# Tracking the reaction networks of acetaldehyde oxide and glyoxal oxide Criegee intermediates in the ozone-assisted oxidation reaction of crotonaldehyde

Alec De cecco, Alan Conrad, Nath-Eddy Moddy, Ahren Jasper, Nils Hansen, Philippe Dagaut, Denisia Popolan-Vaida

<figure><img src="image_1.png" /></figure>

## To cite this version:

Alec De cecco, Alan Conrad, Nath-Eddy Moddy, Ahren Jasper, Nils Hansen, et al.. Tracking the reaction networks of acetaldehyde oxide and glyoxal oxide Criegee intermediates in the ozone-assisted oxidation reaction of crotonaldehyde. ACS Spring Meeting 2024, American Chemical Society, Mar 2024, New Orleans (LA), United States. hal-04597074

HAL Id: hal-04597074

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Submitted on 1 Jun 2024

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<figure><img src="image_1.png" /></figure>

# Tracking the Reaction Network of Acetaldehyde Oxide and Glyoxal Oxide Criegee Intermediates in the Ozone-Assisted Oxidation of Crotonaldehyde

Alec DeCecco,¹ Alan Conrad,¹ Nath-Eddy Moddy,¹ Ahren Jasper,² Nils Hansen,³ Philippe Dagaut,⁴ and Denisia Popolan-Vaida¹

¹Department of Chemistry, University of Central Florida, Orlando, FL, USA, ²Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA, ³Combustion Research Facility, Sandia National Laboratories, Livermore, CA, USA, ⁴Centre National de la Recherche Scientifique, INSIS, ICARE, 45071 Orléans Cedex 2, France

## Abstract

The reaction of unsaturated compounds with ozone is recognized to lead to the formation of Criegee intermediates (CIs), which play a key role in controlling the atmospheric budget of hydroxyl radicals and secondary organic aerosols. The reaction network of two CIs (CH₃CHOO and CHOCHOO) formed in the ozone-assisted oxidation reaction of crotonaldehyde (CA), is investigated over a temperature range between 390 K and 800 K in an atmospheric pressure jet stirred reactor (JSR). Molecular beam in conjunction with single photon tunable synchrotron VUV radiation is used to identify elusive intermediates and separate structural isomers. Addition of ozone (1000 ppm) is observed to trigger the oxidation of CA already at 390 K, below the temperature where the oxidation reaction of CA in the absence of ozone was observed. The observed CA + O₃ product, C₄H₆O₄, is found to be linked to the ketohydroperoxide resulting from the isomerization of the primary ozonide. A network of Cl reactions identified in the temperature region below 600 K is characterized by CIs addition to species like alkenes and aldehydes. The results of these studies provide new mechanistic insights into ozone-assisted oxidation reactions of aldehydes, which is critical for the development of improved kinetics models.

## Reaction of Crotonaldehyde and Ozone

<figure><img src="image_2.png" /><figcaption>Typical mass spectra recorded after the ozone-assisted oxidation reaction of crotonaldehyde at a temperature of 390 K and ionization energy of 11.0 eV.</figcaption></figure>

<figure><img src="image_3.png" /></figure>

(Left) Photo-ionization efficiency curve of the signal recorded at m/z 60.021. The recorded signal is attributed to glycolaldehyde an isomer of Cl1 and acetic acid.

(Right) Temperature profile of the signal recorded at m/z 60.021 and ionization energy of 10.5 eV and 11.0 eV, respectively.

<figure><img src="image_4.png" /></figure>

## Reactions of Criegee intermediates

<figure><img src="image_5.png" /></figure>

<figure><img src="image_6.png" /></figure>

<figure><img src="image_7.png" /></figure>

<figure><img src="image_8.png" /></figure>

<figure><img src="image_9.png" /></figure>

<figure><img src="image_10.png" /><figcaption>(Top row) Photo-ionization efficiency curves for m/z 88 and m/z 102.06 corresponding to mass of Cl1 + C₂H₄ and C₃H₆, respectively (Middle row) Photo-ionization efficiency curve for m/z 102.03 and m/z 116 corresponding to mass of Cl2 + C₂H₄ and C₃H₆, respectively. (Bottom row) Temperature profiles of both C₂H₄ and C₃H₆, respectively.</figcaption></figure>

## Experimental setup

<figure><img src="image_11.png" /><figcaption>Schematic representation of the jet-stirred reactor (JSR) used in conjunction with a high-resolution time-of-flight mass spectrometer coupled to tunable synchrotron-generated radiation. This setup was used to detect and identify key products and intermediates formed during the ozone-assisted low-temperature oxidation of crotonaldehyde.</figcaption></figure>

<figure><img src="image_12.png" /></figure>

(Top) Primary unimolecular processes and bimolecular reactions involved in the ozone-assisted oxidation of crotonaldehyde. The numbers in parentheses correspond to the nominal mass of the respective structure.

(Right) Photo-ionization efficiency curve of the signal recorded at m/z 118.026 corresponding to mass of either POZ, SOZ, or KHP. The signal is attributed in part to the KHP based on the calculated ionization energy that matches the signal onset.

