Frozen Hydrogen Peroxide and Nitrite Solution: The Acceleration of Benzoic Acid Oxidation via the Decreased pH in Ice

We investigated benzoic acid oxidation via the reaction of hydrogen peroxide (H₂O₂) and nitrite (NO₂^-). The oxidation of benzoic acid by reactive nitrous acid (HONO) was negligible, and the reactivity of the H₂O₂/NO₂^- system decreased with a decrease in temperature under aqueous conditions. However, freezing markedly accelerated the chemical reaction. Based on Raman microscope measurements, concentrated species were confirmed in certain regions of the ice. We proposed that the change in nitrite speciation (accordingly, a decrease in the pH below pK_a), derived from the freezing concentration effect, was the reason for the accelerated reactions. The oxidation characteristics of the system were monitored under varying conditions, such as initial pH, dosage ratio, benzoic acid concentration, and reaction with various benzene derivatives. The ultrahigh-performance liquid chromatography/electrospray ionization/mass spectrometry (UHPLC/ESI/MS) measurement showed that peroxynitrous acid (HOONO)-mediated oxidation generated hydroxylated and nitrated byproducts. Additionally, decarboxylated products were detected, indicating direct electron transfer from the organic compounds to HOONO. As freezing is a global phenomenon, and H₂O₂ and NO₂^- are ubiquitous in the environment, the transformation of aromatic compounds with H₂O₂/NO₂^- in cold environments must be considered in environmental chemistry.