Journal ArticleDOI
Reaction Rate Constant of CH2O + H = HCO + H2 Revisited: A Combined Study of Direct Shock Tube Measurement and Transition State Theory Calculation
Reads0
Chats0
TLDR
By designing the experiments to maintain relatively constant H atom concentrations, the current study significantly boosted the measurement sensitivity of the target reaction and suppressed the influence of interfering reactions.Abstract:
The rate constant of the H-abstraction reaction of formaldehyde (CH2O) by hydrogen atoms (H), CH2O + H = H2 + HCO, has been studied behind reflected shock waves with use of a sensitive mid-IR laser absorption diagnostic for CO, over temperatures of 1304–2006 K and at pressures near 1 atm. C2H5I was used as an H atom precursor and 1,3,5-trioxane as the CH2O precursor, to generate a well-controlled CH2O/H reacting system. By designing the experiments to maintain relatively constant H atom concentrations, the current study significantly boosted the measurement sensitivity of the target reaction and suppressed the influence of interfering reactions. The measured CH2O + H rate constant can be expressed in modified Arrhenius from as kCH2O+H(1304–2006 K, 1 atm) = 1.97 × 1011(T/K)1.06 exp(−3818 K/T) cm3 mol–1s–1, with uncertainty limits estimated to be +18%/–26%. A transition-state-theory (TST) calculation, using the CCSD(T)-F12/VTZ-F12 level of theory, is in good agreement with the shock tube measurement and ext...read more
Citations
More filters
Journal ArticleDOI
Atom Tunneling in Chemistry.
Jan Meisner,Johannes Kästner +1 more
TL;DR: The tunnel effect, for example, changes reaction paths and branching ratios, enables chemical reactions in an astrochemical environment that would be impossible by thermal transition, and influences biochemical processes.
Journal ArticleDOI
High-pressure oxidation of methane
Hamid Hashemi,Jakob Munkholt Christensen,Sander Gersen,Howard Levinsky,Stephen J. Klippenstein,Peter Glarborg +5 more
TL;DR: In this paper, a model for high-pressure methane oxidation was established, with particular emphasis on the peroxide chemistry, and the model yielded satisfactory predictions for the onset temperature as well as for most major species upon ignition in the flow reactor, but the concentration of particularly CH3OH was severely underpredicted, indicating that further work is desirable on reactions of CH3O and CH3OO.
Journal ArticleDOI
Atom-Tunneling in Chemistry
Jan Meisner,Johannes Kästner +1 more
TL;DR: In this paper, the influence of tunneling on the reaction rates can directly be monitored using computational investigations, and it is shown that the tunnel effect changes reaction paths and branching ratios, enables chemical reactions in an astrochemical environment that would be impossible by thermal transition.
Journal ArticleDOI
A detailed combined experimental and theoretical study on dimethyl ether/propane blended oxidation
TL;DR: In this article, a binary fuel model for dimethyl ether (DME) and propane is developed, with a focus on engine-relevant conditions (10 −50 ǫ atm and 550 −2000ǫ k).
Journal ArticleDOI
Uncertainty quantification of a newly optimized methanol and formaldehyde combustion mechanism
TL;DR: In this article, a detailed reaction mechanism for methanol combustion that is capable of describing ignition, flame propagation and species concentration profiles with high accuracy has been developed, starting from a modified version of the methanoline combustion mechanism of Li et al. (2007) and adopting the H 2 /CO base chemistry from the joint optimized hydrogen and syngas combustion mechanism.
References
More filters
Journal ArticleDOI
The HITRAN 2008 molecular spectroscopic database
Laurence S. Rothman,Iouli E. Gordon,Yurii L. Babikov,A. Barbe,D. Chris Benner,Peter F. Bernath,Manfred Birk,Luca Bizzocchi,Vincent Boudon,Linda R. Brown,Alain Campargue,Kelly Chance,Edward A. Cohen,L. H. Coudert,V. M. Devi,Brian J. Drouin,André Fayt,Jean-Marie Flaud,Robert R. Gamache,Jeremy J. Harrison,Jean-Michel Hartmann,Christian Hill,Joseph T. Hodges,D. Jacquemart,Antoine Jolly,Julien Lamouroux,R. J. Le Roy,Gang Li,David A. Long,O.M. Lyulin,C.J. Mackie,Steven T. Massie,Semen Mikhailenko,Holger S. P. Müller,Olga V. Naumenko,Andrei Nikitin,Johannes Orphal,V.I. Perevalov,Agnes Perrin,E. R. Polovtseva,Charlotte Richard,Mary Ann H. Smith,Evgeniya Starikova,Keeyoon Sung,S.A. Tashkun,Jonathan Tennyson,Geoff Toon,Vl.G. Tyuterev,G. Wagner +48 more
TL;DR: The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additional absorption phenomena, added line-shape formalisms, and validity, and molecules, isotopologues, and perturbing gases have been added that address the issues of atmospheres beyond the Earth.
Journal ArticleDOI
Evaluated Kinetic Data for Combustion Modelling
Donald L. Baulch,Carlos J. Cobos,Richard A. Cox,C. Esser,P. Frank,Th. Just,J. A. Kerr,Michael J. Pilling,Jürgen Troe,Raymond W. Walker,J. Warnatz +10 more
TL;DR: In this paper, the authors present a compilation of critically evaluated kinetic data on elementary homogeneous gas phase chemical reactions for use in modelling combustion processes Data sheets are presented for some 196 reactions each data sheet sets out relevant thermodynamic data, rate coefficient measurements, an assessment of the reliability of the data, references and recommended rate parameters Tables summarizing the preferred rate data are also given
Journal ArticleDOI
Chemical Kinetic Data Base for Combustion Chemistry. Part I. Methane and Related Compounds
W. Tsang,R. F. Hampson +1 more
TL;DR: In this paper, the authors evaluated data on the kinetics and thermodynamic properties of species that are of importance in methanepyrolysis and combustion, including H, H2, O, O2, OH, HO2, CH2O, CH4, C2H6, HCHO, CO2, CO, HCO, CH3, CH5, CH6, CH7, CH8, CH9, CH10, CH11, CH12, CH13, CH14, CH15, CH16, CH17, CH
Evaluated kinetic data for combustion modelling supplement I
Donald L. Baulch,Carlos J. Cobos,Richard A. Cox,P. Frank,Garry Hayman,Th. Just,J. A. Kerr,T. Murrells,M. A. Pilling,Jürgen Troe,Raymond W. Walker,J. Warnatz +11 more
TL;DR: In this article, a compilation of kinetic data on elementary, homogeneous, gas phase reactions of neutral species involved in combustion systems has been presented under the auspices of the European Community Energy Research and Development Program.