Rate constants for the OH reactions with oxygenated organic compounds in aqueous solution

Gligorovski, Sasho; Rousse, Davy; George, Christian; Herrmann, Hartmut

doi:10.1002/kin.20405

Cited by 34 publications

(50 citation statements)

References 74 publications

(80 reference statements)

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“…A number of compounds of interest because of their industrial use have been investigated in the MOST EC project in studies by Gligorovski et al, [26] Moise et al [27] and Monod et al [28] The reactivity of substituted ethers was also studied by Mezyk et al [29] Within this compound class, a number of temperature dependences are available now. Finally, in the studies of Bardouki et al [30] and Zhu et al, [31] aqueous phase reaction data of interest for the atmospheric multiphase oxidation of dimethyl sulfide (DMS) are available.…”

Section: Oxygenated Compoundsmentioning

confidence: 97%

“…To clarify the situation for this reaction of large interest for atmospheric chemistry, another remeasurement of this reaction is currently under progress in our laboratory. [26] including the temperature dependences. Ershov et al [32] and Martin et al [33] determined the rate constants for the reactions of OH with oxalic and lactic acid, respectively, at room temperature.…”

Section: Oxygenated Compoundsmentioning

confidence: 99%

“…However, mesoxalic acid is absorbing light at the photolysis wavelength of 248 nm used in the study of Gligorovski and co-workers. [26] Therefore, photolysis processes of mesoxalic acid and mesoxalate dianion might have an influence on the reactant concentrations and the chemistry during the measurements in their study. The same is also valid for the measurements of Gligorovski [26] at pH 1.…”

Section: Oxygenated Compoundsmentioning

confidence: 99%

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Tropospheric Aqueous‐Phase Free‐Radical Chemistry: Radical Sources, Spectra, Reaction Kinetics and Prediction Tools

et al. 2010

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The most important radicals which need to be considered for the description of chemical conversion processes in tropospheric aqueous systems are the hydroxyl radical (OH), the nitrate radical (NO(3)) and sulphur-containing radicals such as the sulphate radical (SO(4)(-)). For each of the three radicals their generation and their properties are discussed first in the corresponding sections. The main focus herein is to summarize newly published aqueous-phase kinetic data on OH, NO(3) and SO(4)(-) radical reactions relevant for the description of multiphase tropospheric chemistry. The data compilation builds up on earlier datasets published in the literature. Since the last review in 2003 (H. Herrmann, Chem. Rev. 2003, 103, 4691-4716) more than hundred new rate constants are available from literature. In case of larger discrepancies between novel and already published rate constants the available kinetic data for these reactions are discussed and recommendations are provided when possible. As many OH kinetic data are obtained by means of the thiocyanate (SCN(-)) system in competition kinetic measurements of OH radical reactions this system is reviewed in a subchapter of this review. Available rate constants for the reaction sequence following the reaction of OH+SCN(-) are summarized. Newly published data since 2003 have been considered and averaged rate constants are calculated. Applying competition kinetics measurements usually the formation of the radical anion (SCN)(2)(-) is monitored directly by absorption measurements. Within this subchapter available absorption spectra of the (SCN)(2)(-) radical anion from the last five decades are presented. Based on these spectra an averaged (SCN)(2)(-) spectrum was calculated. In the last years different estimation methods for aqueous phase kinetic data of radical reactions have been developed and published. Such methods are often essential to estimate kinetic data which are not accessible from the literature. Approaches for rate constant prediction include empirical correlations as well as structure activity relationships (SAR) either with or without the usage of quantum chemical descriptors. Recently published estimation methods for OH, NO(3) and SO(4)(-) radical reactions in aqueous solution are finally summarized, compared and discussed.

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Section: Oxygenated Compoundsmentioning

confidence: 97%

Section: Oxygenated Compoundsmentioning

confidence: 99%

Section: Oxygenated Compoundsmentioning

confidence: 99%

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Tropospheric Aqueous‐Phase Free‐Radical Chemistry: Radical Sources, Spectra, Reaction Kinetics and Prediction Tools

et al. 2010

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“…The aqueous phase oxidation of organic compounds has mainly been investigated at 298 K, which is not relevant to the temperatures encountered in cloud/fog waters, and only a limited number of studies have explored the temperature dependence of the rate constants for reaction of OH with organic compounds at low ionic strength, representative of cloud/fog droplets (Chin and Wine, 1994;Buxton et al, 1997;Ervens et al, 2003b;Gligorovski and Herrmann, 2004;Poulain et al, 2007;Gligorovski et al, 2009). Based on these studies, structure activity relationships have been proposed to predict rate constants for the reaction of OH radicals with organic compounds at 298 K (Gligorovski and Herrmann, 2004;Monod et al, 2005;Monod and Doussin, 2008;Morozov et al, 2008;Gligorovski et al, 2009). Nevertheless, many aqueous phase oxidation reactions have yet to be investigated, especially for non-aliphatic compounds, and therefore are not considered in current models.…”

Section: Aqueous Phase Oxidation Of Organic Compoundsmentioning

confidence: 99%

The formation, properties and impact of secondary organic aerosol: current and emerging issues

et al. 2009

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Abstract. Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

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“…The latter data arising from an exhaustive literature search are displayed in Table 4. On the contrary, there was no intention in Table 1 to build an exhaustive list of experimental data for the hydration equilibrium as this work has already been performed by Gomez-Bombarelli et al (2009). It was hence limited to the species included in Table 4.…”

Section: Databasementioning

confidence: 99%

Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase

2013

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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 OHoxidation 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).

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Rate constants for the OH reactions with oxygenated organic compounds in aqueous solution

Cited by 34 publications

References 74 publications

Tropospheric Aqueous‐Phase Free‐Radical Chemistry: Radical Sources, Spectra, Reaction Kinetics and Prediction Tools

Tropospheric Aqueous‐Phase Free‐Radical Chemistry: Radical Sources, Spectra, Reaction Kinetics and Prediction Tools

The formation, properties and impact of secondary organic aerosol: current and emerging issues

Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase

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