Corrosion of iron exposed to H2S saturated solution at pH 4 was studied by electrochemical impedance spectroscopy, weight loss coupons and surface analysis. Hydrogen permeation was also used as indirect means of evaluating the intensity of the proton reduction reaction leading to hydrogen entry into the metal. Since corrosion in this type of test solution results in the rapid build-up of a conductive and highly porous iron sulfide scale, a specific contribution of the film has to be considered. An impedance model was thus proposed. The faradaic anodic impedance consists of a two-step reaction with charge transfer and adsorptiondesorption. An additional contribution, associated with the conductive and highly porous iron sulfide film was added in parallel. This contribution, mostly visible in the 2 low frequency domain, presents a 45° tail associated with a porous electrode behavior. This model was well adapted to describe impedance diagrams measured at various exposure times, up to 620 hours. Charge transfer resistance determined from impedance analysis allowed calculating the evolution with time of the corrosion current density. A very good correlation was found between this corrosion current density and the hydrogen permeation current density. As expected in our experimental conditions, a permeation efficiency close to 100 % is demonstrated. Corrosion rate of 490 µm/year was measured by weight-loss specimens, confirming the validity of the impedance analysis, which resulted in a calculated corrosion rate of 530 µm/year.
Materials selection in the oil and gas industry relies on engineering standards, such as NACE TM0177 and NACE TM0284, which stipulate that oxygen pollution should be avoided during materials testing in H 2 S-containing media. In this paper, we explore the manner in which traces of oxygen can modify the test solution chemistry and the corrosion of/ hydrogen permeation across iron membranes in H 2 S-containing solutions. Oxygen pollution is shown to strongly influence solution chemistry, through the introduction of sulfur-oxygen reaction products resulting in bulk acidification. Weight loss, electrochemical methods, and solution chemistry measurements conclude that iron corrosion rates in the presence of oxygen pollution are doubled, when compared against the control system (without oxygen pollution). Unexpectedly, despite a lower pH and higher corrosion rates in the oxygen-polluted H 2 S-containing solutions, the hydrogen permeation rate decreases monotonically, relative to the control. We discuss how this observation is most likely related to a disruption of sulfur adsorbates involved in hydrogen entry promotion.
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