Low-temperature infrared studies of simple alkene-ozone reactions

Hull, Leslie A.; Hisatsune, I. C.; Heicklen, Julian

doi:10.1021/ja00769a010

Cited by 75 publications

(50 citation statements)

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“…All three organics have electron-rich π systems, and the formation of weak π complexes between ozone and alkenes has been reported at low temperatures, [62][63][64] suggesting that perhaps partial electron transfer is a key step in the oxidation.…”

Section: Resultsmentioning

confidence: 99%

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

et al. 2004

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The oxidation of organics adsorbed on surfaces by ozone is of fundamental chemical interest and potentially important in the lower atmosphere. Studies of the oxidation of the three-carbon and eight-carbon vinylterminated self-assembled monolayers (SAMs, C3d and C8d) on a silicon ATR (attenuated total reflectance) crystal by gas-phase O 3 at 296 K are reported. Oxidation of the SAMs was followed in real time by ATR-FTIR using ozone concentrations that spanned 5 orders of magnitude, from ∼10 11 to 10 16 molecules cm -3 . For comparison, some studies of the saturated C8 SAM were also carried out. The films were also characterized by atomic force microscopy and water contact angle measurements. The loss of CdC and the formation of CdO were measured in real time and shown to be consistent with a Langmuir-Hinshelwood mechanism in which O 3 is rapidly adsorbed on the surface and then reacts more slowly with the alkene moiety. This is supported by molecular dynamics (MD) calculations which show that O 3 does not simply undergo elastic collisions but has a significant residence time on the surface. However, the kinetics measurements indicate a much longer residence time than the MD calculations, suggesting a chemisorption of O 3 . Formaldehyde was observed as a gas-phase product by infrared cavity ring down spectroscopy. Possible mechanisms of the ozonolysis and its atmospheric implications are discussed.

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Section: Resultsmentioning

confidence: 99%

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

et al. 2004

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“…The low-temperature infrared cell made of Pyrex glass was the same cell used in an earlier study of the olefinozone reactions (11). The operation of the cell had been described in detail in that study.…”

Section: Methodsmentioning

confidence: 99%

Infrared Spectroscopic Study of Ammonia – Sulfur Dioxide – Water Solid State System

Hisatsune¹,

Heicklen²

1975

Can. J. Chem.

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Products formed during the solid state reactions between ammonia and sulfur dioxide in the presence or absence of water have been investigated by infrared spectroscopy. Warming of a low-temperature matrix of SO2 with excess NH3 produces (NH3)2•SO2 at −90 °C. This adduct decomposes near −50 °C into NH3•SO2 which has a yellow color. With excess SO2 only NH3•SO2 appears at −150 °C. The 1:1 complex disappears from the low-temperature infrared window at about −20 °C. With H2O present in the matrix, (NH3)2•SO2 is converted at −80 °C into ammonium sulfite which is stable to room temperature where it can be pumped off readily from the infrared window. With less than the stoichiometric amount of water, the final product of the warming sequence is ammonium pyrosulfite whose infrared spectrum varies considerably with experimental conditions. The pyrosulfite reacts further with water to give ammonium bisulfite. The infrared spectra of solid ammonium bisulfite and perdeuteroammonium bisulfite show that the hydrogen in the bisulfite ion is bonded to the sulfur atom. Vibrational assignments have been made for all the compounds.

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“…Assignment of the bands is shown in Table 1. [27][28][29][30][31] band is formed at B1110 cm À1 that is characteristic of the peroxide C-O bond 32,33 of the secondary ozonide ring (1,2,4-trioxolane, SOZ) known to be formed in ozone-alkene reactions. 14,[34][35][36][37][38][39][40] New bands at B1385 and 1347 cm À1 are also assigned to the SOZ.…”

Section: Auger Spectroscopymentioning

confidence: 99%

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

Karagulian

Lea

Dilbeck

et al. 2008

Phys. Chem. Chem. Phys.

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PERSPECTIVEThe ozonolysis of an approximately one monolayer film of 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine (OPPC) on NaCl was followed in real time using diffuse reflection infrared Fourier transform spectrometry (DRIFTS) at 23 1C. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry and Auger electron spectroscopy were used to confirm the identification of the products. Ozone concentrations ranged from 1.7 Â 10 12 to 7.0 Â 10 13 molecules cm À3 (70 ppb to 2.8 ppm). Upon exposure to O 3 , there was a loss of CQC accompanied by the formation of a strong band at B1110 cm À1 due to the formation of a stable secondary ozonide (1,2,4-trioxolane, SOZ). The yield of the SOZ was smaller when the reaction was carried out in the presence of water vapor at concentrations corresponding to relative humidities between 2 and 25%.

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Low-temperature infrared studies of simple alkene-ozone reactions

Cited by 75 publications

References 1 publication

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

Interaction of Gas-Phase Ozone at 296 K with Unsaturated Self-Assembled Monolayers: A New Look at an Old System

Infrared Spectroscopic Study of Ammonia – Sulfur Dioxide – Water Solid State System

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

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