Criegee intermediate-hydrogen sulfide chemistry at the air/water interface.

Criegee intermediate-hydrogen sulfide chemistry at the air/water interface† †Electronic supplementary information (ESI) available: Radial distribution functions for the H2S–H2O and CH2OO–H2O interactions; probability distributions P(θ 1,θ 2) for H2S at the air–water interface; videos of trajectories of the BOMD simulations for the concerted and stepwise reactions between CH2OO and H2S at the air/water interface; BLYP/aug-cc-pVTZ-optimized geometries of key stationary points for the gas-phase reactions of CH2OO with H2S and H2S–H2O, respectively. See DOI: 10.1039/c7sc01797a Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file. Click here for additional data file.

Direct evidence for a substantive reaction between the Criegee intermediate, CH2OO, and the water vapour dimer.

The C1 Criegee intermediate, CH2OO, reaction with water vapour has been studied. The removal rate constant shows a quadratic dependence on [H2O], implying reaction with the water dimer, (H2O)2. The rate constant, kCH2OO+(H2O)2 = (4.0 ± 1.2) × 10(-12) cm(3) molecule(-1) s(-1), is such that this is the major atmospheric sink for CH2OO.

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO2.

Criegee intermediates are thought to play a role in atmospheric chemistry, in particular, the oxidation of SO2, which produces SO3 and subsequently H2SO4, an important constituent of aerosols and acid rain. However, the impact of such oxidation reactions is affected by the reactions of Criegee intermediates with water vapor, because of high water concentrations in the troposphere. In this work,...

Barrierless tautomerization of Criegee intermediates via acid catalysis.

The tautomerization of Criegee intermediates via a 1,4 β-hydrogen atom transfer to yield a vinyl hydroperoxide has been examined in the absence and presence of carboxylic acids. Electronic structure calculations indicate that the organic acids catalyze the tautomerization reaction to such an extent that it becomes a barrierless process. In contrast, water produces only a nominal catalytic effec...

Effect of Complementary Hydrogen Bonding Additives in Subphase on the Structure and Properties of the 2-Amino-4,6-dioctadecylamino-1,3,5-triazine Amphiphile at the Air-Water Interface: Studies by Ultraviolet-Visible Absorption Spectroscopy and Brewster Angle Microscopy

The present work is focused on the effects of hydrogen bonding on the 2-D properties of aminotriazine amphiphile 1 (2C18TAZ) by incorporating different complementary hydrogen bonding components in the subphase. The structural organization of 1 at the air-water interface in the presence of barbituric acid (BA), barbital (BT), andcyanuricacid (CA)wasexaminedbysurfacepressure-area isothermmeasurem...