis for the corrosion-promoting properties of these ions at stainless steel surfaces.