Infrared characterization of hydrated products of glyoxal in aqueous solution

Abstract

The simplest and most abundant dicarbonyl in the atmosphere, glyoxal ((CHO)2), and its geminal diols via stepwise hydration reactions, monohydrate (CHOCH(OH)2) and dihydrate ((HC(OH)2)2), are proposed to be responsible for the generation of atmospheric acid and the increase in aerosol viscosity. In this work, the hydrates of glyoxal were prepared by dissolving glyoxal trimer dihydrate (C6H10O8) in H2O and D2O and probed by infrared absorption spectrometry at varied temperatures. In glyoxal aqueous solution at a concentration of < 1 wt%, the monomeric dihydrate is predominant. Coupled with the predicted vibrational wavenumbers and the corresponding intensities using the B3LYP/aug-cc-pVTZ method, the intense IR bands at 1075 cm−1 and 1073 cm−1 are attributed to the C–O stretching modes of dihydrate and deuterium substituted dihydrate at the hydroxyl groups, denoted as d4-dihydrate ((HC(OD)2)2). Upon heating of the d4-dihydrate solution to cause dehydration, a new band generated at 1745 cm−1 was attributed to the C=O stretching mode of d2-monohydrate (CHOCH(OD)2). Comparing the predicted wavenumbers of glyoxal monohydrate and the observed vibrational wavenumbers of the glycolaldehyde (HCOCH2OH), the wavenumber of the C=O stretching mode of monohydrate is reasonably presumed to be 1745 ± 5 cm−1. These infrared characterizations of the glyoxal hydrates provide suitable detection windows for further investigating the roles of glyoxal and its hydrates in atmospheric and aerosol chemistry, as well as studying the relevant reaction kinetics.