Shock Tube Study on the Thermal Decomposition of <i>n</i>-Butanol

Rosado-Reyes, Claudette M.; Tsang, Wing

doi:10.1021/jp305120h

Cited by 21 publications

(51 citation statements)

References 16 publications

(41 reference statements)

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“…The pre-exponential factor for the CH 3 OH = CH 3 + OH reaction has been reported by the different groups and they are on the order of 10 17 −10 18 . 29−31 Moreover, the pre-exponential factor for the C 2 H 5 OH = C 2 H 5 + OH reaction has also been reported to be of the same Reaction R2 has been assumed to be barrierless and the initial guess of pre-exponential factor was taken from OH recombination with CH 3 The rate parameters for reaction R9 were approximated to those of reaction R8 as attempts to optimize transition state for H abstraction in propenal by OH radical were not successful. Available data on C 3 H 3 dimerization gave a range of rate constants varying from a factor of 10 10 to 10 13 .…”

Section: ■ Chemical Kinetic Mechanismmentioning

confidence: 99%

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Thermal Decomposition of Propargyl Alcohol: Single Pulse Shock Tube Experimental and ab Initio Theoretical Study

2014

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Thermal decomposition of propargyl alcohol (C3H3OH), a molecule of interest in interstellar chemistry and combustion, was investigated using a single pulse shock tube in the temperature ranging from 953 to 1262 K. The products identified include acetylene, propyne, vinylacetylene, propynal, propenal, and benzene. The experimentally observed overall rate constant for thermal decomposition of propargyl alcohol was found to be k = 10((10.17 ± 0.36)) exp(-(39.70 ± 1.83)/RT) s(-1). Ab initio theoretical calculations were carried out to understand the potential energy surfaces involved in the primary and secondary steps of propargyl alcohol thermal decomposition. Transition state theory was used to predict the rate constants, which were then used and refined in a kinetic simulation of the product profile. The first step in the decomposition is C-O bond dissociation, leading to the formation of two important radicals in combustion, OH and propargyl. This has been used to study the reverse OH + propargyl radical reaction, about which there appears to be no prior work. Depending on the site of attack, this reaction leads to propargyl alcohol or propenal, one of the major products at temperatures below 1200 K. A detailed mechanism has been derived to explain all the observed products.

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Section: ■ Chemical Kinetic Mechanismmentioning

confidence: 99%

“…Kinetic Mechanism Used To Explain Thermal Decomposition of Propargyl Alcohol a Units: A in cm3 mol s, temperature in K, E a in kcal mol −1 . b The reactions with lower energy barriers can proceed after test time.…”

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confidence: 99%

Thermal Decomposition of Propargyl Alcohol: Single Pulse Shock Tube Experimental and ab Initio Theoretical Study

2014

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“…The investigation of their fundamental properties assists in the design of advanced engines to control the combustion processes. This is evident as there have been numerous fundamental combustion studies of butanols conducted on laminar premixed and non-premixed flames [e.g., [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25], flow reactors [e.g., [26][27][28][29][30][31], ignition delays in shock tubes [e.g., [32][33][34][35][36][37][38][39][40][41] and rapid compression machines [e.g., [42][43][44][45], fuel pyrolysis [e.g., [46][47][48][49][50], and jet stirred reactors [e.g., 7,13,…”

Section: Introductionmentioning

confidence: 99%

Soot formation in non-premixed counterflow flames of butane and butanol isomers

Singh

Hui

Sung

2016

Combustion and Flame

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Soot formation processes for butane and butanol isomers have been experimentally investigated and compared in a counterflow non-premixed flame configuration at atmospheric pressure. Nonintrusive laser-based diagnostic techniques, including Laser Induced Incandescence and Light Extinction, have been adopted for soot volume fraction measurements. Experimental results of these C 4 fuels have been compared to illustrate the effects of hydroxyl (-OH) group and the isomeric structures on soot formation process. Under the investigated conditions, butane isomers were observed to form more soot than butanol isomers, thereby showing the effect of the hydroxyl group. The effects of isomeric structural differences on sooting propensity were also observed within the butane and butanol isomers. In addition, while soot volume fraction was seen to increase with increasing fuel mole fraction, the ranking of sooting propensity for these C 4 fuels remained unchanged. Effects of varying strain rate and oxygen mole fraction on soot formation were studied herein as well. For each isomeric class, two chemical kinetic models available in the literature were used to simulate and compare the spatially-resolved profiles of the soot precursors. The amount of soot precursors predicted by the models were different and the initial fuel breaking pathways were also found to differ significantly. Furthermore, no direct correlation between the computed mole fractions of soot precursors and the measured amount of soot formed in the present experimental conditions was observed.

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“…Based upon the above analysis, it is likely that the disparities between the experimental and numerical results cannot be resolved without additional specification of the nature of both butanol and butene breakdown chemistry. With regards to fuel breakdown, Vasu and Sarathy [42] provided minor updates to n-butanol unimolecular decomposition reactions based on the shock tube study of Rosado-Reyes and Tsang [43], and additionally increased the rate constant for H-abstraction from formaldehyde, showing slightly improved matching with the data of Stranic et al [20]. In a recent review of alcohol combustion chemistry, Sarathy et al [41] also pointed out that significant uncertainties remain in the description of H-abstraction reactions from the butanol isomers, particularly by OH and HO 2 .…”

Section: Potential Areas For Model Improvementmentioning

confidence: 99%

Comparative study of the counterflow forced ignition of the butanol isomers at atmospheric and elevated pressures

Brady

Hui

Sung

2016

Combustion and Flame

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In support of the development of robust combustion models, the present study describes experimental and computational results on the non-premixed counterflow ignition of all four butanol isomers against heated air for pressures of 1-4 atm, pressure-weighted strain rates of 200-400 s-1 , and fuel molar fractions in nitrogen-diluted mixtures of 0.05-0.25. Comparison of the parametric effects of varied pressure, strain rate, and fuel loading amongst the isomers facilitates a comprehensive evaluation of the effect of varied structural isomerism on transportaffected ignition. The experimental results are simulated using isomer-specific skeletal mechanisms developed from two comprehensive butanol models available in the literature, and are used to validate and assess the performance of these models. Comparison of the experimental and computational results reveal that while both models largely capture the trends in ignition temperature as functions of pressure-weighted strain rate, fuel loading, and pressure, for all isomers both models over-predict the experimental data to an appreciable extent. In addition, neither model captures the experimentally-observed ignition temperature rankings, with both models predicting a large spread amongst n-/iso-/sec-butanol which does not appear in the experimental results. Sensitivity and path analyses reveal that the butene isomers play a significant role in determining the ignition temperatures of the butanol isomers in both models, with the relative branching ratios likely accounting for the ignition temperature rankings observed using each model. It is observed that the reactivity of the butene isomers varies appreciably between the two butanol models, which may account for some of the variability in predictions between the two models. Furthermore, effects of transport properties and their uncertainties on ignition temperature predictions are discussed.

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Shock Tube Study on the Thermal Decomposition of n-Butanol

Cited by 21 publications

References 16 publications

Thermal Decomposition of Propargyl Alcohol: Single Pulse Shock Tube Experimental and ab Initio Theoretical Study

Thermal Decomposition of Propargyl Alcohol: Single Pulse Shock Tube Experimental and ab Initio Theoretical Study

Soot formation in non-premixed counterflow flames of butane and butanol isomers

Comparative study of the counterflow forced ignition of the butanol isomers at atmospheric and elevated pressures

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