RE-EVALUATION OF SPECTRAL AND KINETIC-PROPERTIES OF HO2 AND (0--)2 FREE-RADICALS

Abstract— The spectra and molar absorbances of the HO2 and O2‐ free radicals have been redetermined in aqueous formate solutions by pulse and stopped‐flow radiolysis as well as by 60Co gamma‐ray studies. The extinction coefficients at the corresponding maxima and 23°C are 225= 1400 ± 80 M‐1 cm‐1 and 225= 2350 ± 120 M‐1 cm‐1 respectively. Reevaluation of earlier published rate data in terms of the new extinction coefficients yielded the following rate constants for the spontaneous decay of HO2 and O2‐: KHo2+HO2= (8.60 ± 0.62) × 105M‐1 s‐1; KHo2+O2‐= (1.02 ± 0.49) × 108M‐1 s‐1; KHo2+O2‐ < 0.35 M‐1 s‐1. For the equilibrium HO2→ O2‐+ H+ the dissociation constant is KHo2= (2.05 ± 0.39) × 10‐5M or pKHO2= 4.69 ± 0.08. G(O2‐) has been evaluated as a function of formate concentration. Copyright © 1978, Wiley Blackwell. All rights reserved