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Surface Spectroscopic Analysis of HCN/NH3 Corrosion Products on Iron by Fourier Transform Infrared Photoacoustic Spectroscopy and X-ray Photoelectron Spectroscopy

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Surface analysis of the corrosion products formed on iron metal exposed to off gas from a HCN production process has been performed. The atmosphere contains HCN(g), NH3(g), and H2O(g) plus other trace gases. Iron gratings exposed to the atmosphere form a dark blue coating which pits the surface of the iron. Samples of the corroded iron surface were analyzed by FT-IR/photoacoustic spectroscopy (PAS) and x-ray photoelectron spectroscopy (XPS or ESCA). The mid-IR spectrum from PAS yielded peaks due to NH4 +, CN, and H2O. ESCA analysis confirmed that the surface iron was divalent, coordinated to cyanide, and no iron(II) oxide was present. Relative quantitation from ESCA showed a 1:4 ratio of NH4/CN type nitrogen, thus a specific single stoichiometry was not postulated for the corrosion product. Peak positions of the cyanide stretching frequencies suggest a mixed ferro(ferrocyanide) complex, with some ammonium as a counterion. This study illustrates the detailed structural information obtainable from FT-IR/PAS with ESCA and the applicability of FT-IR/PAS to corrosion problems.

Keywords: Infrared; Interferometry, mid-IR (photoacoustic), Photoacoustic, Surface analysis

Document Type: Research Article

DOI: http://dx.doi.org/10.1366/0003702824639358

Affiliations: 1: Department of Chemistry, University of Utah, Salt Lake City, Utah 84112 2: Department of Chemistry University of Pittsburgh, Pittsburgh, Pennsylvania 15260 3: Ciba Geigy Corporation, P.O. Box 11, River Road, St. Gabriel, Louisiana 70776

Publication date: September 1, 1982

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