Uptake kinetics of 3-buten-1-ol, 4-penten-1-ol and 3-methyl-3-buten-1-ol into sulfuric acid solutions

Abstract

Unsaturated alcohols are important components in complex mixtures of oxygenated volatile organic compounds, and play a significant role in atmospheric chemistry. The uptake kinetics of 3-buten-1-ol (BO31), 4-penten-1-ol (PO41) and 3-methyl-3-buten-1-ol (MBO331) into 20 wt%-80 wt% H 2 SO 4 solutions were studied, using a rotated wetted-wall reactor coupled to a differentially pumped single-photon ionization time of flight mass spectrometer (SPI-TOFMS). With increasing acidity, the uptake processes changed from reversible to irreversible (reactive). Reactive uptake was observed in 60 wt%-80 wt%, 50 wt%-80 wt% and 30 wt%-80 wt% H 2 SO 4 solutions for BO31, PO41 and MBO331, respectively. Reactive uptake coefficients were acquired and are reported here for the first time. Reactivity order followed the trend: BO31<PO41<MBO331. An electrophilic addition mechanism of H 2 SO 4 to the C==C double bond was used to explain this trend. Atmospheric implications were discussed, based on the reactive uptake coefficients. This heterogeneous reaction with sulfuric acid aerosols may be a potential degradation pathway of unsaturated alcohols, and should not be neglected.heterogeneous reaction, unsaturated alcohols, reactive uptake coefficients, sulfuric acid, OVOCs Citation:Xu Z F, Liu Z, Ge M F, et al. Uptake kinetics of 3-buten-1-ol, 4-penten-1-ol and 3-methyl-3-buten-1-ol into sulfuric acid solutions.

Heterogeneous Uptake Kinetics of Limonene and Limonene Oxide by Sulfuric Acid Solutions

“…The mechanism of H2SO4 reacting with C＝C is an electrophilic addition. 20 The first step of acid catalyzed reactions of limonene is the protonation to form pro-tonated hydrocarbon. 21 As H2SO4 is a weak electrophilic reagent, the heterogeneous reaction will happen when the acid solution reaches higher concentration, which has also been proved by other research.…”

O2–·[Polar VOC] Complexes: H-Bonding versus Charge–Dipole Interactions, and the Noninnocence of Formaldehyde

“…Ethanol (EtOH) not only supplements the automobile fuel supply 26−28 but also poses health threats, 29 and its atmospheric sources and sinks are not well-understood. 30,31 Oxygenated VOCs such as 2-propenol (allyl alcohol), 3-buten-1-ol, and 3-buten-2-ol are largely anthropogenic 32,33 and lead to secondary aerosol formation. 34 A significant difference between the O 2 − •[polar VOC] complexes in the current study and the O 2 − •[nonpolar VOC] complexes studied previously 16 arises from the strong charge− dipole interactions and hydrogen bonding that favor a distinct structural orientation between the O 2 − anion and the neutral VOC.…”

“…Formaldehyde is an atmospherically important carcinogen that is a common byproduct of numerous VOC oxidation reactions, and subsequently forms radicals , that contribute to tropospheric ozone formation. , Acetone is primarily formed by terrestrial vegetation and (anthropogenic) isoalkanes − and offers a methylated analog for comparison to formaldehyde. Ethanol (EtOH) not only supplements the automobile fuel supply − but also poses health threats, and its atmospheric sources and sinks are not well-understood. , Oxygenated VOCs such as 2-propenol (allyl alcohol), 3-buten-1-ol, and 3-buten-2-ol are largely anthropogenic , and lead to secondary aerosol formation …”

Partikelbildung bei der Alkenozonolyse und ihre Kopplung an die Radikalchemie

“…durch Verletzungen oder Trocknung abgegeben [62] oder entstehen durch die atmosphärische Oxidation von Alkenen [63]. Auch 3-Buten-1-ol kommt in der natürlichen Atmosphäre vor, allerdings wird es nicht nur biogen, sondern auch anthropogen in Polymersyntheseprozessen der Plastikindustrie freigesetzt [64]. O'DWYER et al [61] schlagen für 1-Penten-3-ol und 1-Penten-3-on Mechanismen vor, deren Folgereaktionen nach Bildung der CI ausschließlich unimolekulare Zerfälle bzw.…”