Formation of hexamethylenetetramine by aqueous solutions of formaldehyde and ammonium sulfate

Formaldehyde and ammonium sulfate are prominent compounds found in cloudwater. Electronic structure calculations and lab experiments were carried out to explore the oligomerization reactions between formaldehyde and ammonia. Density functional theory calculations along with solvation and thermodynamic corrections were performed to map the kinetic and thermodynamic landscape for the reactions leading to the formation of hexamethylenetetramine (hmta). Three general classes of reactions were considered: nucleophilic addition of amine to formaldehyde, nucleophilic addition of ammonia to imine intermediates ammonia, and dehydration of alkanolamines. The reaction was studied experimentally using bulk-phase aqueous solutions of formaldehyde, ammonium sulfate, and in some experiments, iron (III) sulfate (chosen because Fe3+ forms a brown complex with hmta). Aqueous standard solutions of the reaction product hmta were also made. Reaction mixtures were analyzed using NMR, UV-Vis spectroscopy and LCMS. Compound hmta was the main product observed by both NMR and LCMS. Using LCMS a large peak was observed within minutes of mixing the reactants. The absorbance of the reaction mixture increased strongly below 225 nm but little to no absorbance was observed in the visible spectrum.