A new methodology for the real-time in situ monitoring of atmospheric corrosion processes is presented. The mid-infrared spectra of surface films formed on polished copper substrates exposed to humid air containing sub-ppm levels of sulfur dioxide, nitric oxide, and hydrogen chloride were obtained by using a novel surface-sensitive infrared technique: real-time polarization modulation grazing angle reflection-absorption spectroscopy. The new methodology demonstrated improved signal-to-noise ratios, by a factor of 2.5, as compared to conventional Fourier transform infrared reflection absorption spectroscopy. Molecular spectroscopic data for water- and hydroxyl-containing species present at the metal surface were obtained with no interference from water vapor. Over the spectral region 4000-800 cm-1, bands were identified and assigned to nitro and nitrito adsorbates, to sulfite ions, and to bound water on the copper surface. Analysis of the time evolution and the profile composition of these bands is possible because of the sensitivity of this new optical sampling technique.
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