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The effect of Cl- ion on the anodic iron dissolution in H2SO4 solutions containing H2S has been studied by using electrochemical polarization curve measurements. The competitive adsorption for Cl- and HS- ions at an anodic potential has been calculated using the CNDO/2 method. The results show that a certain concentration of the Cl- ion can be adsorbed steadily and inhibit the anodic reaction of iron catalyzed by HS-. However, when the Cl- ion reaches the saturation adsorption, it begins to promote the anodic reaction of iron due to the increased negative charge of iron atoms.