DOE OSTI2018
The effect of HCO 3 – (aq) on CO 2 corrosion of carbon steel was investigated in deaerated 3.5 wt% NaCl solutions at 30 °C from pH 3.96 to 7.15. In the CO 2 -saturated solutions, the pH was adjusted with different HCO 3 – (aq) concentrations, c[HCO 3 – (aq)]. The corrosion rate decreased by a factor of 2 as the pH and c[HCO 3 – (aq)] increased. The cathodic current density during polarization increased at higher pH with higher c[HCO 3 – (aq)], indicating that HCO 3 – (aq) acted as an additional hydrogen source for the hydrogen evolution reaction. As the pH increased, the active dissolution regions displayed similar anodic Tafel slopes and suggested a modified Bockris mechanism for the Fe oxidation reaction. The exchange current densities for the half reactions were calculated to study kinetics of the anodic and cathodic half reactions independently. The anodic exchange current density ( j 0,a ) increased by one order of magnitude in the presence of CO 2 , indicating the involvement of CO 2 (aq) in the Fe oxidation reaction. As the pH and c[HCO 3 – (aq)] increased, the cathodic exchange current density ( j 0,c ) decreased by a factor of 50 because the increase in j 0,c [HCO 3 – (aq)] was not high enough to compensate the decline from the other hydrogen sources, especially j 0,c [H + (aq)]; and j 0,a decreased by a factor of 2.4 because HCO 3 – (aq) may have competed with CO 2 (aq) for the surface coverage and the increase in j 0,a [CO 2 (aq)] could not compensate the decrease in j 0,a [CO 2 (aq)]. It suggests that the reaction rate constant of HCO 3 – (aq) was smaller than CO 2 (aq) for the anodic half reaction and was smaller than H + (aq) for the cathodic half reaction. The XPS results verified that the corrosion products transitioned from iron carbonate to hydroxide as the pH increased while iron carbonate remained the major product. As the pH increased with HCO 3 – (aq), a second time constant was observed at lower frequencies of the electrochemical impedance spectroscopy (EIS) results.