Akademik Veri Yönetim Sistemi
ATMOSPHERIC ENVIRONMENT, cilt.39, sa.4, ss.763-771, 2005 (SCI-Expanded, Scopus)
Peroxy radicals play an important role as reaction intermediates in the atmospheric oxidation of volatile organic compounds (VOCs). The rate coefficients for the self-reactions vary by up to six orders of magnitude (e.g. 3.0 x 10(-17) cm(3) molecule(-1) s(-1) for t-C4H9O2 and 1.5 x 10(-11) cm(3) molecule(-1) s(-1) for CH3C(O)O-2) with, up to now, no clear pattern. This work represents the first rationalisation of peroxy radical self-reaction trends in reactivity. A correlation between the logarithm of the rate coefficient of peroxy radical self-reactions with the stabilisation energy, the difference in the enthalpy of formation of peroxy radicals with that of the tetraoxide adduct {DeltaH(f)(RO4R)-2DeltaH(f)(RO2)}, is presented. The equation, log(10)k = -{DeltaH(f)(RO4R)-2DeltaH(f)(RO2) + 235.95}/13.32 (where energy is in kJmol(-1)) is given to predict the room temperature rate coefficients of peroxy radical self-reactions. The correlation was extended to predict rate coefficients for the cross-reactions of peroxy radicals with CH3O2. Furthermore, favourable comparisons are made between the predicted rate coefficients and very recent studies of complex peroxy radical systems. (C) 2004 Elsevier Ltd. All rights reserved.