Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method

Mohamed Ghalaieny; Asan Bacak; Max McGillen; Damien Martin; Alan V. Knights; Simon O'Doherty; Dudley E. Shallcross; Carl J. Percival

doi:10.1039/c2cp23988d

Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method

Mohamed Ghalaieny, Asan Bacak, Max McGillen, Damien Martin, Alan V. Knights, Simon O'Doherty, Dudley E. Shallcross, Carl J. Percival

Research output: Contribution to journal › Article (Academic Journal) › peer-review

9 Citations (Scopus)

Abstract

The rates of ozonolysis of four sesquiterpenes, beta-caryophyllene, alpha-humulene, isolongifolene and alpha-cedrene, are determined in the gas phase at an elevated temperature of 366 +/- 3 K and a pressure of similar to 780 Torr using the EXTreme RAnge chamber (EXTRA). The experimentally obtained rate coefficients agree with extrapolated room temperature rate coefficients for isolongifolene and alpha-cedrene but not for beta-caryophyllene and alpha-humulene, which were found to be three orders of magnitude slower than this in the literature. These new measurements support the hypothesis that operating under ambient conditions, kinetic measurements of condensable species can be influenced adversely by heterogeneous processes and should therefore be treated with caution.

Original language	English
Pages (from-to)	6596-6602
Number of pages	7
Journal	Physical Chemistry Chemical Physics
Volume	14
Issue number	18
DOIs	https://doi.org/10.1039/c2cp23988d
Publication status	Published - 2012

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Isoprene oxidation and OH recycling
Shallcross, D. E. (Principal Investigator)
1/10/12 → 1/10/15
Project: Research
Laboratory studies of Criegee radical reactions
Shallcross, D. E. (Principal Investigator)
14/03/11 → 14/03/14
Project: Research
The gas phase atmospheric photolysis and reactions of key alkyl nitrates and their role in NOy partitioning.
Shallcross, D. E. (Principal Investigator) & Orr-Ewing, A. J. (Co-Principal Investigator)
1/10/09 → 1/04/13
Project: Research

Cite this

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title = "Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method",

abstract = "The rates of ozonolysis of four sesquiterpenes, beta-caryophyllene, alpha-humulene, isolongifolene and alpha-cedrene, are determined in the gas phase at an elevated temperature of 366 +/- 3 K and a pressure of similar to 780 Torr using the EXTreme RAnge chamber (EXTRA). The experimentally obtained rate coefficients agree with extrapolated room temperature rate coefficients for isolongifolene and alpha-cedrene but not for beta-caryophyllene and alpha-humulene, which were found to be three orders of magnitude slower than this in the literature. These new measurements support the hypothesis that operating under ambient conditions, kinetic measurements of condensable species can be influenced adversely by heterogeneous processes and should therefore be treated with caution.",

author = "Mohamed Ghalaieny and Asan Bacak and Max McGillen and Damien Martin and Knights, {Alan V.} and Simon O'Doherty and Shallcross, {Dudley E.} and Percival, {Carl J.}",

year = "2012",

doi = "10.1039/c2cp23988d",

language = "English",

volume = "14",

pages = "6596--6602",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "Royal Society of Chemistry",

number = "18",

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TY - JOUR

T1 - Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method

AU - Ghalaieny, Mohamed

AU - Bacak, Asan

AU - McGillen, Max

AU - Martin, Damien

AU - Knights, Alan V.

AU - O'Doherty, Simon

AU - Shallcross, Dudley E.

AU - Percival, Carl J.

PY - 2012

Y1 - 2012

N2 - The rates of ozonolysis of four sesquiterpenes, beta-caryophyllene, alpha-humulene, isolongifolene and alpha-cedrene, are determined in the gas phase at an elevated temperature of 366 +/- 3 K and a pressure of similar to 780 Torr using the EXTreme RAnge chamber (EXTRA). The experimentally obtained rate coefficients agree with extrapolated room temperature rate coefficients for isolongifolene and alpha-cedrene but not for beta-caryophyllene and alpha-humulene, which were found to be three orders of magnitude slower than this in the literature. These new measurements support the hypothesis that operating under ambient conditions, kinetic measurements of condensable species can be influenced adversely by heterogeneous processes and should therefore be treated with caution.

AB - The rates of ozonolysis of four sesquiterpenes, beta-caryophyllene, alpha-humulene, isolongifolene and alpha-cedrene, are determined in the gas phase at an elevated temperature of 366 +/- 3 K and a pressure of similar to 780 Torr using the EXTreme RAnge chamber (EXTRA). The experimentally obtained rate coefficients agree with extrapolated room temperature rate coefficients for isolongifolene and alpha-cedrene but not for beta-caryophyllene and alpha-humulene, which were found to be three orders of magnitude slower than this in the literature. These new measurements support the hypothesis that operating under ambient conditions, kinetic measurements of condensable species can be influenced adversely by heterogeneous processes and should therefore be treated with caution.

U2 - 10.1039/c2cp23988d

DO - 10.1039/c2cp23988d

M3 - Article (Academic Journal)

C2 - 22456861

SN - 1463-9076

VL - 14

SP - 6596

EP - 6602

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 18

ER -

Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method

Abstract

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Projects

Isoprene oxidation and OH recycling

Laboratory studies of Criegee radical reactions

The gas phase atmospheric photolysis and reactions of key alkyl nitrates and their role in NOy partitioning.

Cite this