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Kinetics of the bimolecular initiation process in the thermal reactions of ethylene
Author(s) -
Ayranci G.,
Back M. H.
Publication year - 1981
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550130913
Subject(s) - chemistry , ethylene , thermal decomposition , activation energy , reaction rate constant , thermodynamics , kinetics , frequency factor , decomposition , atmospheric temperature range , thermal , analytical chemistry (journal) , organic chemistry , catalysis , quantum mechanics , physics
The initial rates of formation of the major products in the thermal reactions of ethylene at temperatures in the neighborhood of 750 K have been measured in the presence and absence of the additive butene‐1. It has been shown that this ratio of rates is related to the ratio of rate constants for the two initiation processes:The ratio k ′ 1 / k 1 has been measured over the temperature range of 700–773 K and may be expressed as (R = 1.987 cal/mol deg) log k ′ 1 k 1 (mol/L) = 2.8 − 4400/2.3 RT. Assuming a value for k ′ 1 of log k ′ 1 (s −1 ) = 16 − 71,500/2.3 RT , the value of k 1 may be expressed as log k 1 (L/mol) = 13.2 − 67,000/2.3 RT. The values for the frequency factor and activation energy for reaction (1) are discussed in relation to the heat of formation of the vinyl radical, and it is concluded that reaction (1) is the main initiation process in the thermal decomposition of ethylene under the present conditions.