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A comprehensive kinetic mechanism for CO, CH2O, and CH3OH combustion

Published on Mar 1, 2007in International Journal of Chemical Kinetics1.42
· DOI :10.1002/kin.20218
Juan Li8
Estimated H-index: 8
(Princeton University),
Zhenwei Zhao13
Estimated H-index: 13
(Princeton University)
+ 3 AuthorsJames J. Scire3
Estimated H-index: 3
Cite
Abstract
New experimental profiles of stable species concentrations are reported for formaldehyde oxidation in a variable pressure flow reactor at initial temperatures of 850–950 K and at constant pressures ranging from 1.5 to 6.0 atm. These data, along with other data published in the literature and a previous comprehensive chemical kinetic model for methanol oxidation, are used to hierarchically develop an updated mechanism for CO/H2O/H2/O2, CH2O, and CH3OH oxidation. Important modifications include recent revisions for the hydrogen–oxygen submechanism (Li et al., Int J Chem Kinet 2004, 36, 565), an updated submechanism for methanol reactions, and kinetic and thermochemical parameter modifications based upon recently published information. New rate constant correlations are recommended for CO + OH = CO2 + H (R23) and HCO + M = H + CO + M (R24), motivated by a new identification of the temperatures over which these rate constants most affect laminar flame speed predictions (Zhao et al., Int J Chem Kinet 2005, 37, 282). The new weighted least-squares fit of literature experimental data for (R23) yields k23 = 2.23 × 105T1.89exp(583/T) cm3/mol/s and reflects significantly lower rate constant values at low and intermediate temperatures in comparison to another recently recommended correlation and theoretical predictions. The weighted least-squares fit of literature results for (R24) yields k24 = 4.75 × 1011T0.66exp(−7485/T) cm3/mol/s, which predicts values within uncertainties of both prior and new (Friedrichs et al., Phys Chem Chem Phys 2002, 4, 5778; DeSain et al., Chem Phys Lett 2001, 347, 79) measurements. Use of either of the data correlations reported in Friedrichs et al. (2002) and DeSain et al. (2001) for this reaction significantly degrades laminar flame speed predictions for oxygenated fuels as well as for other hydrocarbons. The present C1/O2 mechanism compares favorably against a wide range of experimental conditions for laminar premixed flame speed, shock tube ignition delay, and flow reactor species time history data at each level of hierarchical development. Very good agreement of the model predictions with all of the experimental measurements is demonstrated. © 2007 Wiley Periodicals, Inc. 39: 109–136, 2007
  • References (107)
  • Citations (443)
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References107
Newest
Published on Mar 2, 2007in Combustion Science and Technology1.56
Frederick L. Dryer66
Estimated H-index: 66
(Princeton University),
Marcos Chaos22
Estimated H-index: 22
(Princeton University)
+ 3 AuthorsChristopher J. Homer1
Estimated H-index: 1
(Princeton University)
This paper demonstrates the "spontaneous ignition" (autoignition/inflammation and sustained diffusive combustion) from sudden compressed hydrogen releases that is not well documented in the present literature, for which little fundamental explanation, discussion or research foundation exists, and which is apparently not encompassed in recent formulations of safety codes and standards for piping, storage, and use of high pressure compressed gas systems handling hydrogen. Accidental or intended, r...
Published on Jan 1, 2007
R. Sivaramakrishnan21
Estimated H-index: 21
(UIC: University of Illinois at Chicago),
Andrea Comandini10
Estimated H-index: 10
(UIC: University of Illinois at Chicago)
+ 3 AuthorsHai Wang54
Estimated H-index: 54
(SC: University of Southern California)
Abstract The high pressure oxidation of dilute CO mixtures doped with 150–200 ppm of H 2 has been studied behind reflected shock waves in the UIC high pressure single pulse shock tube. The experiments were performed over the temperature range from 1000 to 1500 K and pressures spanning 21–500 bars for stoichiometric ( Φ = 1) and fuel lean ( Φ = 0.5) oxidation. Stable species sampled from the shock tube were analyzed by standard GC, GC/MS techniques. The experimental data obtained in this work wer...
