Interactions of CO2 and CO at fractional atmosphere pressures with iron and iron oxide surfaces: one possible mechanism for surface contamination?

The interactions of carbon dioxide and carbon monoxide at moderately high pressures with clean iron surfaces have been studied using x‐ray photoelectron spectroscopy (XPS) and static time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Clean iron surfaces were analysed after exposure to CO2 or CO gas having pressures of 10–104 Pa at 25 °C. Exposure to either gas results first in a thin surface film of FeO. In addition, this oxide is completely or partially covered with a carbonaceous layer. The thickness of the carbon layer is influenced by the type of gas used and its pressure. The ToF‐SIMS studies using isotopically labelled 13CO2 under the same reaction conditions show that the labelled carbon is not enriched on the surface and therefore no direct reaction occurs between the labelled carbon and the surface. It is proposed that the influence of either gas on the carbonaceous layer formed may be indirect: these gases may alter the equilibrium partial pressures of other adsorbates on the walls of the vacuum chamber. Copyright © 2002 John Wiley & Sons, Ltd.