Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase
- 1Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), CNRS UMR7583, Université Paris-Est Créteil et Université Paris Diderot, Institut Pierre Simon Laplace (IPSL), Créteil, France
- 2University of Colorado, CIRES, Boulder, CO 80309, USA
- 3Aix-Marseille Université, CNRS, LCE FRE 3416, 13331, Marseille, France
Abstract. In the atmosphere, one important class of reactions occurs in the aqueous phase in which organic compounds are known to undergo oxidation towards a number of radicals, among which OH radicals are the most reactive oxidants. In 2008, Monod and Doussin have proposed a new structure–activity relationship (SAR) to calculate OH-oxidation rate constants in the aqueous phase. This estimation method is based on the group-additivity principle and was until now limited to alkanes, alcohols, acids, bases and related polyfunctional compounds. In this work, the initial SAR is extended to carbonyl compounds, including aldehydes, ketones, dicarbonyls, hydroxy carbonyls, acidic carbonyls, their conjugated bases, and the hydrated form of all these compounds. To do so, only five descriptors have been added and none of the previously attributed descriptors were modified. This extension leads now to a SAR which is based on a database of 102 distinct compounds for which 252 experimental kinetic rate constants have been gathered and reviewed. The efficiency of this updated SAR is such that 58% of the rate constants could be calculated within ±20% of the experimental data and 76% within ±40% (respectively 41 and 72% for the carbonyl compounds alone).