Published on Jan 1, 2007
Venkatesh Vasudevan7
Estimated H-index: 7
(Stanford University),
David F. Davidson39
Estimated H-index: 39
(Stanford University)
+ 2 AuthorsDavid M. Golden43
Estimated H-index: 43
(Stanford University)
Abstract The two-channel thermal decomposition of formaldehyde [CH 2 O], (1a) CH 2 O + Ar → HCO + H + Ar, and (1b) CH 2 O + Ar → H 2 + CO + Ar, was studied in shock tube experiments in the 2258–2687 K temperature range, at an average total pressure of 1.6 atm. OH radicals, generated on shock heating trioxane–O 2 –Ar mixtures, were monitored behind the reflected shock front using narrow-linewidth laser absorption. 1,3,5 trioxane [C 3 H 6 O 3 ] was used as the CH 2 O precursor in the current exper...
Published on Jan 1, 2007
Gaurav Mittal15
Estimated H-index: 15
(Case Western Reserve University),
Chih-Jen Sung49
Estimated H-index: 49
(Case Western Reserve University)
+ 3 AuthorsKevin J. Hughes19
Estimated H-index: 19
(University of Leeds)
Abstract This paper constitutes an experimental and numerical study, using uncertainty analysis of the most important parameters, to evaluate the mechanism for the combustion of CO + H 2 mixtures at high pressures in the range 15–50 bar and temperatures from 950 to 1100 K. Experiments were performed in a rapid compression machine. Autoignition delays were measured for stoichiometric compositions of CO + H 2 containing between 0 and 80% CO in the total fuel mixture. The experimental results showe...
Published on Aug 1, 2006in International Journal of Chemical Kinetics1.42
Gaurav Mittal15
Estimated H-index: 15
(Case Western Reserve University),
Chih-Jen Sung49
Estimated H-index: 49
(Case Western Reserve University),
Richard A. Yetter29
Estimated H-index: 29
(PSU: Pennsylvania State University)
Autoignition of H2/O2 and H2/CO/O2 mixtures has been studied in a rapid compression machine at pressures from 15 to 50 bar, temperatures from 950 to 1100 K, and equivalence ratios from 0.36 to 1.6. In addition, the effect of change in relative concentrations of H2 and CO is investigated by replacing H2 with CO, while keeping the total fuel mole fraction of the combined H2/CO fuel constant. Under the experimental conditions of intermediate temperature and high pressure, reactions involving format...
Published on Jun 1, 2006in Journal of Physical Chemistry A2.64
Branko Ruscic38
Estimated H-index: 38
,
Reinhardt Pinzón8
Estimated H-index: 8
+ 4 AuthorsJ. V. Michael22
Estimated H-index: 22
Through the use of the Active Thermochemical Tables approach, the best currently available enthalpy of formation of HO2 has been obtained as ΔfH298°(HO2) = 2.94 ± 0.06 kcal mol-1 (3.64 ± 0.06 kcal mol-1 at 0 K). The related enthalpy of formation of the positive ion, HO2+, within the stationary electron convention is ΔfH298°(HO2+) = 264.71 ± 0.14 kcal mol-1 (265.41 ± 0.14 kcal mol-1 at 0 K), while that for the negative ion, HO2- (within the same convention), is ΔfH298°(HO2-) = −21.86 ± 0.11 kcal ...
Published on Jun 1, 2006in Journal of Physical Chemistry A2.64
Andrei F. Kazakov24
Estimated H-index: 24
,
Marcos Chaos22
Estimated H-index: 22
+ 1 AuthorsFrederick L. Dryer66
Estimated H-index: 66
Computational singular perturbation (CSP) analysis has been used to gain understanding of the complex kinetic behavior associated with two-stage ignition of large hydrocarbon molecules. To this end, available detailed and reduced chemical kinetics models commonly used in numerical simulations of n-heptane oxidation phenomena are directly analyzed to interpret the underlying fundamental steps leading to two-stage ignition. Unlike previous implementations of the CSP methodology, temperature is inc...
Published on Jan 1, 2006in International Journal of Chemical Kinetics1.42
Ameya V. Joshi5
Estimated H-index: 5
(UD: University of Delaware),
Hai Wang54
Estimated H-index: 54
(SC: University of Southern California)
The rate coefficient of CO + OH products is analyzed with RRKM/master equation analyses and Monte Carlo simulations. The analyses are based on the recent CCSD(T)/cc-pvTZ potential energy surface of Yu et al. Chem Phys Lett 2001, 349, 547–554). It is shown that the experimental data over the temperature range of 80–2500 K and pressure from 1 Torr to 800 bar can be satisfactorily reproduced by lowering the CCSD(T)/cc-pvTZ energy barrier for the CO2 + H exit channel by 1 kcal/mol and more important...
