Accurate rate constants for decomposition of aqueous nitrous acid

Decomposition of nitrous acid in aqueous solution has been studied by stopped flow spectrophotometry to resolve discrepancies in literature values for the rate constants of the decomposition reactions. Under the conditions employed, the rate-limiting reaction step comprises the hydrolysis of NO(2). A simplified rate law based on the known elementary reaction mechanism provides an excellent fit to the experimental data. The rate constant, 1.34 × 10(-6) M(-1) s(-1), is thought to be of higher accuracy than those in the literature as it does not depend on the rate of parallel reaction pathways or on the rate of interphase mass transfer of gaseous reaction products. The activation energy for the simplified rate law was established to be 107 kJ mol(-1). Quantum chemistry calculations indicate that the majority of the large activation energy results from the endothermic nature of the equilibrium 2HNO(2) ? NO + NO(2) + H(2)O. The rate constant for the reaction between nitrate ions and nitrous acid, which inhibits HNO(2) decomposition, was also determined.