Journal of Physical Chemistry p. 134 - 141 (1990)
Update date:2022-08-11
Topics:
Collin, Guy J.
Deslauriers, Helene
Mare, George R. de
Poirier, Raymond A.
A systematic study of the 213.8-nm (zinc line ) photochemistry of 1,3-butadiene has been made either in the absence or in the presence of various additives - such as radical scavengers (O2,NO,DI) and collisional quenchers - in the gas phase (pressure between 1 and 500 Torr).The major fate of the photoexcited 1,3-butadiene molecule is isomerization to the 1,2-butadiene structure which may then decompose to methyl and C3H3 radicals (Φ = 0.64 +/- 0.04 at 1 Torr of 1,3-butadiene).Minor processes include decomposition to the acetylene + ethylene couple (Φ = 0.22 +/- 0.02) or to vinylacetylene (Φ = 0.038 +/- 0.003) and molecular hydrogen.These two minor processes occur from different excited states.Some 2-butyne (Φ < 0.015) is formed by an unimolecular isomerization process.The photolysis of 1,3-butadiene-1,1,4,4-d4 indicates that at least three different intermediates are involved in the formation of molecular ethylene and acetylene.The C3H3 radicals are not easily intercepted by DI: k(C3H3 + 1,3-butadiene )/k(C3H3 + DI) = 0.09 +/- 0.03.Also at 21 deg C and for
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