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Chemical kinetics at a critical point
Author(s) -
Snyder R. B.,
Eckert C. A.
Publication year - 1973
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690190608
Subject(s) - critical point (mathematics) , chemistry , triethylamine , thermodynamics , kinetics , reaction rate , isoprene , gel point , maleic anhydride , iodide , organic chemistry , physics , catalysis , mathematics , geometry , classical mechanics , polymer , copolymer
The rate of the Diels‐Alder reaction of isoprene with maleic anhydride has been measured in the vicinity of the upper critical solution points of two liquid‐liquid mixtures, and the rate of the Menschutkin reaction of ethyl iodide and triethylamine has been investigated near a lower critical solution point. Anomalous behavior has been observed, with the former reaction rate augmented by up to 40% and the latter apparently running 25–30% too slow. A possible explanation for these results is presented in terms of transition state theory and the abrupt behavior of the solution activities of dilute solutes near a critical point.