Variable-temperature rate coefficients of proton-transfer equilibrium reaction C2H4 + H3O+ ↔ C 2H5+ + H2O measured with a coaxial molecular beam radio frequency ring electrode ion trap

Mark A. Smith, Bing Yuan, Andrei M Sanov

Research output: Contribution to journalArticle

Abstract

The rate coefficients for the forward and reverse proton-transfer reactions C2H4 + H3O+ ↔ C 2H5+ + H2O are studied with respect to independent varied neutral molecule and ion temperatures. The measurements are performed using a coaxial molecular beam radio frequency ring electrode ion trap at trap temperatures down to 23 K and beam temperatures up to 450 K. The temperature-dependent rate coefficients suggest that in this temperature window, the reaction proceeds through a statistically equilibrated complex. In order to explain the observed rate coefficients, a new type of reaction temperature was defined in these studies that considered collisional and internal (rotational and vibrational) degrees of freedom of both H3O+ and C2H4. The enthalpy and entropy of the equilibrium reaction deduced from a Van't Hoff plot are δH = (5.1 ± 0.5) kJ̇mol-1 and δS = (-15.0 ± 0.9) J̇mol -1̇K-1, respectively.

Original languageEnglish (US)
Pages (from-to)11596-11600
Number of pages5
JournalJournal of Physical Chemistry A
Volume116
Issue number47
DOIs
StatePublished - Nov 29 2012

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Proton transfer
Molecular beams
molecular beams
radio frequencies
Ions
Electrodes
electrodes
protons
rings
coefficients
Temperature
temperature
ion temperature
trucks
Enthalpy
Entropy
degrees of freedom
plots
enthalpy
traps

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

@article{707941039047488eb06f809a09e2a1bb,
title = "Variable-temperature rate coefficients of proton-transfer equilibrium reaction C2H4 + H3O+ ↔ C 2H5+ + H2O measured with a coaxial molecular beam radio frequency ring electrode ion trap",
abstract = "The rate coefficients for the forward and reverse proton-transfer reactions C2H4 + H3O+ ↔ C 2H5+ + H2O are studied with respect to independent varied neutral molecule and ion temperatures. The measurements are performed using a coaxial molecular beam radio frequency ring electrode ion trap at trap temperatures down to 23 K and beam temperatures up to 450 K. The temperature-dependent rate coefficients suggest that in this temperature window, the reaction proceeds through a statistically equilibrated complex. In order to explain the observed rate coefficients, a new type of reaction temperature was defined in these studies that considered collisional and internal (rotational and vibrational) degrees of freedom of both H3O+ and C2H4. The enthalpy and entropy of the equilibrium reaction deduced from a Van't Hoff plot are δH = (5.1 ± 0.5) kJ̇mol-1 and δS = (-15.0 ± 0.9) J̇mol -1̇K-1, respectively.",
author = "Smith, {Mark A.} and Bing Yuan and Sanov, {Andrei M}",
year = "2012",
month = "11",
day = "29",
doi = "10.1021/jp306372v",
language = "English (US)",
volume = "116",
pages = "11596--11600",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "47",

}

TY - JOUR

T1 - Variable-temperature rate coefficients of proton-transfer equilibrium reaction C2H4 + H3O+ ↔ C 2H5+ + H2O measured with a coaxial molecular beam radio frequency ring electrode ion trap

AU - Smith, Mark A.

AU - Yuan, Bing

AU - Sanov, Andrei M

PY - 2012/11/29

Y1 - 2012/11/29

N2 - The rate coefficients for the forward and reverse proton-transfer reactions C2H4 + H3O+ ↔ C 2H5+ + H2O are studied with respect to independent varied neutral molecule and ion temperatures. The measurements are performed using a coaxial molecular beam radio frequency ring electrode ion trap at trap temperatures down to 23 K and beam temperatures up to 450 K. The temperature-dependent rate coefficients suggest that in this temperature window, the reaction proceeds through a statistically equilibrated complex. In order to explain the observed rate coefficients, a new type of reaction temperature was defined in these studies that considered collisional and internal (rotational and vibrational) degrees of freedom of both H3O+ and C2H4. The enthalpy and entropy of the equilibrium reaction deduced from a Van't Hoff plot are δH = (5.1 ± 0.5) kJ̇mol-1 and δS = (-15.0 ± 0.9) J̇mol -1̇K-1, respectively.

AB - The rate coefficients for the forward and reverse proton-transfer reactions C2H4 + H3O+ ↔ C 2H5+ + H2O are studied with respect to independent varied neutral molecule and ion temperatures. The measurements are performed using a coaxial molecular beam radio frequency ring electrode ion trap at trap temperatures down to 23 K and beam temperatures up to 450 K. The temperature-dependent rate coefficients suggest that in this temperature window, the reaction proceeds through a statistically equilibrated complex. In order to explain the observed rate coefficients, a new type of reaction temperature was defined in these studies that considered collisional and internal (rotational and vibrational) degrees of freedom of both H3O+ and C2H4. The enthalpy and entropy of the equilibrium reaction deduced from a Van't Hoff plot are δH = (5.1 ± 0.5) kJ̇mol-1 and δS = (-15.0 ± 0.9) J̇mol -1̇K-1, respectively.

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U2 - 10.1021/jp306372v

DO - 10.1021/jp306372v

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