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Kinetics and mechanism study of aniline addition to ethyl propiolate
Author(s) -
NoriShargh Davood,
Soltani Bita,
SarooghFarahani Nasrin,
Deyhimi Farzad
Publication year - 2006
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.20147
Subject(s) - chemistry , aniline , arrhenius equation , reaction rate constant , kinetics , reaction mechanism , order of reaction , first order , solvent , reaction rate , chemical kinetics , activation energy , computational chemistry , organic chemistry , catalysis , physics , mathematics , quantum mechanics
The kinetics of the addition reaction of aniline to ethyl propiolate in dimethylsulfoxide (DMSO) as solvent was studied. Initial rate method was used to determine the order of the reaction with respect to the reactants, and pseudo‐first‐order method was used to calculate the rate constant. This reaction was monitored by UV–Vis spectrophotometer at 399 nm by the variable time method. On the basis of the experimental results, the Arrhenius equation for this reaction was obtained as log k = 6.07 ‐ (12.96/2.303 RT ). The activation parameters, E a , Δ H # , Δ G # , and Δ S # at 300 K were 12.96, 13.55, 23.31 kcal mol −1 and −32.76 cal mol −1 K −1 , respectively. The results revealed a first‐order reaction with respect to both aniline and ethyl propiolate. In addition, based on the experimental results and using also density functional theory (DFT) at B3LYP/6‐31G* level, a mechanism for this reaction was proposed. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 38: 144–151, 2006