Very low‐pressure pyrolysis (VLPP) of t‐butylmethyl ether

Abstract

The thermal decomposition of t-butylmethyl ether has been studied using the VLPP technique. The recommended Arrhenius parameters for the molecular elimination, reaction ( I ) , are A(800OK) = 1013,9 sec-I and E, (800'K) = 59.0 & 1.0 kcal/mole. No radical reactions occur under the conditions used. CH,These parameters are in good agreement with earlier experimental work and with theoretical estimates of both A and E.

Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates

“…The rate constants used in the models were in line with previous work of the literature [57,173] and were the following : Nancy [107].…”

“…The chemistry of the oxidation of saturated branched ethers seems to be very close to that of alkanes, as shown by the mechanistic studies of the oxidation of MTBE, ETBE and TAME made by the team of Baronnet [53][54] and the modelling study of the oxidation of dimethyl ether (DME) made by the team of Dryer [55][56]. The only specificity of ethers is a molecular reaction involving the transfer of a H-atom bound to an atom of carbon in β position of the atom of oxygen to give an alcohol molecule and an alkyl radical as proposed by Choo et al [57]. This molecular reaction was proven to be very sensitive to wall effects [58].…”

Progress in detailed kinetic modeling of the combustion of oxygenated components of biofuels

“…Figure 4 presents typical molecular pericyclic reactions in the case of ethers, alcohols and esters. In the case of ethers, a molecular reaction involving the transfer of a H-atom bound to an atom of carbon in β position of the atom of oxygen to give an alcohol molecule and an alkyl radical via a favored four centered cyclic transition state (see first reaction in figure 4) should be taken into account as proposed by Choo et al [131]. The activation energies of the rate constants used in EXGAS for this reaction class are 52 kcal/mol for ethyl tert-butyl ether and 59 kcal/mol for methyl tert-butyl ether [123].…”

Experimental study of fuel decomposition and hydrocarbon growth processes for practical fuel components in nonpremixed flames: MTBE and related alkyl ethers

“…Simple fission predominantly occurs at the C O bonds and produces an alkyl radical (R•) and an alkoxy radical (•O R ) [6]; these radicals then dissociate by β scission to produce alkenes and aldehydes/ketones. Shock tube studies show that the dominant complex fission for alkyl ethers is a four-center elimination that produces an alkene and an alcohol [7]. The diagram in the lower right corner of Fig.…”