An investigation of the D/H addition-elimination and H atom abstraction channels in the reaction D + H2CO in the temperature range 296 K ≤ T ≤ 780 K

C. Oehlers, H. Gg Wagner, H. Ziemer, F. Temps, S. Dóbé

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Abstract

The reactions of H and D atoms with H2CO (H + H2CO → H2 + HCO (1.1), D + H2CO → HD + HCO (2.1), and D + H2CO → H + HDCO (2.2)) have been studied in the temperature range 296 K ≤ T ≤ 780 K in an isothermal discharge flow reactor with EPR detection of D and H atoms and LIF detection of HCO. Simultaneous measurements of the absolute concentration-time profiles of the three species established the occurrence of the D/H isotope exchange reaction (2.2) in addition to the H atom abstraction channel (2.1). The rate constants for the three reactions could be represented by the Arrhenius expressions k1.1(T) = (8.7 ± 1.9) × 1012 exp[-(14.5 ± 0.7) kJ mol-1/RT] cm3 mol-1 s-1 k2.1(T) = (1.2 ± 0.5) × 1013 exp[-(15.8 ± 0.8) kJ mol-1/RT] cm3 mol-1 s-1, and k2.2(T) = (5.9 ± 1.5) × 1012 exp[-(14.7 ± 1.0) kJ mol-1/RT] cm3 mol-1 s-1. A mechanistic analysis of reaction 2.2 using the unimolecular rate theory gave these estimates for the classical potential energy barrier heights in the addition of D and H atoms to H2CO: ΔE0(D + H2CO) = 1360 ± 100 cm-1 and ΔE0(H + H2CO) = 1540 ± 150 cm-1.

Original languageEnglish
Pages (from-to)10500-10510
Number of pages11
JournalJournal of Physical Chemistry A
Volume104
Issue number45
Publication statusPublished - Nov 16 2000

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elimination
Atoms
atoms
Temperature
temperature
Energy barriers
Potential energy
Isotopes
laser induced fluorescence
Paramagnetic resonance
Rate constants
isotopes
potential energy
reactors
occurrences
estimates
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An investigation of the D/H addition-elimination and H atom abstraction channels in the reaction D + H2CO in the temperature range 296 K ≤ T ≤ 780 K. / Oehlers, C.; Wagner, H. Gg; Ziemer, H.; Temps, F.; Dóbé, S.

In: Journal of Physical Chemistry A, Vol. 104, No. 45, 16.11.2000, p. 10500-10510.

Research output: Contribution to journalArticle

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abstract = "The reactions of H and D atoms with H2CO (H + H2CO → H2 + HCO (1.1), D + H2CO → HD + HCO (2.1), and D + H2CO → H + HDCO (2.2)) have been studied in the temperature range 296 K ≤ T ≤ 780 K in an isothermal discharge flow reactor with EPR detection of D and H atoms and LIF detection of HCO. Simultaneous measurements of the absolute concentration-time profiles of the three species established the occurrence of the D/H isotope exchange reaction (2.2) in addition to the H atom abstraction channel (2.1). The rate constants for the three reactions could be represented by the Arrhenius expressions k1.1(T) = (8.7 ± 1.9) × 1012 exp[-(14.5 ± 0.7) kJ mol-1/RT] cm3 mol-1 s-1 k2.1(T) = (1.2 ± 0.5) × 1013 exp[-(15.8 ± 0.8) kJ mol-1/RT] cm3 mol-1 s-1, and k2.2(T) = (5.9 ± 1.5) × 1012 exp[-(14.7 ± 1.0) kJ mol-1/RT] cm3 mol-1 s-1. A mechanistic analysis of reaction 2.2 using the unimolecular rate theory gave these estimates for the classical potential energy barrier heights in the addition of D and H atoms to H2CO: ΔE0(D + H2CO) = 1360 ± 100 cm-1 and ΔE0(H + H2CO) = 1540 ± 150 cm-1.",
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AU - Wagner, H. Gg

AU - Ziemer, H.

AU - Temps, F.

AU - Dóbé, S.

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N2 - The reactions of H and D atoms with H2CO (H + H2CO → H2 + HCO (1.1), D + H2CO → HD + HCO (2.1), and D + H2CO → H + HDCO (2.2)) have been studied in the temperature range 296 K ≤ T ≤ 780 K in an isothermal discharge flow reactor with EPR detection of D and H atoms and LIF detection of HCO. Simultaneous measurements of the absolute concentration-time profiles of the three species established the occurrence of the D/H isotope exchange reaction (2.2) in addition to the H atom abstraction channel (2.1). The rate constants for the three reactions could be represented by the Arrhenius expressions k1.1(T) = (8.7 ± 1.9) × 1012 exp[-(14.5 ± 0.7) kJ mol-1/RT] cm3 mol-1 s-1 k2.1(T) = (1.2 ± 0.5) × 1013 exp[-(15.8 ± 0.8) kJ mol-1/RT] cm3 mol-1 s-1, and k2.2(T) = (5.9 ± 1.5) × 1012 exp[-(14.7 ± 1.0) kJ mol-1/RT] cm3 mol-1 s-1. A mechanistic analysis of reaction 2.2 using the unimolecular rate theory gave these estimates for the classical potential energy barrier heights in the addition of D and H atoms to H2CO: ΔE0(D + H2CO) = 1360 ± 100 cm-1 and ΔE0(H + H2CO) = 1540 ± 150 cm-1.

AB - The reactions of H and D atoms with H2CO (H + H2CO → H2 + HCO (1.1), D + H2CO → HD + HCO (2.1), and D + H2CO → H + HDCO (2.2)) have been studied in the temperature range 296 K ≤ T ≤ 780 K in an isothermal discharge flow reactor with EPR detection of D and H atoms and LIF detection of HCO. Simultaneous measurements of the absolute concentration-time profiles of the three species established the occurrence of the D/H isotope exchange reaction (2.2) in addition to the H atom abstraction channel (2.1). The rate constants for the three reactions could be represented by the Arrhenius expressions k1.1(T) = (8.7 ± 1.9) × 1012 exp[-(14.5 ± 0.7) kJ mol-1/RT] cm3 mol-1 s-1 k2.1(T) = (1.2 ± 0.5) × 1013 exp[-(15.8 ± 0.8) kJ mol-1/RT] cm3 mol-1 s-1, and k2.2(T) = (5.9 ± 1.5) × 1012 exp[-(14.7 ± 1.0) kJ mol-1/RT] cm3 mol-1 s-1. A mechanistic analysis of reaction 2.2 using the unimolecular rate theory gave these estimates for the classical potential energy barrier heights in the addition of D and H atoms to H2CO: ΔE0(D + H2CO) = 1360 ± 100 cm-1 and ΔE0(H + H2CO) = 1540 ± 150 cm-1.

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