37. The kinetics of the dehydrochlorination of substituted hydrocarbons. Part III. The mechanisms of the thermal decompositions of ethyl chloride and of 1 : 1-dichloroethane

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

doi:10.1039/jr9490000165

Cited by 39 publications

(11 citation statements)

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“…Whereas alkyl bromides 1 often decompose by mixed molecular and free-radical mechanisms, and alkyl iodides 2 show complicating features associated with the reactions of hydrogen iodide and iodine atoms, it was found by Barton and Howlett 3 9 5 and emphasized by Semenov4 that the pyrolyses of alkyl chlorides fall into two groups. One group comprising the simple alkyl chlorides (apart from methyl chloride) shows the characteristics of simple unimolecular reactions producing olefin and hydrogen chloride, viz.,…”

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confidence: 99%

Unimolecular gas-phase pyrolysis of ethyl chloride

Holbrook¹,

Marsh²

1967

Trans. Faraday Soc.

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The pyrolysis of ethyl chloride in the gas-phase, yielding ethylene and hydrogen chloride, has been studied at four temperatures in the range 402-521 "C and at pressures down to 0.2 mm Hg. The experimental results are compared with the predictions of Kassel, Slater and Marcus-Rice theories, all of which can be modified to give agreement. The unimolecular nature of the pyrolysis has been confirmed by comparing the behaviour of ethyl chloride and 1 ,Zdichlorethane towards chain-reaction inhibitors. A re-investigation of the high-pressure rate constant has given the Arrhenius expression : k, = 1014.03*0*44 exp (-58,43Of1500/RT) sec-1. 643RCH2CH2Cl -tRCH=CH2 + HCl.

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Unimolecular gas-phase pyrolysis of ethyl chloride

Holbrook¹,

Marsh²

1967

Trans. Faraday Soc.

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“…A final example can be taken from the work on the reaction of butene-2 with HI, leading to a single set of products, «-butane + I2 (13). The data fitted quite Homogeneous catalysis by consecutive transfer reactions involving well over a range of conditions and composition to a simple second order rate law of the form: = &6 (olefin) (HI) (6) at However inspection of the Arrhenius parameters of hi gave values which were about 3 kcal. too small in E and 102 too small in A.…”

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confidence: 90%

Predictability of Chain Reactions

Benson¹

1964

Ind. Eng. Chem.

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The characteristic of a chain reaction is that the sum of the chain (or propagation) steps yields the overall reaction stoichiometry-the chain carriers canceling out in the addition. The closed reaction sequence involving the intermediates in a pyrolytic reaction is shown above (see Equation E). Reactant is consumed and products produced, but the concentration of intermediates which propagate the reaction is controlled only by distinct initiation and termination steps. The number of over-all reactions between the initiation and termination steps is called the chain length.In this article, pyrolytic and metathetical chain reactions are discussed in terms of our recently acquired knowledge of prototypes of their component steps-initiation, transfer, propagation, and termination.Predictability of products and product ratios is shown to be fairly good using Rice-Hertzfeld mechanisms and known data for radical reactions. Some semiquantitative generalizations concerning radical step reactions lead to about order-of-magnitude ability to predict overall chain rates.

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“…One of the best-known examples of a radical-chain decomposition is the gas-phase pyrolysis of EDC to vinyl chloride, an excellent review of which is given by Shelton et al (1971). For the uninhibited reaction the following mechanism is proposed (Barton and Howlett, 1949) initiation…”

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“…The compounds and the respective references are as follows: (a) 1,2-dichloroethane, Barton and Howlett (1949); (b) 1,1,2-trichloroethane, Teramoto et al (1964); (c) 1,2-dichloroethene, Goodall and Howlett (1956) Barton and Howlett (1951); (e) 1,4-dichlorobutane, Williams (1953); (f) chloroethane, Hoolbrook and March (1967) Heydtmann and Rinck (1961); (i) ieri-butyl chloride, Barton and Onyon (1949); VCM by-product sample, this investigation. composition (Moller et al, 1971).…”

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confidence: 99%