Premium
Kinetics of the thermal reactions of bicyclo[4.2.2]deca‐3,7‐diene and endo‐and exo‐5‐vinylbicyclo[2.2.2]oct‐2‐ene 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.550140305
Subject(s) - chemistry , kinetics , diene , reagent , ene reaction , bicyclic molecule , gas phase , torr , homogeneous , thermal , phase (matter) , stereochemistry , thermodynamics , analytical chemistry (journal) , computational chemistry , organic chemistry , natural rubber , physics , quantum mechanics
The kinetics of the thermal reactions of bicyclo[4.2.2]deca‐3,7‐diene (BDD) and endo‐ and exo‐5‐vinylbicyclo[2.2.2]oct‐2‐ene (endo‐ and exo‐VBO) have been studied in the gas phase. The temperature range was 459–526 K for BDD, 476–563 K for endo‐VBO, and 513–578 K for exo‐VBO. The initial pressures were varied from 2 to about 40 torr. These compounds isomerize to cis ‐1,2,4a,5,8,8a‐hexahydronaphtalene (HHN) and into each other, and decompose to 1,3‐butadiene (BD) + cyclohexa‐1,3‐diene (CHD). The reactions are homogeneous and first order. Their rate constants (in s −1 ) are given by:where the superscripts represent the reagents and the subscripts the products. The heats of formation and the entropies of endo‐VBO, exo‐VBO, and BDD are estimated.