Premium
Kinetics of the Diels–Alder addition of acrolein to cyclohexa‐1,3‐diene and its reverse reaction in the gas phase
Author(s) -
Huybrechts G.,
Paternoster G.,
Baetens P.
Publication year - 1976
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.550080502
Subject(s) - chemistry , acrolein , reaction rate constant , diene , diels–alder reaction , torr , pyrolysis , medicinal chemistry , kinetics , photochemistry , organic chemistry , catalysis , thermodynamics , natural rubber , physics , quantum mechanics
The Diels–Alder addition of acrolein to cyclohexa‐1,3‐diene has been studied between 486 and 571°K at pressures ranging from 55 to 240 torr. The products are endo‐ and exo‐5‐formylbicyclo[2.2.2]oct‐2‐ene (endo‐ and exo‐FBO), and their formations are second order. The rate constants (in l./mole · sec) are given by\documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm}k_{{\rm endo}} = -(19,470 \pm 50)/4.576T + (5.65 \pm 0.02)$$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm}k_{{\rm exo}} = - (20,630 \pm 50)/4.576T + (5.51 \pm 0.02)$$\end{document}The retro‐Diels–Alder pyrolysis of endo‐FBO has also been studied. In the ranges of 565–638°K and 6–38 torr, the reaction is first order, and its rate constant (in sec −1 ) is given by\documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} {\rm}k_{{\rm p}} = - (46,390 \pm 110)/4.576T + (12.98 \pm 0.04)$$\end{document}The reaction mechanism is discussed. The heat of formation and the entropy of endo‐FBO are estimated.