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Kinetics and mechanism of the addition of 1,3‐butadiene to cyclohexa‐1,3‐diene in the gas phase
Author(s) -
Huybrechts G.,
Hubin Y.,
Narmon M.,
Van Mele B.
Publication year - 1982
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.550140306
Subject(s) - chemistry , torr , diene , homogeneous , kinetics , reagent , 1,3 butadiene , gas phase , reaction rate constant , phase (matter) , thermodynamics , organic chemistry , catalysis , natural rubber , physics , quantum mechanics
The thermal reactions of 1,3‐butadiene (BD) with cyclohexa‐1,3‐diene (CHD) have been studied in a static system between 437 and 526 K. The pressures of BD and CHD were varied from 61 to 397 torr and from 50 to 93 torr, respectively. The percentages of consumed BD and CHD were always kept lower than 14%. The reactions—in the order of importance—areAll the reactions are homogeneous and of the first order with respect to the reagents. Their rate constants (in L/mol·s) are given by\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} \log _{10} k_{{\rm HHN}} = - (25,370 \pm 70)/4.576T + (7.02 \pm 0.03) \\ \log _{10} k_{{\rm KNDO}} = - (24,840 \pm 50)/4.576T + (6.58 \pm 0.02) \\ \log _{10} k_{{\rm BDD}} = - (25,530 \pm 50)/4.576T + (6.61 \pm 0.02) \\ \log _{10} k_{{\rm EXO}} = - (26,760 \pm 50)/4.576T + (7.06 \pm 0.02) \\ \end{array} $$\end{document} A thermochemical analysis of a biradical mechanism is in agreement with these results.