36. The kinetics of the dehydrochlorination of substituted hydrocarbons. Part II. The mechanism of the thermal decomposition of 1 : 2-dichloroethane

Barton, D. H. R.; Howlett, K. E.

doi:10.1039/jr9490000155

Cited by 44 publications

(12 citation statements)

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“…The values of log fa from C2H3CI to C2HCI3 are in good agreement with recent results (10,12,13,54,115) if zero activation energy is assumed. The resulting dissociation energies of chlorinated free radicals D(C-C1) are in good agreement with data obtained from pyrolysis reactions (16,18,19,21,22,111,113) and refer to nonactivated species. The overall activation energies and quantum yields of these reactions have been reviewed (107); combined with more recent data on the over-all reaction rates in steady and intermittent light (12,13,54), these permit one to calculate fa, fa.…”

Section: Chlorination Of Other Derivatives Of C%h4 and Cjitsupporting

confidence: 84%

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Chiltz¹,

Goldfinger²,

Huybrechts³

et al. 1963

Chem. Rev.

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Section: Chlorination Of Other Derivatives Of C%h4 and Cjitsupporting

confidence: 84%

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Chiltz¹,

Goldfinger²,

Huybrechts³

et al. 1963

Chem. Rev.

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“…These data can be used in order to match the overall conversion of EDC but are mainly useful in order to characterize the fouling or the polymerization process taking place inside the pyrolysis coils. Literature data on EDC pyrolysis (Barton and Howlett 1949;Holbrook et al, 1971;Huybrechts et al, 1972;Yano et al, 1980;Ashmore et al, 1982) usually report some mechanistic considerations and the overall rate expressions, but are very poor if the attention is towards the minor or trace components. Thermal dehydrochlorination of EDC is a very selective process and VC yields are usually higher than 95% with conversions in the range of 50-60%.…”

Section: Validation Of the Kinetic Model And Comparison With Experimementioning

confidence: 98%

Pyrolysis and Chlorination of Small Hydrocarbons

Ranzi

Dente

Rovaglio

et al. 1992

Chemical Engineering Communications

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The bases of the kinetic modeling of Chlorine containing systems are addressed in this article, A kinetic scheme, involving more than 300 elementary reactions and 46 molecular and radicalic species, has been developed based on general thermochemical kinetic theories as well as the consolidated know-how in the field of hydrocarbon pyrolysis.Several comparisons with commercial and laboratory experimental data indicate a fair agreement in a wide area of lower and higher pressures (up to 30 atm) also covering the high temperature range of methylchloride pyrolysis (1000"C). Mathematical model of EDC pyrolysis furnaces already allows to evaluate process performances and alternatives accounting for fouling rates and on-stream times.The kinetic scheme can be applied to study the methane chlorination reaction system and the dichloroethane (EDC) pyrolysis system. The kinetic scheme is coupled with a furnace model and appropriate mathematical techniques to solve the resulting system of material, energy and momentum conservation equations. A coking model has also been incorporated as fouling of coils determines the run length of the furnaces. Simulation of the pyrolysis of EDC to produce vinyl chloride shows that the results are in reasonable agreement with observed values and trends. Application of the model for the design of coils and evaluation of process alternatives is discussed.

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“…From the "maximally inhibited" rate of pyrolysis [30]. This value contains a heterogenous contribution as stated by the authors.…”

mentioning

confidence: 97%

Pyrolysis of 1,2‐dichloropropane

Martens

Godfroid

Ramoisy

1970

Int J of Chemical Kinetics

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The thermal decomposition of 1,2-dichloropropane at atmospheric pressure has been studied in the temperature range 227-59OoC, in a flow system. Above 45OoC, the reaction is homogenous and unimolecular with a rate constant:Below 45OoC, a low activation energy, probably heterogenous process competes with the gas phase reaction.The primary reaction products are HCl and the monochloropropene isomers; the relative amounts of each isomer depend on the temperature in the low but not in the high temperature region. The direction of the HCl elimination is discussed in terms of substituent effects at the a-and ,%carbon positions and compared with literature data on similar reactions.Secondary products are formed principally by further pyrolysis of ally1 chloride. The first-order rate constant of this reaction is given by: k = 10*.54*0.2 exp (-37,275 f 700/RT) sec-l.

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36. The kinetics of the dehydrochlorination of substituted hydrocarbons. Part II. The mechanism of the thermal decomposition of 1 : 2-dichloroethane

Cited by 44 publications

References 0 publications

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Atomic Chlorination of Simple Hydrocarbon Derivatives in the Gas Phase.

Pyrolysis and Chlorination of Small Hydrocarbons

Pyrolysis of 1,2‐dichloropropane

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