Letter: Determination of Ionization Energies of a Monoterpene Series by Atmospheric Pressure Photoionization Using Tunable Vacuum Ultraviolet Synchrotron Radiation

Méjean, Marie; Giuliani, Alexandre; Brunelle, Alain; Touboul, David

doi:10.1255/ejms.1291

Cited by 6 publications

(7 citation statements)

References 22 publications

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“…Méjean et al measured ionization energies of several monoterpenes by atmospheric pressure photoionization (APPI) at the SOLEIL synchrotron in France and determined an IE of 8.54 eV for limonene [30]. This value is significantly higher than the IE of α-pinene and there is also no increase in the measured PIE spectrum at this photon energy, which would indicate the formation of limonene in the flame.…”

Section: Unimolecular Dissociation Of Myrcene and Comparison Of Species Poolmentioning

confidence: 99%

Experimental flat flame study of monoterpenes: Insights into the combustion kinetics of α-pinene, β-pinene, and myrcene

Bierkandt

Hoener

Gaiser

et al. 2021

Proceedings of the Combustion Institute

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Pinenes and pinene dimers have similar energy densities to petroleum-based fuels and are regarded as alternative fuels. The pyrolysis of the pinenes is well studied, but information on their combustion kinetics is limited. Three stoichiometric, flat premixed flames of the C 10 H 16 monoterpenes α-pinene, β-pinene, and myrcene were investigated by synchrotron-based photoionization molecular-beam mass spectrometry (PI-MBMS) at the Advanced Light Source (ALS). This technique allows isomerresolved identification and quantification of the flame species formed during the combustion process.Flame-sampling molecular-beam mass spectrometry even enables the detection of very reactive radical species. Myrcene was chosen because of its known formation during β-pinene pyrolysis. The quantitative speciation data and the discussed decomposition steps of the fuels provide important information for the development of future chemical kinetic reaction mechanisms concerning pinene combustion. The main decomposition of myrcene starts with the unimolecular cleavage of the carbon-carbon single bond between the two allylic carbon atoms. Further decompositions by βscission to stable combustion intermediates such as isoprene (C 5 H 8 ), 1,2,3-butatriene (C 4 H 4 ) or allene (aC 3 H 4 ) are consistent with the observed species pool. Concentrations of all detected hydrocarbons in the β-pinene flame are closer to the myrcene flame than to the α-pinene flame.These similarities and the direct identification of myrcene by its photoionization efficiency spectrum during β-pinene combustion indicate that β-pinene undergoes isomerization to myrcene under the studied flame conditions. Aromatic species such as phenylacetylene (C 8 H 6 ), styrene (C 8 H 8 ), xylenes (C 8 H 10 ), and indene (C 9 H 8 ) could be clearly identified and have higher concentrations in the αpinene flame. Conclusively, a higher sooting tendency can generally be expected for this monoterpene. The presented quantitative speciation data of flat premixed flames of the three monoterpenes α-pinene, β-pinene, and myrcene give insights into their combustion kinetics.

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Section: Unimolecular Dissociation Of Myrcene and Comparison Of Species Poolmentioning

confidence: 99%

Experimental flat flame study of monoterpenes: Insights into the combustion kinetics of α-pinene, β-pinene, and myrcene

Bierkandt

Hoener

Gaiser

et al. 2021

Proceedings of the Combustion Institute

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“…To our knowledge, the only other terpene, known to have even lower ionization thresholds is α-terpinene, for which an adiabatic ionization energy of 7.47 eV (ref. 56) and vertical energies of 7.57–7.67 eV (ref. 48 and 57) have been reported.…”

Section: Discussionmentioning

confidence: 99%

Analysis of the volatile monoterpene composition of citrus essential oils by photoelectron spectroscopy employing continuously monitored dynamic headspace sampling

Ganjitabar,

Hadidi,

Garcia

et al. 2023

Analyst

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“…Very recent experimental values on the monoterpene ionization energies, IEs, are available for α‐pinene (8.35 eV), γ‐terpinene (8.37 eV), β‐pinene (8.65), 3‐carene (8.5 eV), ( R )‐limonene (8.54 eV) and camphene (8.7 eV) from synchrotron atmospheric pressure photoionization experiments . Ionization energies of α‐phellandrene (8.12 eV), ocimene (8.38 eV), sabinene (8.48 eV) and myrcene (8.5 eV) were estimated using a method with the linear regression fit of the dependence of the known experimental IEs on the negative of the calculated energies of the highest occupied molecular orbital, HOMO .…”

Section: Methodsmentioning

confidence: 99%

Styrene radical cations for chemical ionization mass spectrometry analyses of monoterpene hydrocarbons

Spesyvyi

Španěl

Sovová

2019

Rapid Comm Mass Spectrometry

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Rationale Monoterpene hydrocarbons play an important role in the formation of secondary aerosol particles and in atmospheric chemistry. Thus, there is a demand to measure their individual concentrations in situ in real time. Currently, only the total concentration of monoterpenes C10H16 can be determined by chemical ionization mass spectrometry techniques using reagent ions H3O+, NO+ and (C6H6)n+• without gas chromatographic separation. Methods The styrene cation C8H8+• was investigated as a reagent for chemical ionization of monoterpenes. The modified selected ion flow drift tube, SIFDT, technique was used to characterize the differences in product ion distributions between α‐phellandrene, α‐pinene, γ‐terpinene, β‐pinene, ocimene, sabinene, 3‐carene, (R)‐limonene, camphene and myrcene. Results The monoterpene molecular cation C10H16+• is the main product (about 90%) for all isomers except (R)‐limonene and camphene with an efficient channel of C8H8+•C10H16 adduct formation and γ‐terpinene with unexpectedly significant product ions at m/z 134 and 135 corresponding to losses of H2 and H. Conclusions Utilization of the styrene cation for the ionization of monoterpenes is beneficial due to the very low fragmentation of the product ions. Specific association product ions for camphene and (R)‐limonene and fragment product ions for γ‐terpinene allow them to be distinguished from other isomers that produce mostly the molecular cation.

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Letter: Determination of Ionization Energies of a Monoterpene Series by Atmospheric Pressure Photoionization Using Tunable Vacuum Ultraviolet Synchrotron Radiation

Cited by 6 publications

References 22 publications

Experimental flat flame study of monoterpenes: Insights into the combustion kinetics of α-pinene, β-pinene, and myrcene

Experimental flat flame study of monoterpenes: Insights into the combustion kinetics of α-pinene, β-pinene, and myrcene

Analysis of the volatile monoterpene composition of citrus essential oils by photoelectron spectroscopy employing continuously monitored dynamic headspace sampling

Styrene radical cations for chemical ionization mass spectrometry analyses of monoterpene hydrocarbons

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