title: Semicontinuum Solvation Modeling Improves Predictions of Carbamate Stability in the CO2 + Aqueous Amine Reaction.
abstract: Quantum chemistry computations with a semicontinuum (cluster + continuum) solvation model have been used to cure long-standing misprediction of aqueous carbamate anion energies in the industrially important CO2 + aqueous amine reaction. Previous errors of over 10 kcal mol(-1) are revealed. Activation energies were also estimated with semicontinuum modeling, and a refined discussion of the competing hypothetical mechanisms for CO2 + monoethanolamine (MEA) is presented. Further results are also presented to demonstrate that the basicity of an amine (aqueous proton affinity) correlates only with CO2 affinity within an amine class: secondary amines have an extra CO2 affinity that primary amines do not have.
authors.affiliation: Department of Industrial Systems Engineering and ‡Department of Chemistry and Biochemistry, University of Regina , 3737 Wascana Parkway, Regina, Saskatchewan S4S 0A2, Canada.
authors.forename: Kazi Z
authors.initials: KZ
authors.lastname: Sumon
authors.affiliation: Department of Industrial Systems Engineering and ‡Department of Chemistry and Biochemistry, University of Regina , 3737 Wascana Parkway, Regina, Saskatchewan S4S 0A2, Canada.
authors.forename: Chatin H
authors.initials: CH
authors.lastname: Bains
authors.affiliation: Department of Industrial Systems Engineering and ‡Department of Chemistry and Biochemistry, University of Regina , 3737 Wascana Parkway, Regina, Saskatchewan S4S 0A2, Canada.
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Markewich
authors.affiliation: Department of Industrial Systems Engineering and ‡Department of Chemistry and Biochemistry, University of Regina , 3737 Wascana Parkway, Regina, Saskatchewan S4S 0A2, Canada.
authors.forename: Amr
authors.initials: A
authors.lastname: Henni
authors.affiliation: Department of Industrial Systems Engineering and ‡Department of Chemistry and Biochemistry, University of Regina , 3737 Wascana Parkway, Regina, Saskatchewan S4S 0A2, Canada.
authors.forename: Allan L L
authors.initials: AL
authors.lastname: East