Title

Thermodynamics and Kinetics of Imidazole Formation from Glyoxal, Methylamine, and Formaldehyde: A Computational Study

Document Type

Article

Publication Date

2-15-2011

Abstract

Density functional theory calculations, including Poisson−Boltzmann implicit solvent and free energy corrections, are applied to study the mechanism of experimentally observed imidazole formation from the reaction of glyoxal and methylamine in solution. Our calculations suggest that a diimine species is an important intermediate in the reaction. Under acidic conditions, we find that the diimine acts as a nucleophile in attacking the carbonyl group of either formaldehyde or glyoxal to first generate an acyclic enol intermediate, which then goes on to close the ring and form imidazoles. Our results confirm that formaldehyde and, by extension, other small aldehydes are likely to be incorporated into imidazole ions in the presence of glyoxal and primary amines in clouds and aqueous aerosol. This is a new mechanism of aerosol formation by formaldehyde, the most abundant aldehyde in the atmosphere. The amount of aerosol formed will depend on the amounts of glyoxal and amines present.

Publication Information

© 2011 American Chemical Society

Published in final form at:

J. Kua, H. E. Krizner, and d. O. De Haan, "Thermodynamics and kinetics of imidazole formation from glyoxal and methylamine: a computational study." J. Phys. Chem. A 115 (9) 1667-1675 (2011)