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UV spectroscopic determination of the chlorine monoxide (ClO) / chlorine peroxide (ClOOCl) thermal equilibrium constant

Abstract. The thermal equilibrium constant between the chlorine monoxide radical (ClO) and its dimer, chlorine peroxide (ClOOCl), was determined as a function of temperature between 228–301 K in a discharge flow apparatus using broadband UV absorption spectroscopy. A third law fit of the equilibrium values determined from the experimental data provides the expression: Keq = 2.16 × 10−27 e(8533 ± 25 K/T) cm3 molecule−1. A second law analysis of the data deviates minimally: Keq = (2.06 ± 1.27) × 10−27 e(8546 ± 123 K/T) cm3 molecule−1. From the slope of the van't Hoff plot in the third law analysis, the enthalpy of formation for ClOOCl is calculated, ∆H◦f (298 K) = 129.9 ± 0.6 kJ mol−1. The equilibrium constant results from this study suggest that the uncertainties in Keq recommended in the most recent (year 2015) NASA JPL Data Evaluation can be significantly reduced.
