Sequential determination of urea and HMTA in the process solution of sol-gel route of advanced nuclear fuel fabrication

Determinations of hexamethylene tetramine (HMTA) and urea in the process solutions are required to optimize their concentrations for obtaining high quality ceramic oxide microspheres, for monitoring the washing procedure and for their subsequent recovery, recycling or waste disposal. Determination of urea is the feed solution by conventional procedures is difficult as it contains HMTA. It is more so in the effluent as it contains hydrolytic products like formaldehyde, methylol derivatives of urea, ammonium nitrate and ammonium hydroxide used for washing the gel microspheres. A derivative potentiometric method using a microprocessor-based autotitrator is described. Peaks on the first derivative of the titration plot corresponded to constituents of different basicities. Urea was selectively hydrolyzed at room temperature by the catalytic action of urease enzyme leaving HMTA unaffected. Ammonium hydroxide and ammonium bicarbonate produced from urea and HMTA were sequentially titrated for the analysis of the feed solution to obtain the three corresponding peaks respectively. Two separate titrations were required for the analysis of the effluent solution, which contained free ammonia also. One aliquot was first titrated directly without adding urease (for free ammonia and HMTA) and another aliquot was titrated after treatment with urease. The end points due to the ammonia used for washing and that from urea hydrolysis merged resulting in the appearance of three peaks again. Using this sequential method the relative standard deviations were found to be 0.81% and 1.38% for urea and HMTA, respectively, in eight determinations when the aliquots contained 50 to 75 mg of urea and 75 to 125 mg of HMTA. Feed and effluent solutions of the process stream were analyzed. (author)