High-temperature laser absorption diagnostics for CH2O and CH3CHO and their application to shock tube kinetic studies

Wang, Shengkai; Davidson, David F.; Hanson, Ronald K.

doi:10.1016/j.combustflame.2013.05.004

Cited by 58 publications

(61 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Wang et al 16 data at high temperatures. Our values of the rate coefficients (±30%) measured (1) at low temperatures.…”

Section: Resultsmentioning

confidence: 99%

“…This adjustment of the barrier height is reasonable considering the uncertainties associated with these ab-initio calculations. Furthermore, we note that the RRKM results reported here are for neon as bath gas while Irdam and Kiefer 14 used krypton and Wang et al 16 used argon as bath gas in their experiments. However, the bath gas is expected to cause negligible change in the calculated values of the rate coefficient.…”

mentioning

confidence: 97%

“…[1][2][3] Its importance in combustion led to a number of high temperature kinetic studies for its pyrolytic dissociation [3][4][5][6] and bimolecular reactions. 1,[7][8][9][10] A substantial number of earlier studies 5,7,9,[11][12][13][14][15][16] consisted of utilizing 1,3,5-trioxane (C 3 H 6 O 3 ) as a clean thermolytic source of formaldehyde to avoid the problem of formaldehyde polymerization. These studies assumed reaction (1)…”

Section: Formaldehyde (Ch 2 O) Is An Important Intermediate In the Comentioning

confidence: 99%

See 2 more Smart Citations

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

Alquaity

Giri

et al. 2015

J. Phys. Chem. A

View full text Add to dashboard Cite

Unimolecular dissociation of 1,3,5-trioxane was investigated experimentally and theoretically over a wide range of conditions. Experiments were performed behind reflected shock waves over the temperature range of 775 -1082 K and pressures near 900 Torr using a fast response time-of-flight mass spectrometer (TOF-MS) coupled to a shock tube (ST). Reaction products were identified directly and it was found that formaldehyde is the sole product of 1,3,5-trioxane dissociation. Reaction rate coefficients were extracted by the best fit to the experimentally measured concentration time-histories. Additionally, high-level quantum chemical and RRKM calculations were employed to study the fall off behavior of 1,3,5-trioxane dissociation. Molecular geometries and frequencies of all the species were obtained at the B3LYP/cc-pVTZ, MP2/cc-pVTZ and MP2/aug-cc-pVDZ levels of theory, whereas the single-point energies of the stationary points were calculated using coupled-cluster with

show abstract

“…Wang et al 16 data at high temperatures. Our values of the rate coefficients (±30%) measured (1) at low temperatures.…”

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 97%

Section: Formaldehyde (Ch 2 O) Is An Important Intermediate In the Comentioning

confidence: 99%

See 1 more Smart Citation

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

Alquaity

Giri

et al. 2015

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Formaldehyde (CH 2 O) and acetaldehyde (CH 3 CHO) are the main aldehydes formed in many oxidation processes. 1 The most plentiful carboxylic acid in the troposphere is formic acid and its presence is due to processes such as the oxidation of volatile organic compounds, burning of biomass, engine emissions, among others. 2 In combustion relevant conditions, hydrogen atom abstraction reactions byḢ atoms andȮH, HȮ 2 andĊH 3 radicals vary in importance depending on the temperature (ȮH: > 500 K, HȮ 2 : 800−1300 K,Ḣ andĊH 3 : > 1300 K).…”

Section: Introductionmentioning

confidence: 99%

Theoretical Chemical Kinetic Study of the H-Atom Abstraction Reactions from Aldehydes and Acids by Ḣ Atoms and ȮH, HȮ₂, and ĊH₃ Radicals

2014

View full text Add to dashboard Cite

We have performed a systematic, theoretical chemical kinetic investigation of H atom abstraction by Ḣ atoms and ȮH, HȮ2, and ĊH3 radicals from aldehydes (methanal, ethanal, propanal, and isobutanal) and acids (methanoic acid, ethanoic acid, propanoic acid, and isobutanoic acid). The geometry optimizations and frequencies of all of the species in the reaction mechanisms of the title reactions were calculated using the MP2 method and the 6-311G(d,p) basis set. The one-dimensional hindered rotor treatment for reactants and transition states and the intrinsic reaction coordinate calculations were also determined at the MP2/6-311G(d,p) level of theory. For the reactions of methanal and methanoic acid with Ḣ atoms and ȮH, HȮ2, and ĊH3 radicals, the calculated relative electronic energies were obtained with the CCSD(T)/cc-pVXZ (where X = D, T, and Q) method and were extrapolated to the complete basis set limit. The electronic energies obtained with the CCSD(T)/cc-pVTZ method were benchmarked against the CCSD(T)/CBS energies and were found to be within 1 kcal mol(-1) of one another. Thus, the energies calculated using the less expensive CCSD(T)/cc-pVTZ method were used in all of the reaction mechanisms and in calculating our high-pressure limit rate constants for the title reactions. Rate constants were calculated using conventional transition state theory with an asymmetric Eckart tunneling correction, as implemented in Variflex. Herein, we report the individual and average rate constants, on a per H atom basis, and total rate constants in the temperature range 500-2000 K. We have compared some of our rate constant results to available experimental and theoretical data, and our results are generally in good agreement.

show abstract

“…Tunable diode laser absorption spectroscopy (TDLAS) has been widely used for concentration and temperature sensing in combustion and aerospace research [1][2][3][4][5][6]. The nonintrusive nature of TDLAS has also been exploited in industrial applications and in environmental monitoring [1,7,8].…”

Section: Introductionmentioning

confidence: 99%

Baseline correction for stray light in log-ratio diode laser absorption measurements

2014

View full text Add to dashboard Cite

Log-ratio detection is a convenient technique for making temperature and concentration measurements using sensors based on tunable diode laser absorption spectroscopy. In many practical sensing applications, it is difficult to avoid stray light falling on the signal photodiode of the sensor. This stray light acts as noncommon-mode interference and introduces a systematic error in absorption measurements, which is not removed by baseline subtraction. This paper analyzes the factors that determine this systematic error and also presents a calibration method that can correct for it. This correction method is verified using a simple experiment.

show abstract

High-temperature laser absorption diagnostics for CH2O and CH3CHO and their application to shock tube kinetic studies

Cited by 58 publications

References 34 publications

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

Theoretical Chemical Kinetic Study of the H-Atom Abstraction Reactions from Aldehydes and Acids by Ḣ Atoms and ȮH, HȮ₂, and ĊH₃ Radicals

Baseline correction for stray light in log-ratio diode laser absorption measurements

Contact Info

Product

Resources

About

High-temperature laser absorption diagnostics for CH2O and CH3CHO and their application to shock tube kinetic studies

Cited by 58 publications

References 34 publications

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

High-Temperature Experimental and Theoretical Study of the Unimolecular Dissociation of 1,3,5-Trioxane

Theoretical Chemical Kinetic Study of the H-Atom Abstraction Reactions from Aldehydes and Acids by Ḣ Atoms and ȮH, HȮ2, and ĊH3 Radicals

Baseline correction for stray light in log-ratio diode laser absorption measurements

Contact Info

Product

Resources

About

Theoretical Chemical Kinetic Study of the H-Atom Abstraction Reactions from Aldehydes and Acids by Ḣ Atoms and ȮH, HȮ₂, and ĊH₃ Radicals