Kinetic and modeling studies on ETBE pyrolysis behind reflected shock waves

Yasunaga, Kōjirō; Kuraguchi, Yuma; Hidaka, Yoshiaki; Takahashi, Osamu; Yamada, Hiroshi; Koike, Takao

doi:10.1016/j.cplett.2007.11.097

Cited by 12 publications

(7 citation statements)

References 14 publications

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“…The rate calculated in this study agrees very well with the rate from Yasunaga et al. for ethyl tert‐butyl ether 48 . Agreement with the more analogous reaction from Sumathi 2003 54 is not quite as good but still within a factor of four at high temperatures.…”

Section: Methodssupporting

confidence: 84%

Oxidation and pyrolysis of methyl propyl ether

Johnson

Nimlos

Ninnemann

et al. 2021

Int J of Chemical Kinetics

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The ignition, oxidation, and pyrolysis chemistry of methyl propyl ether (MPE) was probed experimentally at several different conditions, and a comprehensive chemical kinetic model was constructed to help understand the observations, with many of the key parameters computed using quantum chemistry and transition state theory. Experiments were carried out in a shock tube measuring time variation of CO concentrations, in a flow tube measuring product concentrations, and in a rapid compression machine (RCM) measuring ignition delay times. The detailed reaction mechanism was constructed using the Reaction Mechanism Generator software. Sensitivity and flux analyses were used to identify key rate and thermochemical parameters, which were then computed using quantum chemistry to improve the mechanism. Validation of the final model against the 1–20 bar 600–1500 K experimental data is presented with a discussion of the kinetics. The model is in excellent agreement with most of the shock tube and RCM data. Strong non‐monotonic variation in conversion and product distribution is observed in the flow‐tube experiments as the temperature is increased, and unusually strong pressure dependence and significant heat release during the compression stroke is observed in the RCM experiments. These observations are largely explained by a close competition between radical decomposition and addition to O2 at different sites in MPE; this causes small shifts in conditions to lead to big shifts in the dominant reaction pathways. The validated mechanism was used to study the chemistry occurring during ignition in a diesel engine, simulated using Ignition Quality Test (IQT) conditions. At the IQT conditions, where the MPE concentration is higher, bimolecular reactions of peroxy radicals are much more important than in the RCM.

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Section: Methodssupporting

confidence: 84%

Oxidation and pyrolysis of methyl propyl ether

Johnson

Nimlos

Ninnemann

et al. 2021

Int J of Chemical Kinetics

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“…The high pressure limit rate constant of 1.0 × 10 14 exp(−32 335/ T ) s −1 was adopted for reaction . This is estimated by analogy with the unimolecular elimination reaction of ethyl tert -butyl ether (ETBE) as described by Yasunaga et al, who showed that not only does ETBE undergo a four-centered elimination to form iso -butene and ethanol, reaction , but also undergoes a similar elimination to form tert -butanol and ethylene, reaction . ETBE = i C 4 H 8 + C 2 H 5 OH ETBE = ( C H 3 ) 3 COH + C 2 H 4 Taking into account the number of methyl groups in DEE, double the value of the frequency factor proposed by Yasunaga et al for reaction was adopted for reaction .…”

Section: Methodsmentioning

confidence: 99%

A Multiple Shock Tube and Chemical Kinetic Modeling Study of Diethyl Ether Pyrolysis and Oxidation

et al. 2010

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The pyrolysis and oxidation of diethyl ether (DEE) has been studied at pressures from 1 to 4 atm and temperatures of 900-1900 K behind reflected shock waves. A variety of spectroscopic diagnostics have been used, including time-resolved infrared absorption at 3.39 mum and time-resolved ultraviolet emission at 431 nm and absorption at 306.7 nm. In addition, a single-pulse shock tube was used to measure reactant, intermediate, and product species profiles by GC samplings at different reaction times varying from 1.2 to 1.8 ms. A detailed chemical kinetic model comprising 751 reactions involving 148 species was assembled and tested against the experiments with generally good agreement. In the early stages of reaction the unimolecular decomposition and hydrogen atom abstraction of DEE and the decomposition of the ethoxy radical have the largest influence. In separate experiments at 1.9 atm and 1340 K, it is shown that DEE inhibits the reactivity of an equimolar mixture of hydrogen and oxygen (1% of each).

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“…H-atom abstraction reactions by hydroxyl radicals from an allylic carbon atom inhibit reactivity for all three isomers at all temperatures. The rate constants of C4H8-1 + ȮH and C4H8-2 + ȮH are adopted from the experimental work and theoretical study of Vasu et al [21] at the CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d)) level of theory, while the rate constant of iC4H8 + ȮH is calculated at the QCISD(T)/CBS//M062X/6-311++G(d,p) level of theory as part of this study. Figure 7 (a)…”

Section: Influence Of Isomeric Structure On Ignition Delay Timementioning

confidence: 99%