Specific-Ion Effects Unveil a Route for Modulating Oxidatively Triggered Acid Systems for Reservoir Applications

On-demand in situ preparation of industrially relevant organic acids, namely, methanesulfonic acid, triflic acid, and trifluoroacetic acid, is demonstrated in this study. Sodium and potassium bromate were found to selectively oxidize a series of ammonium salts NH₄X, where X = OMs, OTf, or OTFAc, with characteristic clock reaction behavior. The redox system undergoes rapid acid formation following an extended induction time at 150 °C and is identified as a potential candidate for high-temperature oil field chemistry applications where on-demand acid placement is required. Although the reaction kinetics for acid formation from NH₄X salts where X = Cl, Br, F, or SO₄^2- follows a pK_a trend, the rates of formation of the organic acids are much slower and deviate from this trend. Furthermore, we demonstrate that the rate of acid formation can be modulated by the addition of alkali metal salts, with the strongest effect observed from LiBr. Spectroscopic studies implicate the formation of lithium bromate ion pairs that slow or altogether inhibit the oxidation of NH₄⁺. Additionally, the presence of Br^- alters the reaction path, eliminating the clock behavior and creating a pathway for Li⁺ to strongly inhibit the redox reaction. From these studies, a method for slowing ammonium oxidation under reservoir conditions to sufficiently delay acid formation until the precursors are placed in the zone of interest is identified.