Kinetics of the Gas-Phase Reactions of Alcohols, Aldehydes, Carboxylic Acids, and Water with the C13 Stabilized Criegee Intermediate Formed from Ozonolysis of 1-Tetradecene

Abstract

Previous studies in our laboratory have shown that the major aerosol products formed in gas-phase ozonolysis of 1-tetradecene in the presence of excess alcohols, carboxylic acids, water vapor, and aldehydes are R-alkoxytridecyl, R-acyloxytridecyl, R-hydroxytridecyl hydroperoxides, and secondary ozonides. These low volatility compounds are formed from reactions of C13 stabilized Criegee intermediates with the acidic compounds and aldehydes. To obtain a more quantitative understanding of the chemical mechanism and determine the importance of such reactions in the atmosphere, relative rate constant measurements were made using real-time quantitative thermal desorption particle beam mass spectrometry (TDPBMS) for aerosol analysis. The rates of reaction of methanol, 2-propanol, formic acid, water, and formaldehyde with C13 stabilized Criegee intermediates were measured relative to heptanoic acid. The results show that the reactivity of the studied compounds varies over 4 orders of magnitude and increases in the order: water , methanol < 2-propanol , formaldehyde < formic acid < heptanoic acid. The rate constants depend primarily on the nature of the functional group and correlate well with the gas-phase acidities, indicating a relatively polar transition state for the reaction. The relative rate constants depend only slightly on the size of the reactant species and are similar to those measured previously for a C1 stabilized Criegee intermediate. The atmospheric implications of these results are also discussed.

Reactions between Criegee Intermediates and the Inorganic Acids HCl and HNO3: Kinetics and Atmospheric Implications

“…where 0 ′ represents the background, acid-free loss rate that can be attributed largely to reaction Linear fits to the data shown in Figure 2 yield bimolecular rate constants of HCl = (4.6±1)×10 [41] The suggestion that the transition states (TSs) are highly polar is supported by quantum chemistry calculations, described below.…”

The SOA/VOC/NO&lt;sub&gt;x&lt;/sub&gt; system: an explicit model of secondary organic aerosol formation

“…At low NO x , gaseous reactions with HO 2 may form peroxides (e.g., Atkinson, 2000). Gas/particle partitioning of hydroperoxides at low NO x has been shown in both laboratory chamber experiments (Docherty et al, 2005;Tobias and Ziemann, 2001) and modelling studies (Bonn et al, 2004;Johnson et al, 2004Johnson et al, , 2005 to represent a dominant fraction of SOA. Under high NO x , gaseous reaction of RO 2 with NO produces organic nitrates among other products.…”

A new mechanism for ozonolysis of unsaturated organics on solids: phosphocholines on NaCl as a model for sea salt particles

“…Additional reaction paths are available for CI's, including isomerization to the acid or reaction with water vapor, if present. 14,43,[46][47][48][49][50][51][52][53] The spectrum in Fig. 3 shows that even in the absence of added water vapor, adsorbed water is present on the surface of the OPPC/NaCl.…”

“…43, [46][47][48][49][50][51][52][53] However, the spectra in Fig. 4 also show that -CH 2 -groups are lost during the reaction.…”