Active Thermochemical Tables: accurate enthalpy of formation of hydroperoxyl radical, HO2.

Through the use of the Active Thermochemical Tables approach, the best currently available enthalpy of formation of HO2 has been obtained as delta(f)H(o)298 (HO2) = 2.94 +/- 0.06 kcal mol(-1) (3.64 +/- 0.06 kcal mol(-1) at 0 K). The related enthalpy of formation of the positive ion, HO2+, within the stationary electron convention is delta(f)H(o)298 (HO2+) = 264.71 +/- 0.14 kcal mol(-1) (265.41 +/- 0.14 kcal mol(-1) at 0 K), while that for the negative ion, HO2- (within the same convention), is delta(f)H(o)298 (HO2-) = -21.86 +/- 0.11 kcal mol(-1) (-21.22 +/- 0.11 kcal mol(-1) at 0 K). The related proton affinity of molecular oxygen is PA298(O2) = 100.98 +/- 0.14 kcal mol(-1) (99.81 +/- 0.14 kcal mol(-1) at 0 K), while the gas-phase acidity of H2O2 is delta(acid)G(o)298 (H2O2) = 369.08 +/- 0.11 kcal mol(-1), with the corresponding enthalpy of deprotonation of H2O2 of delta(acid)H(o)298 (H2O2) = 376.27 +/- 0.11 kcal mol(-1) (375.02 +/- 0.11 kcal mol(-1) at 0 K). In addition, a further improved enthalpy of formation of OH is briefly outlined, delta(f)H(o)298 (OH) = 8.93 +/- 0.03 kcal mol(-1) (8.87 +/- 0.03 kcal mol(-1) at 0 K), together with new and more accurate enthalpies of formation of NO, delta(f)H(o)298 (NO) = 21.76 +/- 0.02 kcal mol(-1) (21.64 +/- 0.02 kcal mol(-1) at 0 K) and NO2, delta(f)H(o)298 (NO2) = 8.12 +/- 0.02 kcal mol(-1) (8.79 +/- 0.02 kcal mol(-1) at 0 K), as well as H(2)O(2) in the gas phase, delta(f)H(o)298 (H2O2) = -32.45 +/- 0.04 kcal mol(-1) (-31.01 +/- 0.04 kcal mol(-1) at 0 K). The new thermochemistry of HO2, together with other arguments given in the present work, suggests that the previous equilibrium constant for NO + HO2 --> OH + NO2 was underestimated by a factor of approximately 2, implicating that the OH + NO2 rate was overestimated by the same factor. This point is experimentally explored in the companion paper of Srinivasan et al. (next paper in this issue).