Kinetics of CO2 with primary and secondary amines in aqueous solutions - II. Influence of temperature on zwitterion formation and deprotonation rates

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Littel, R.J. and Versteeg, G.F. and Swaaij, W.P.M. van (1992) Kinetics of CO2 with primary and secondary amines in aqueous solutions - II. Influence of temperature on zwitterion formation and deprotonation rates. Chemical Engineering Science, 47 (8). pp. 2037-2045. ISSN 0009-2509

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Abstract:The kinetics of the reaction of CO2 with various alkanolamines (MEA, DGA, DIPA, DEA, MMEA) in aqueous solutions has been studied as a function of temperature. Also kinetic data at 303 K were obtained for the reaction between CO2 and the cyclic amine morpholine in aqueous solutions. All observed phenomena can be explained very satisfactorily with the zwitterion mechanism proposed by Caplow. With respect to the temperature influence on the overall reaction rate for primary and secondary amines, two classes can be distinguished: when the zwitterion formation is rate determining a significant temperature influence is observed whereas only a slight temperature dependence is observed when the zwitterion deprotonation is rate determining. All kinetic experiments were interpreted with the aid of a numerically solved absorption model which describes gas absorption accompanied by reversible chemical reactions. For last reversible reactions like those in the present study, only in this way reliable reaction-rate data can be deduced from absorption experiments. The Brønsted relationship between the zwitterion-formation rate constant and the acid dissociation constant of the alkanolamine, as proposed by Versteeg and van Swaaij (1988a), seems to be valid over a wide range of temperatures and for a great variety of alkanolamines. This relationship is not valid for cyclic amines like MOR.
Item Type:Article
Copyright:© 1992 Elsevier Science
Faculty:
Science and Technology (TNW)
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Link to this item:http://purl.utwente.nl/publications/11172
Official URL:http://dx.doi.org/10.1016/0009-2509(92)80320-C
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