Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products: from methylcyclohexenes toward understanding α-pinene

Matti P. Rissanen; Theo Kurtén; Mikko Sipilä; Joel A. Thornton; Oskari Kausiala; Olga Garmash; Henrik Grum Kjærgaard; Tuukka Petäjä; Douglas R. Worsnop; Mikael Ehn; Markku Kulmala

doi:10.1021/jp510966g

Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products: from methylcyclohexenes toward understanding α-pinene

Matti P. Rissanen^*, Theo Kurtén, Mikko Sipilä, Joel A. Thornton, Oskari Kausiala, Olga Garmash, Henrik Grum Kjærgaard, Tuukka Petäjä, Douglas R. Worsnop, Mikael Ehn, Markku Kulmala

^*Corresponding author for this work

Department of Chemistry

68 Citations (Scopus)

Abstract

Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4-methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO<inf>3</inf><sup>-</sup>) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO<inf>2</inf>) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. These conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D<inf>2</inf>O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.

Original language	English
Journal	Journal of Physical Chemistry A
Volume	119
Issue number	19
Pages (from-to)	4633-4650
Number of pages	18
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp510966g
Publication status	Published - 2015

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Rissanen, M. P., Kurtén, T., Sipilä, M., Thornton, J. A., Kausiala, O., Garmash, O., Kjærgaard, H. G., Petäjä, T., Worsnop, D. R., Ehn, M., & Kulmala, M. (2015). Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products: from methylcyclohexenes toward understanding α-pinene. Journal of Physical Chemistry A, 119(19), 4633-4650. https://doi.org/10.1021/jp510966g

Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products : from methylcyclohexenes toward understanding α-pinene. / Rissanen, Matti P.; Kurtén, Theo; Sipilä, Mikko et al.

In: Journal of Physical Chemistry A, Vol. 119, No. 19, 2015, p. 4633-4650.

Research output: Contribution to journal › Journal article › Research › peer-review

Rissanen, MP, Kurtén, T, Sipilä, M, Thornton, JA, Kausiala, O, Garmash, O, Kjærgaard, HG, Petäjä, T, Worsnop, DR, Ehn, M & Kulmala, M 2015, 'Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products: from methylcyclohexenes toward understanding α-pinene', Journal of Physical Chemistry A, vol. 119, no. 19, pp. 4633-4650. https://doi.org/10.1021/jp510966g

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title = "Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products: from methylcyclohexenes toward understanding α-pinene",

abstract = "Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4-methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO3-) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO2) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. These conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D2O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.",

author = "Rissanen, {Matti P.} and Theo Kurt{\'e}n and Mikko Sipil{\"a} and Thornton, {Joel A.} and Oskari Kausiala and Olga Garmash and Kj{\ae}rgaard, {Henrik Grum} and Tuukka Pet{\"a}j{\"a} and Worsnop, {Douglas R.} and Mikael Ehn and Markku Kulmala",

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T1 - Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products

T2 - from methylcyclohexenes toward understanding α-pinene

AU - Rissanen, Matti P.

AU - Kurtén, Theo

AU - Sipilä, Mikko

AU - Thornton, Joel A.

AU - Kausiala, Oskari

AU - Garmash, Olga

AU - Kjærgaard, Henrik Grum

AU - Petäjä, Tuukka

AU - Worsnop, Douglas R.

AU - Ehn, Mikael

AU - Kulmala, Markku

PY - 2015

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N2 - Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4-methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO3-) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO2) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. These conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D2O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.

AB - Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4-methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO3-) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO2) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. These conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D2O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.

U2 - 10.1021/jp510966g

DO - 10.1021/jp510966g

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SN - 1089-5639

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JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 19

ER -

Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products: from methylcyclohexenes toward understanding α-pinene

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