Published on Jan 1, 2006in Journal of Physical Chemistry A2.64
Colberg M1
Estimated H-index: 1
,
Friedrichs G1
Estimated H-index: 1
The rate of the reaction 1, HCO + O2 → HO2 + CO, has been determined (i) at room temperature using a slow flow reactor setup (20 mbar < p < 500 mbar) and (ii) in the temperature range 739 K < T < 1108 K behind reflected shock waves (0.82 bar < p < 1.84 bar) employing a perturbation approach. Following the 193 nm excimer laser photolysis of mixtures of glyoxal in Ar, concentration−time profiles were measured using frequency modulation (FM) detection of HCO at a wavelength of λ = 614.752 nm. Obser...
Branko Ruscic38
Estimated H-index: 38
(Argonne National Laboratory),
James E. Boggs41
Estimated H-index: 41
(University of Texas at Austin)
+ 11 AuthorsJohn F. Stanton55
Estimated H-index: 55
(University of Texas at Austin)
This is the first part of a series of articles reporting critically evaluated thermochemical properties of selected free radicals. The present article contains datasheets for 11 radicals: CH, CH2(triplet), CH2(singlet), CH3, CH2OH, CH3O, CH3CO, C2H5O, C6H5CH2, OH, and NH2. The thermochemical properties discussed are the enthalpy of formation, as well as the heat capacity, integrated heat capacity, and entropy of the radicals. One distinguishing feature of the present evaluation is the systematic...
Cited By443
Newest
Published on Jan 1, 2020
Ziyu Wang6
Estimated H-index: 6
,
Guangying Yu5
Estimated H-index: 5
,
Hameed Metghalchi17
Estimated H-index: 17
Published on Jan 1, 2020in Experimental Thermal and Fluid Science3.49
Santanu Pramanik4
Estimated H-index: 4
(IISc: Indian Institute of Science),
Rv Ravikrishna14
Estimated H-index: 14
(IISc: Indian Institute of Science)
Abstract The present study investigates the combustion dynamics of low-calorific value syngas in the reverse-flow configuration at P = 1 atm using OH* chemiluminescence (5 kHz), noise (50 kHz), and emissions (NOx and CO) measurements. The combustion dynamics have been investigated as a function of the global equivalence ratio (0.32 - 0.89), percentage O2 in the coflow (7.6 - 21%), and the oxidizer preheat temperature (∼ 400 - 800 K). The variation of these parameters resulted in different operat...
Published on Dec 1, 2019in Fuel5.13
Yongxiang Zhang (Hunan University), Jianqin Fu13
Estimated H-index: 13
(Hunan University)
+ 3 AuthorsYanshan Yin1
Estimated H-index: 1
(CSUST: Changsha University of Science and Technology)
Abstract With the increasingly restrictive emission regulations, the emission requirements for internal combustion (IC) engines become more stringent, especially the amount of nitrogen oxides (NOx) emissions. In this investigation, a convenient thermodynamic model was employed to study the effects of operating parameters on NOx emissions for a liquefied methane fueled spark-ignition engine. The selected GRI-MECH 3.0 mechanism was verified by the experimental data and the thermodynamic model was ...
Published on Dec 1, 2019in Fuel5.13
Yang Hua (Hefei University of Technology), Fushui Liu10
Estimated H-index: 10
(BIT: Beijing Institute of Technology)
+ 2 AuthorsShun Meng2
Estimated H-index: 2
(Hefei University of Technology)
Abstract Alcohols have been considered as promising clean alternative fuels for IC engines. At present, the difference and mechanism of particle dynamics for different alcohols is unclear. In this work, numerical simulation of laminar diffusion flame of gasoline blended with different alcohols was carried out by coupling a gas-phase chemical kinetic model and fixed sectional particle model, then the micro-processes of particle nucleation, growth and oxidation were analyzed. The results show that...
