Shock tube/laser absorption measurement of the rate constant of the reaction: H₂O₂ + CO₂ 2OH + CO₂

We address the role of the linear mixing rule in the kinetics of the H₂O₂ decomposition system by reporting the rate constant for H₂O₂ + M = 2OH + M (M = Ar and CO₂) in the temperature range of 1087–1234 K at low pressures in a mixture of 20% CO₂ in Argon. The reaction rate constant was inferred from H₂O concentrations monitored by using a laser-absorption spectroscopy-based water diagnostic. To the best of our knowledge, this is the first measurement of the rate constant of this reaction in a mixture to be reported in literature. A significant discrepancy was found between the rate constants derived using the traditional linear mixing rule and the reduced pressure linear mixing rule. This discrepancy can have serious implications on the predictive accuracy of these kinetic models, especially under conditions relevant to the operation of supercritical CO₂ (sCO₂) power cycles that rely on oxy-fuel combustion in a working fluid comprised almost entirely of CO₂.