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Kinetics and mechanism for the acid‐catalyzed addition of propionic acid to tetradecenes and hexadecenes
Author(s) -
Gee Jeffrey C.,
Kurukji Daniel
Publication year - 2010
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.20490
Subject(s) - chemistry , isomerization , carbenium ion , limiting , olefin fiber , kinetics , catalysis , rate determining step , reaction mechanism , double bond , computational chemistry , kinetic energy , mechanism (biology) , organic chemistry , mechanical engineering , physics , quantum mechanics , engineering , philosophy , epistemology
We developed a kinetic model for the reversible direct addition of propionic acid to linear tetradecences and linear hexadecenes on Amberlyst 15 at 93°C. The model addresses concurrent double bond isomerization of the olefins and assumes carbenium ion formations to be rate limiting for all conversions; it is detailed enough to include terms for multiple isomers of esters and olefins. The reaction was first order in olefin and in ester but was one‐half order in propionic acid. Gas chromatography was the analytical method employed to follow the reactions, and this study represents a novel use of this analytical method to elucidate carbenium ion behavior. The model includes five rate‐determining steps and five fast steps. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 354–371, 2010