Method for measuring carbon kinetic isotope effects of gas-phase reactions of light hydrocarbons with the hydroxyl radical

Rebecca S. Anderson; Eva Czuba; Darrell Ernst; Lin Huang; Alexandra E. Thompson; Jochen Rudolph

doi:10.1021/jp034256d

Method for measuring carbon kinetic isotope effects of gas-phase reactions of light hydrocarbons with the hydroxyl radical

Rebecca S. Anderson
, Eva Czuba
, Darrell Ernst
, Lin Huang
, Alexandra E. Thompson
, Jochen Rudolph

Research output: Contribution to journal › Article › peer-review

36 Scopus citations

Abstract

A technique for the accurate measurement of the carbon kinetic isotope effects (KIEs) of the reactions of light non-methane hydrocarbons (NMHC) with OH radicals in the gas phase is presented. The method uses a variant of established relative rate techniques, which has been optimized for measurements of KIEs. The instrumentation consists of three basic components: (1) a gas-phase reaction chamber, (2) a gas chromatograph (GC) for separating the components of the reaction mixture, and (3) an isotope ratio mass spectrometer coupled on-line to the GC. Using this technique, measurements of hydroxyl radical reaction KIEs with C₂-C₉ saturated and unsaturated hydrocarbons having rate constants between 10^-11 and 10^-13 cm³ molecule^-1 s^-1 are achievable. This method has been used successfully to measure the carbon KIE for the reactions of OH with a wide range of hydrocarbons in the gas phase.

Original language	English
Pages (from-to)	6191-6199
Number of pages	9
Journal	Journal of Physical Chemistry A
Volume	107
Issue number	32
DOIs	https://doi.org/10.1021/jp034256d
State	Published - Aug 14 2003
Externally published	Yes

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title = "Method for measuring carbon kinetic isotope effects of gas-phase reactions of light hydrocarbons with the hydroxyl radical",

abstract = "A technique for the accurate measurement of the carbon kinetic isotope effects (KIEs) of the reactions of light non-methane hydrocarbons (NMHC) with OH radicals in the gas phase is presented. The method uses a variant of established relative rate techniques, which has been optimized for measurements of KIEs. The instrumentation consists of three basic components: (1) a gas-phase reaction chamber, (2) a gas chromatograph (GC) for separating the components of the reaction mixture, and (3) an isotope ratio mass spectrometer coupled on-line to the GC. Using this technique, measurements of hydroxyl radical reaction KIEs with C2-C9 saturated and unsaturated hydrocarbons having rate constants between 10-11 and 10-13 cm3 molecule-1 s-1 are achievable. This method has been used successfully to measure the carbon KIE for the reactions of OH with a wide range of hydrocarbons in the gas phase.",

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doi = "10.1021/jp034256d",

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TY - JOUR

T1 - Method for measuring carbon kinetic isotope effects of gas-phase reactions of light hydrocarbons with the hydroxyl radical

AU - Anderson, Rebecca S.

AU - Czuba, Eva

AU - Ernst, Darrell

AU - Huang, Lin

AU - Thompson, Alexandra E.

AU - Rudolph, Jochen

PY - 2003/8/14

Y1 - 2003/8/14

N2 - A technique for the accurate measurement of the carbon kinetic isotope effects (KIEs) of the reactions of light non-methane hydrocarbons (NMHC) with OH radicals in the gas phase is presented. The method uses a variant of established relative rate techniques, which has been optimized for measurements of KIEs. The instrumentation consists of three basic components: (1) a gas-phase reaction chamber, (2) a gas chromatograph (GC) for separating the components of the reaction mixture, and (3) an isotope ratio mass spectrometer coupled on-line to the GC. Using this technique, measurements of hydroxyl radical reaction KIEs with C2-C9 saturated and unsaturated hydrocarbons having rate constants between 10-11 and 10-13 cm3 molecule-1 s-1 are achievable. This method has been used successfully to measure the carbon KIE for the reactions of OH with a wide range of hydrocarbons in the gas phase.

AB - A technique for the accurate measurement of the carbon kinetic isotope effects (KIEs) of the reactions of light non-methane hydrocarbons (NMHC) with OH radicals in the gas phase is presented. The method uses a variant of established relative rate techniques, which has been optimized for measurements of KIEs. The instrumentation consists of three basic components: (1) a gas-phase reaction chamber, (2) a gas chromatograph (GC) for separating the components of the reaction mixture, and (3) an isotope ratio mass spectrometer coupled on-line to the GC. Using this technique, measurements of hydroxyl radical reaction KIEs with C2-C9 saturated and unsaturated hydrocarbons having rate constants between 10-11 and 10-13 cm3 molecule-1 s-1 are achievable. This method has been used successfully to measure the carbon KIE for the reactions of OH with a wide range of hydrocarbons in the gas phase.

UR - https://www.scopus.com/pages/publications/0041467632

U2 - 10.1021/jp034256d

DO - 10.1021/jp034256d

M3 - Article

AN - SCOPUS:0041467632

SN - 1089-5639

VL - 107

SP - 6191

EP - 6199

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 32

ER -

Method for measuring carbon kinetic isotope effects of gas-phase reactions of light hydrocarbons with the hydroxyl radical

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