Corrosion process of silver in environments containing 0.1 ppm H₂S and 1.2 ppm NO₂

Abstract

Abstract The effects of sub‐ppm levels of nitrogen dioxide and hydrogen sulfide, and the adsorbed water on the corrosion of silver were studied in order to get a better understanding of the atmospheric corrosion process. An in situ mass balance was taken to monitor the kinetic behavior and the surface and the corrosion film were analyzed by X‐ray photoelectron spectroscopy (XPS). In H 2 S environments, the tarnish film consisted of silver sulfide, and the corrosion rate depended upon oxygen as well as relative humidity. Silver was oxidized by only oxygen and the corrosion behavior conformed to a type of a parabolic law. In NO 2 environments, the corrosion film consisted of nitrate and oxide, and the corrosion rate depended upon oxygen as well as relative humidity. Compared to hydrogen sulfide, the formation of silver nitrate being strong hydroscopic reduced the effect of humidity on corrosion rate. In H 2 S + NO 2 environment, the corrosion process was independent of both oxygen and humidity, and the kinetic behavior conformed to a linear law. The difference of corrosion process between H 2 S or NO 2 environments and H 2 S + NO 2 environments is thought to be due to the role of nitrogen dioxide as an ionic conductor and the presence of strong oxidizing species such as elemental sulfur which can be produced from the following reaction: H 2 S + 2NO 2 → S + 2HNO 2 . In addition, the role of adsorbed water affecting atmospheric corrosion process was mentioned based on the amount of adsorbed water from the three types of exposure environments.