Ma. Grela et Aj. Colussi, QUANTITATIVE STRUCTURE-STABILITY RELATIONSHIPS FOR OXIDES AND PEROXIDES OF POTENTIAL ATMOSPHERIC SIGNIFICANCE, Journal of physical chemistry, 100(24), 1996, pp. 10150-10158
A critical analysis of the most recent experimental and ab initio ther
mochemical data on gas-phase species reveals that (1) isodesmic metath
etical reactions among simple oxides, 1/2XOX + 1/2YOY <-> XOY, and tho
se exclusively involving peroxides 1/2XOOX + 1/2YOOY <-> XOOY, are nea
rly thermoneutral (Delta H-t = 0 +/- 3 kcal/mol), but exchange reactio
ns between oxides and peroxides, XOX + YOOY <-> YOY + XOOX, are genera
lly not, (2) bond additivity values BAV[X-(O-O)-X]'s for the contribut
ions of the peroxide bond to the heats of formation of H-, C-, N-, S-,
F-, and Cl-containing peroxides decrease linearly with Pauling electr
onegativities chi(X)'s and (3) semiempirically evaluated (MOPAC) therm
ochemical datasets, even when inaccurate in absolute terms, are intern
ally consistent with such rules. These findings happen to provide the
basis for the rapid and systematic assessment of the stability of nove
l oxides and peroxides. In this paper, that focuses on species that co
uld be formed in the terrestrial atmosphere, we briefly discuss XOO-H
bond energy trends in hydroperoxides, the existence of stable and meta
stable peroxy XOO(.) radicals, the thermochemistry of peroxyacyl nitra
tes, of Br- and S-containing peroxides, and the mechanism of the (FO ClO), (FO + NO2), (OH + OClO), (HO2 + ClO), (ClO + NO2), and (ClO + N
O3) reactions, among other issues.