Aminoacetaldehyde (glycinal, NH
2CH
2CHO) is a first-generation oxidation product of monoethanolamine (MEA, NH
2CH
2CH
2OH), a solvent widely used for CO
2 gas separation, which is proposed as the basis for a range of carbon capture
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Aminoacetaldehyde (glycinal, NH
2CH
2CHO) is a first-generation oxidation product of monoethanolamine (MEA, NH
2CH
2CH
2OH), a solvent widely used for CO
2 gas separation, which is proposed as the basis for a range of carbon capture technologies. A complete oxidation mechanism for MEA is required to understand the atmospheric transformation of carbon capture plant emissions, as well as the degradation of this solvent during its use and the oxidative destruction of waste solvent. In this study, we have investigated the
•OH radical-initiated oxidation chemistry of aminoacetaldehyde using quantum chemical calculations and RRKM theory/master equation kinetic modeling. This work predicts that aminoacetaldehyde has a tropospheric lifetime of around 6 h and that the reaction predominantly produces the NH
2CH
2C
•O radical intermediate at room temperature, along with minor contributions from NH
2•CHCHO and
•NHCH
2CHO. The dominant radical intermediate NH
2CH
2C
•O is predicted to promptly dissociate to NH
2•CH
2 and CO, where NH
2•CH
2 is known to react with O
2 under tropospheric conditions to form the imine NH = CH
2 + HO
2. The NH
2•CHCHO radical experiences captodative stabilization and is found to form a weakly bound peroxyl radical upon reaction with O
2. Instead, the major oxidation product of NH
2•CHCHO and the aminyl radical
•NHCH
2CHO is the imine NH = CHCHO (+HO
2). In the atmosphere, the dominant fate of imine compounds is thought to be hydrolysis, where NH = CH
2 will form ammonia and formaldehyde, and NH = CHCHO will produce ammonia and glyoxal. Efficient conversion of the dominant first-generation oxidation products of MEA to ammonia is consistent with field observations and supports the important role of imine intermediates in MEA oxidation.
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