EXCITED STATES OF ACETYLENE AND THEIR ROLE IN PYROLYSIS
- 1 January 1958
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 36 (1) , 131-136
- https://doi.org/10.1139/v58-016
Abstract
Previous theories of acetylene pyrolysis are reviewed in the light of recent work by Minkoff, Newitt, and Rutledge. It is shown that the relatively large rates observed at the beginning of the induction period do not agree with mechanisms involving the intervention of comparatively stable dimers. The required kinetic form is obtained, however, if a triplet diradical is produced on the surface in a bimolecular process, followed by gas phase polymerization, with some chain ending on the surface. The detailed mechanism closely resembles Flory's scheme for liquid phase vinyl polymerization. The shape of the radical is discussed, and it is suggested that the trans-configuration leads to polymerization, while the cis facilitates dehydrogenation.Keywords
This publication has 10 references indexed in Scilit:
- Molecular Electronic SpectroscopyAnnual Review of Physical Chemistry, 1956
- Influence of certain foreign gases on the thermal decomposition of paraffins I. Further evidence on chain and non-chain reactionsProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1955
- Studies in polymerization. I. A method for determining the velocity constants in polymerization reactions and its application to styreneProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1948
- Studies in Gaseous Hydrogenation and Polymerization Reactions1Journal of the American Chemical Society, 1942
- The Mechanism of Vinyl Polymerizations1Journal of the American Chemical Society, 1937
- The polymerisation of ethylene and acetylene photosensitised by acetoneTransactions of the Faraday Society, 1937
- The Polymerization and Hydrogenation of AcetyleneThe Journal of Physical Chemistry, 1935
- Polymerisation und thermischer Zerfall des AcetylensHelvetica Chimica Acta, 1930
- THE KINETICS OF THE POLYMERIZATION OF ACETYLENE1Journal of the American Chemical Society, 1929
- CXVII.—The thermal decomposition of hydrocarbons. Part I. [Methane, ethane, ethylene, and acetylene.]Journal of the Chemical Society, Transactions, 1908