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Computational Comparison of the Reactions of Substituted Amines with CO 2
Author(s) -
Mindrup Elaine M.,
Schneider William F.
Publication year - 2010
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201000060
Subject(s) - chemistry , amine gas treating , stoichiometry , molecule , decomposition , computational chemistry , organic chemistry
Substituted amines are a popular choice as molecules to selectively react with and separate CO 2 from gas mixtures. Such separations are of particular interest, for example, for CO 2 separations for carbon capture and sequestration. It is desirable to tune amine–CO 2 reaction energies to suit a particular separation. Herein, we use DFT‐B3LYP simulations to characterize the products and energetics of reactions of CO 2 with a range of substituted amines, considering both 1:1 and 2:1 amine/CO 2 reaction stoichiometries. The results show that by adjusting both the nature and the placement of functional groups, it is possible to tune reaction energies over a substantial range. Decomposition of the 2:1 reaction into separate carbamate and ammonium formation steps shows that the Brønsted basicity and Lewis basicity towards CO 2 are largely uncorrelated and provide an independent means of tuning the overall reaction energies.