02044nas a2200157   4500008004100000022001400041245013100055210006900186260007100255300001400326490000700340520136200347100002501709700002101734856013101755       2006                        eng d  a0021-956800aRe-tooling Benson's group additivity method for estimation of the enthalpy of formation of free radicals: C/H and C/H/O groups0 aRetooling Bensons group additivity method for estimation of the   a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL  a1169-11810 v513 a<p>Enthalpy of formation of free radicals is often required for the discrimination of reaction mechanisms (for complex processes such as combustion, hydrocarbon oxidation, or decomposition of peroxides and hydroperoxides) involving both molecular species and free radicals. Despite the expanding availability of the experimental measurements, the database for the enthalpy of formation of radicals is still not comprehensive. One of the simplest, efficient, and reliable methods for estimating the quantity for organic radicals from their molecular structure is the group-additivity method due to Benson and co-workers. Perusal of the literature shows that the group-additivity values (GAV) for many radical groups have remained either undetermined or obtained by assignment to the corresponding molecular groups without justification. In this paper, we devise simple methodologies to evaluate GAVs for a number of new oxygen-containing radical groups and re-estimate several alkyl and oxygen-containing radical groups using experimental data on the radical enthalpy of formation. The validity of these GAVs has been established by comparing the predicted enthalpies with experimental data. Finally, some of these updated GAVs were used in estimating the enthalpy change associated with the typical elementary steps in a peroxide decomposition reaction.</p>1 aBhattacharya, Arijit1 aShivalkar, Sagar  uhttps://library.ncl.res.in/content/re-tooling-bensons-group-additivity-method-estimation-enthalpy-formation-free-radicals-ch-0