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Thermochemical kinetics of bromine nitrate, bromine nitrite, halogen hydroperoxides, dichlorine pentoxide, peroxycarboxylic acids, and diacyl peroxides
Author(s) -
Colussi Agustín J.,
Grela María A.
Publication year - 1998
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1998)30:1<41::aid-kin5>3.0.co;2-u
Subject(s) - chemistry , bromine , standard enthalpy of formation , radical , exothermic reaction , nitrite , bond dissociation energy , kinetics , dissociation (chemistry) , ab initio , chlorate , decomposition , medicinal chemistry , inorganic chemistry , nitrate , organic chemistry , physics , quantum mechanics
Heats of formation of BrONO 2 , BrONO, BrOOH, FOOH, FOOCl, CF 3 C(O)OOH, HC(O)OOH, CH 3 C(O)OOH, and [CH 3 C(O)O] 2 are estimated from bond contributions taken from J. Phys. Chem., 100, 10150 (1996). They agree within ±2 kcal/mol with recent experimental or ab initio data. The resulting BDE(O(SINGLEBOND)O)=36 kcal/mol value in diacetyl peroxide requires the concerted assistance of exothermic C(SINGLEBOND)C(O) weakening in the transition state of its decomposition into free radicals. It also implies the existence of a previously unrecognized 12 kcal/mol nonbonded repulsion in acyl anhydrides. The formation of chloryl chlorate with Δ H f (O 2 ClOClO 2 )=50 kcal/mol, a marginally stable species toward dissociation into (ClO 3 +OClO), may account for observations made in the [O( 3 P+OClO] system at low temperatures. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 41–45, 1998.