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
03 Dec 2013
2University of Colorado, CIRES, Boulder, CO 80309, USA
3Aix-Marseille Université, CNRS, LCE FRE 3416, 13331, Marseille, France
Received: 10 January 2013 – Published in Atmos. Chem. Phys. Discuss.: 14 June 2013 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).
Revised: 04 October 2013 – Accepted: 11 October 2013 – Published: 03 December 2013
Citation: Doussin, J.-F. and Monod, A.: Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase, Atmos. Chem. Phys., 13, 11625-11641, doi:10.5194/acp-13-11625-2013, 2013.