Aqueous oxidation of substituted dihydroxybenzenes by substituted benzoquinones

Strict anaerobic techniques, HPLC, and spectrophotometry are employed to explore rates of reaction between a series of substituted benzoquinone oxidants and substituted dihydroxybenzene reductants, which represent important redox-active moieties within natural organic matter (NOM). Benzoquinones and dihydroxybenzenes that lack electron-withdrawing substituents exhibit reversible reactions within the acidic range of natural waters. Initial rates for reversible reactions are proportional to [H+]-1, attributable to the greater reactivity of monoprotonated versus diprotonated dihydroxybenzene molecules. Reversible reactions are generally faster for pairs having higher thermodynamic driving force. Concentrations in reversible reactions eventually reach plateau values, which coincide with expected values calculated using standard reduction potentials. If a reactant benzoquinone possesses an electron-withdrawing substituent, reaction progress falls short of expected values. If a product benzoquinone possesses an electron-withdrawing substituent, reaction progress extends beyond what is thermodynamically predicted. Electron-withdrawing substituents raise the susceptibility of benzoquinones to side reactions such as the Michael addition reaction.