Kinetics of the reaction between carbon dioxide and tertiary amines

• Published in: Journal of organic chemistry Vol. 55; no. 4; pp. 1372 - 1374
• Main Authors: Crooks, John E, Donnellan, J. Paul
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.02.1990
• Subjects: 400201 - Chemical & Physicochemical Properties; AMINES; CARBON COMPOUNDS; CARBON DIOXIDE; CARBON OXIDES; CARBONATES; CHALCOGENIDES; CHEMICAL PREPARATION; CHEMICAL REACTION KINETICS; CHEMICAL REACTIONS; Chemistry; Exact sciences and technology; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; KINETICS; Kinetics and mechanisms; Organic chemistry; ORGANIC COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; REACTION KINETICS; Reactivity and mechanisms; SALTS; SYNTHESIS; Aminoalcohol; Carbon dioxide; Tertiary amine; Activation parameter; Aqueous solution; Rate constant; Thermodynamic properties
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo00291a056

The reaction between carbon dioxide and amines is of great technical importance and has been the subject of many investigations. The authors have shown that the reaction for secondary amines in anhydrous ethanol and in aqueous solution is exclusively second-order in amine and that the zwitterion intermediate postulated by Danckwerts is probably of negligible significance in the mechanism. The reaction with tertiary amines has also been studied, but the data are less controversial. In order to complete their studies of the reactions of carbon dioxide with amines, using their conductimetric stopped-flow apparatus, they have studied this reaction for MDEA (methyldiethanolamine, IUPAC name N-methyl-2,2{prime}-iminodiethanol) and TEA (triethanolamine, IUPAC name 2,2{prime},2{double prime}-nitrilotris(ethanol)).