Published on Dec 1, 2019in Chemical Engineering Science3.37
H. Janbazi1
Estimated H-index: 1
(University of Duisburg-Essen),
Yasin Karakaya2
Estimated H-index: 2
(University of Duisburg-Essen)
+ 3 AuthorsS. Peukert3
Estimated H-index: 3
(University of Duisburg-Essen)
Abstract Tetramethysilane (TMS) is a precursor for flame synthesis of silica (SiO2) nanoparticles. A chemical reaction mechanism was developed for the oxidation of TMS in a lean low-pressure (p ≈ 30 mbar) H2/O2/Ar flame using species mole fractions, obtained from molecular-beam mass spectrometry (MBMS) measurements in a matrix-supported flat flame doped with 600 ppm TMS. The thermodynamic data of Si-containing species were determined from quantum-chemical calculations at the G4 level of theory. ...
Published on Nov 1, 2019in Combustion and Flame4.12
Xiaoyuan Zhang5
Estimated H-index: 5
(SJTU: Shanghai Jiao Tong University),
Bowen Mei1
Estimated H-index: 1
(SJTU: Shanghai Jiao Tong University)
+ 3 AuthorsYuyang Li24
Estimated H-index: 24
(SJTU: Shanghai Jiao Tong University)
Abstract In this work, laminar flame speeds of CH4/CO/air mixtures were measured at the unburnt temperature of 353 K and pressures from 1 to 10 atm in a high-pressure constant-volume cylindrical combustion vessel. Effects of pressure, equivalence ratio and CO content in CH4/CO mixtures on laminar flame speeds were investigated. A kinetic model for CH4/CO combustion was developed based on recent progress in elementary reactions and validated against previous and present experimental targets. It i...
Published on Nov 1, 2019in Fuel5.13
Yongliang Xie13
Estimated H-index: 13
(Southwest Jiaotong University),
Xujiang Wang1
Estimated H-index: 1
(UCL: University College London)
+ 1 AuthorsZuohua Huang50
Estimated H-index: 50
(Xi'an Jiaotong University)
Abstract Explosion processes of H 2 /CO/air mixtures with diluents are experimentally investigated with a confined vessel. Explosion pressure and maximum rate of pressure rise are obtained and results show that explosion pressure increases firstly and then decreases with increasing equivalence ratios. The maximum rate of pressure rise increases all the time when the combustible mixture becomes richer. When CO 2 and H 2 O are added into the mixture, both explosion pressure and maximum rate of pre...
Published on Nov 1, 2019in Fuel5.13
Yiran Chen (THU: Tsinghua University), Tong Yao2
Estimated H-index: 2
(THU: Tsinghua University)
+ 1 AuthorsKai H. Luo26
Estimated H-index: 26
(UCL: University College London)
Abstract The dynamic processes of ignition and turbulent flame development in a turbulent impinging flame are studied using large eddy simulation (LES). The Dynamic Thickened Flame (DTF) model is extended to incorporate realistic chemical mechanisms to simulate the partially premixed flames due to flame impingement on a solid wall. A new chemical mechanism with 22 species 66 steps is developed for propane. This LES formulation correctly reproduces the different ignition and turbulent flame dynam...
Published on 2019in Applied Surface Science5.16
Yue Cao1
Estimated H-index: 1
(SDU: Shandong University),
Hongwei Qin22
Estimated H-index: 22
(SDU: Shandong University)
+ 1 AuthorsJifan Hu25
Estimated H-index: 25
(SDU: Shandong University)
Abstract DFT calculations are used to investigate the acetone sensing mechanism of PdO-modified hexagonal WO3 (001) surface. It is concluded that compared to the pure h-WO3 (001) surface, modifying the surface with PdO could increase the available adsorption sites for acetone and leads to a sharp increase in the amount of charge transferred from acetone to the surface of the material, which contributes to a decrease in the resistance of h-WO3 (n-type semiconductor material). Moreover, we found t...
Published on 2019in Journal of Supercritical Fluids3.48
Zhengwei Gao1
Estimated H-index: 1
(ZJU: Zhejiang University),
Haiou Wang11
Estimated H-index: 11
(ZJU: Zhejiang University)
+ 2 AuthorsJianren Fan27
Estimated H-index: 27
(ZJU: Zhejiang University)
Abstract This paper is aimed to investigate the real-fluid effects on both diffusion and premixed laminar hydrothermal flames. The real-fluid effects are examined in three aspects, including the equation of state (EOS), thermodynamic, and transport properties. Results show that, for diffusion flames, the introduction of non-ideal EOS is the most significant adjustment as it modifies the flame location, while the correction of thermodynamic and transport properties has minor impacts on the flame ...
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