Free-radical and molecular processes in the pyrolysis of ethylbenzene

Abstract

From 910 to 1089°K, at pressures of 20 to 36 mm, the pyrolysis of ethylbenzene in a toluene carrier flow system occurs primarily by three reactions[Formula: see text]The Arrhenius equation for the reaction [1], log k1 (s−1) = 14.7 − (70 100/2.3RT), is in agreement with a previous aniline carrier study and with thermochemical calculations. Reaction [11] is surface dependent and yields widely scattered results. For experiments in a conditioned quartz vessel, log k11 (s−1) = 9.06 − (51 700/2.3RT). Values of k1and k12 are unaffected by the nature of the surface and by changes in the surface-to-volume ratio. The rate constants for reaction [12] are somewhat scattered, but yield the approximate equation log k12 (s−1) = 12.7 − (64 000/2.3RT).E1 should possibly be increased by about 1 kcal to allow for the effect of reaction [−1], the recombination of methyl and benzyl species.

Rate of formation of toluene from ethylbenzene

“…The parameters of eq. (7) are in excellent agreement with those found, using carrier techniques, by Clark and Price [5]. In the range measured, the values of kl also agree with those of Szwarc [ 11.…”

“…The parameters of eq. (7) are in excellent agreement with those found, using carrier techniques, by Clark and Price [5]. In the range measured, the values of kl also agree with those of Szwarc [ 11. As was found by these workers, our values of k 1 are lower by factors of up to 2 than those reported by Crowne et al The pyrolysis of ethylbenzene has in common with that of ethane that the stable products of the initiating decomposition can be distinguished among the total products even at fairly high decompositions.…”

“…[GI. In light of the high overall conversion of ethylbenzene studied (2-80%), the industrial-type flow equipment, and the widely differing methods of characterization and analysis, the excellent agreement with the results of [2,3,5] is worthy of note. The data are compatible with current estimates of the heat of formation of benzyl radicals [6,7).…”

Modeling Studies of the Homogeneous Formation of Aromatic Compounds in the Thermal Decomposition of n‐Hexane

“… [6][7][8][9][13][14][15][16][17][18][19][20][21] in which the experimental results are compared with the model simulations.…”

The Pyrolysis of Tetramethyltin

“…In a conditioned reaction vessel this reaction should be completely negligible under the conresults are given in ditions of temperature, pressure, and residence They may be discussed in terms of the time used in the present work (10). However, as following mechanism.…”