Thermal explosions and the linear mixture rule

Clothier, P.Q.E.; Collister, John L.; Glionna, Marsha T. J.; Pritchard, H. O.

doi:10.1039/f29888400035

Cited by 2 publications

(1 citation statement)

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“…In the absence of reliable data, some simplifications had to be made, viz. : (1) that the rate of the free-radical-catalysed isomerisation (3) was independent of the nature of the free radical (ie. CH3 or C2H5); ( 2) that all overall reactions, such as CH3NC+Hg(C2H5)2 -+ C2H5CN+Hg+C3H, etc.…”

Section: Ch3cnmentioning

confidence: 99%

Simulation of thermal explosions in gaseous mixtures

Thang¹,

Pritchard²

1988

J. Chem. Soc., Faraday Trans. 2

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Thermal explosions of three gaseous mixtures, (i) methyl isocyanide-ethyl isocyanide, (ii) methyl isocyanide-diethyl mercury and (iii) methyl isocyanide-di-t-butyl peroxide, at 350 "C in a 2 dm3 sphere, are examined numerically. In case (i), the reactants appear to behave in an almost additive fashion, but in case (ii) the production of ethyl radicals from the diethyl mercury sensitises the explosion of the methyl isocyanide; however, in case (iii), the dominant effect is not a free-radical one, but an acceleration of the explosion due to the energy release in the peroxide decomposition.In an earlier paper, we described experiments on the thermal explosions of mixtures of methyl isocyanide with ethyl isocyanide, diethyl mercury and di-t-butyl peroxide at 350 "C in a 2 dm3 spherical vessel;' thermal conductivities for ethyl isocyanide and diethyl mercury were measured in that work, those for methyl isocyanide' and di-t-butyl peroxide3 being already known. We now describe the results of a straightforward extension of the algorithm described by Moise and Pritchard2 to thermal explosions in these three mixtures; unless otherwise stated, all kinetic and thermodynamic constants for these reactions are taken from these three papers.

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Section: Ch3cnmentioning

confidence: 99%