STUDIES ON THE FORMATION OF HEXAMINE

Rate curves have been determined for the reaction of ammonia and formaldehyde in aqueous solution at 0 °C. and 35 °C., over a range of initial mole ratios (formaldehyde: ammonia) of 0.25 to 2.0. For each set of conditions, three curves have been obtained on the basis of ammonia consumed, formaldehyde consumed, and material precipitated with mercuric chloride respectively.At 0 °C. the three rate curves tend to approximate one another in a large excess of ammonia but are widely separated in excess formaldehyde. The reverse is true at 35 °C. The reaction is characterized by a high initial rate of formation of hexamine, this rapid rate being maintained to a lower yield of hexamine the more dilute the solution. The existence of a stable by-product in excess formaldehyde is indicated by the variation in final yields of hexamine, when these are calculated on the basis of formaldehyde consumed, ammonia consumed, or material precipitated with mercuric chloride.A mechanism for the reaction has been suggested.