Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes

Casale, Mia T.; Richman, Aviva R.; Elrod, Matthew J.; Garland, R. M.; Beaver, M. R.; Tolbert, Margaret A.

doi:10.1016/j.atmosenv.2007.04.002

Cited by 107 publications

(116 citation statements)

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“…While aldol condensation products (e.g. from methylglyoxal) are thermodynamically favorable (Barsanti and Pankow, 2005), both experimental and theoretical studies have shown that rate constants of aldol condensation are too low to be important for significant aqSOA formation under typical atmospheric conditions (0.074 M −1 s −1 < k aldol < 15 M −1 s −1 (Casale et al, 2007;Minerath and Elrod, 2009) Noziere et al, 2006).…”

Section: Dark Reactions Of Carbonyl Compoundsmentioning

confidence: 99%

Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory, field and model studies

2011

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Abstract. Progress has been made over the past decade in predicting secondary organic aerosol (SOA) mass in the atmosphere using vapor pressure-driven partitioning, which implies that SOA compounds are formed in the gas phase and then partition to an organic phase (gasSOA). However, discrepancies in predicting organic aerosol oxidation state, size and product (molecular mass) distribution, relative humidity (RH) dependence, color, and vertical profile suggest that additional SOA sources and aging processes may be important. The formation of SOA in cloud and aerosol water (aqSOA) is not considered in these models even though water is an abundant medium for atmospheric chemistry and such chemistry can form dicarboxylic acids and "humic-like substances" (oligomers, high-molecular-weight compounds), i.e. compounds that do not have any gas phase sources but comprise a significant fraction of the total SOA mass. There is direct evidence from field observations and laboratory studies that organic aerosol is formed in cloud and aerosol water, contributing substantial mass to the droplet mode.This review summarizes the current knowledge on aqueous phase organic reactions and combines evidence that points to a significant role of aqSOA formation in the atmosphere. Model studies are discussed that explore the importance of aqSOA formation and suggestions for model improvements are made based on the comprehensive set of laboratory data presented here. A first comparison is made between aqSOA and gasSOA yields and mass predictions for selected conditions. These simulations suggest that aqSOA might contribute almost as much mass as gasSOA to the SOA budget, with highest contributions from biogenic emissions Correspondence to: B. Ervens (barbara.ervens@noaa.gov) of volatile organic compounds (VOC) in the presence of anthropogenic pollutants (i.e. NO x ) at high relative humidity and cloudiness. Gaps in the current understanding of aqSOA processes are discussed and further studies (laboratory, field, model) are outlined to complement current data sets.

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Section: Dark Reactions Of Carbonyl Compoundsmentioning

confidence: 99%

Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory, field and model studies

2011

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“…(6). We have successfully applied the excess acidity method in the past to acidcatalyzed aldol condensation reactions (Casale et al, 2007) and to the acid-catalyzed hydrolysis of primary organosulfates (Minerath et al, 2008). The following linear equation was found to fit the observed acid-dependence of the rate constants for the kinetics of hydrolysis of primary organosulfates:…”

Section: Kinetics Of Hydrolysis Of Primary and Secondary Organonitratesmentioning

confidence: 99%

Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates

2011

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Abstract. The presence of alcohol, organonitrate, and organosulfate species related to the gaseous precursor isoprene in ambient secondary organic aerosol (SOA) has stimulated investigations of the nature of SOA-phase chemical processing. Recent work has suggested that certain isoprene-derived organonitrates are able to efficiently convert to organosulfates and alcohols on ambient SOA. In order to better understand the structure activity relationships previously observed for the isoprene-derived organonitrates and organosulfates, the hydrolysis reactions of a number of monofunctional and difunctional organonitrates and organosulfates with varying carbon substitution properties were investigated. Nuclear magnetic resonance techniques were used to study the bulk phase aqueous reactions of these organonitrates and organosulfates in order to determine hydrolysis reaction rate and, in some cases, thermodynamics information. Electronic structure calculations were also carried out to determine the enthalpy of hydrolysis for these species, and for the previously studied isoprene-derived species. The results suggest that while organonitrates and organosulfates are thermodynamically unstable with respect to the corresponding alcohols at standard state, only the tertiary organonitrates (and perhaps some tertiary organosulfates) are able to efficiently hydrolyze on SOA timescales and acidities.

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“…The reaction of a hydroperoxide with a carbonyl to give a peroxyhemiacetal, and the reaction of a peroxyacid with a carbonyl to form an acyl peroxyhemiacetal, have reported rate constants in the 10 −4 to 10 −2 M −1 s −1 range depending on reaction conditions, and are relevant to the modeling results presented here. Reactions such as aldol condensation of carbonyls and ester formation from an acid and alcohol are much slower and unlikely to be atmospherically relevant based on both kinetics (Casale et al, 2007) and thermodynamics . The effects of dimer decomposition (reaction reversibility), particle-phase diffusion coefficient, and phase separation are not considered in this work, though we note that all would have the effect of reducing the impact of particle-phase chemistry on composition and growth rate.…”

Section: Particle-phase Chemistrymentioning

confidence: 99%

Nanoparticle growth by particle-phase chemistry

Apsokardu¹,

Johnston²

2018

Atmos. Chem. Phys.

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Abstract. The ability of particle-phase chemistry to alter the molecular composition and enhance the growth rate of nanoparticles in the 2-100 nm diameter range is investigated through the use of a kinetic growth model. The molecular components included are sulfuric acid, ammonia, water, a non-volatile organic compound, and a semi-volatile organic compound. Molecular composition and growth rate are compared for particles that grow by partitioning alone vs. those that grow by a combination of partitioning and an accretion reaction in the particle phase between two organic molecules. Particle-phase chemistry causes a change in molecular composition that is particle diameter dependent, and when the reaction involves semi-volatile molecules, the particles grow faster than by partitioning alone. These effects are most pronounced for particles larger than about 20 nm in diameter. The modeling results provide a fundamental basis for understanding recent experimental measurements of the molecular composition of secondary organic aerosol showing that accretion reaction product formation increases linearly with increasing aerosol volume-to-surface-area. They also allow initial estimates of the reaction rate constants for these systems. For secondary aerosol produced by either OH oxidation of the cyclic dimethylsiloxane (D 5 ) or ozonolysis of β-pinene, oligomerization rate constants on the order of 10 −3 to 10 −1 M −1 s −1 are needed to explain the experimental results. These values are consistent with previously measured rate constants for reactions of hydroperoxides and/or peroxyacids in the condensed phase.

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Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes

Cited by 107 publications

References 40 publications

Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory, field and model studies

Secondary organic aerosol formation in cloud droplets and aqueous particles (aqSOA): a review of laboratory, field and model studies

Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates

Nanoparticle growth by particle-phase chemistry

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