<figure><img src="image_13.png" /><figcaption>CIs + aldehydes</figcaption></figure>

<figure><img src="image_14.png" /></figure>

<figure><img src="image_15.png" /></figure>

<figure><img src="image_16.png" /><figcaption>(Left) Photo-ionization efficiency curve for m/z 130 and (middle) 144 corresponding to the mass of Cl1 + CA and Cl2 + CA, respectively. (Right) temperature profiles for both CIs with CA.</figcaption></figure>

<figure><img src="image_17.png" /></figure>

<figure><img src="image_18.png" /><figcaption>(Left) Photo-ionization efficiency curve for m/z 118 and (right) 132 corresponding to the mass of Cl1 + propionaldehyde and Cl2 + propionaldehyde, respectively</figcaption></figure>
<figure><img src="image_2.png" /></figure>

# Tracking the Reaction Network of Acetaldehyde Oxide and Glyoxal Oxide Criegee Intermediates in the Ozone-Assisted Oxidation of Crotonaldehyde

Alec DeCecco,¹ Alan Conrad,¹ Nath-Eddy Moddy,¹ Ahren Jasper,² Nils Hansen,³ Philippe Dagaut,⁴ and Denisia Popolan-Vaida¹

¹Department of Chemistry, University of Central Florida, Orlando, FL, USA, ²Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA, ³Combustion Research Facility, Sandia National Laboratories, Livermore, CA, USA, ⁴Centre National de la Recherche Scientifique, INSIS, ICARE, 45071 Orléans Cedex 2, France

## Abstract

The reaction of unsaturated compounds with ozone is recognized to lead to the formation of Criegee intermediates (CIs), which play a key role in controlling the atmospheric budget of hydroxyl radicals and secondary organic aerosols. The reaction network of two CIs (CH₃CHOO and CHOCHOO) formed in the ozone-assisted oxidation reaction of crotonaldehyde (CA), is investigated over a temperature range between 390 K and 800 K in an atmospheric pressure jet stirred reactor (JSR). Molecular beam in conjunction with single photon tunable synchrotron VUV radiation is used to identify elusive intermediates and separate structural isomers. Addition of ozone (1000 ppm) is observed to trigger the oxidation of CA already at 390 K, below the temperature where the oxidation reaction of CA in the absence of ozone was observed. The observed CA + O₃ product, C₄H₆O₄, is found to be linked to the ketohydroperoxide resulting from the isomerization of the primary ozonide. A network of Cl reactions identified in the temperature region below 600 K is characterized by CIs addition to species like alkenes and aldehydes. The results of these studies provide new mechanistic insights into ozone-assisted oxidation reactions of aldehydes, which is critical for the development of improved kinetics models.

## Reaction of Crotonaldehyde and Ozone

<figure><img src="image_3.png" /><figcaption>Typical mass spectra recorded after the ozone-assisted oxidation reaction of crotonaldehyde at a temperature of 390 K and ionization energy of 11.0 eV.</figcaption></figure>

<figure><img src="image_4.png" /></figure>

(Left) Photo-ionization efficiency curve of the signal recorded at m/z 60.021. The recorded signal is attributed to glycolaldehyde an isomer of Cl1 and acetic acid. (Right) Temperature profile of the signal recorded at m/z 60.021 and ionization energy of 10.5 eV and 11.0 eV, respectively.

<figure><img src="image_5.png" /></figure>

## Experimental setup

<figure><img src="image_6.png" /><figcaption>Schematic representation of the jet-stirred reactor (JSR) used in conjunction with a high-resolution time-of-flight mass spectrometer coupled to tunable synchrotron-generated radiation. This setup was used to detect and identify key products and intermediates formed during the ozone-assisted low-temperature oxidation of crotonaldehyde.</figcaption></figure>

<figure><img src="image_7.png" /><figcaption>Temperature profile comparison of crotonaldehyde and ozone collected at 10.5 eV and 14.35 eV, respectively</figcaption></figure>

## Reactions of Criegee intermediates

<figure><img src="image_8.png" /></figure>

<figure><img src="image_9.png" /></figure>

<figure><img src="image_10.png" /></figure>

<figure><img src="image_11.png" /></figure>

<figure><img src="image_12.png" /></figure>

<figure><img src="image_13.png" /><figcaption>(Top row) Photo-ionization efficiency curves for m/z 88 and m/z 102.06 corresponding to mass of Cl1 + C₂H₄ and C₃H₆, respectively (Middle row) Photo-ionization efficiency curve for m/z 102.03 and m/z 116 corresponding to mass of Cl2 + C₂H₄ and C₃H₆, respectively. (Bottom row) Temperature profiles of both C₂H₄ and C₃H₆, respectively</figcaption></figure>

(Top) Primary unimolecular processes and bimolecular reactions involved in the ozone-assisted oxidation of crotonaldehyde. The numbers in parentheses correspond to the nominal mass of the respective structure.

(Right) Photo-ionization efficiency curve of the signal recorded at m/z 118.026 corresponding to mass of either POZ, SOZ, or KHP. The signal is attributed in part to the KHP based on the calculated ionization energy that matches the signal onset.

<figure><img src="image_14.png" /></figure>

<figure><img src="image_15.png" /></figure>

<figure><img src="image_16.png" /></figure>

<figure><img src="image_17.png" /><figcaption>(Left) Photo-ionization efficiency curve for m/z 130 and (middle) 144 corresponding to the mass of Cl1 + CA and Cl2 + CA, respectively. (Right) temperature profiles for both CIs with CA.</figcaption></figure>

<figure><img src="image_18.png" /></figure>

<figure><img src="image_19.png" /><figcaption>(Left) Photo-ionization efficiency curve for m/z 118 and (right) 132 corresponding to the mass of Cl1 + propionaldehyde and Cl2 + propionaldehyde, respectively</figcaption></figure>

Acknowledgements: This research was funded by UCF and the U.S. Department of Energy, Office of Basic Energy Sciences