Different nonideality relationships, different databases and their effects on modeling precipitation from concentrated solutions using numerical speciation codes

摘要

Four simple precipitation problems are solved to examine the use of numerical equilibrium codes. The study emphasizes concentrated solutions, assumes both ideal and nonideal solutions, and employs different databases and different activity-coefficient relationships. The study uses the EQ3/6 numerical speciation codes. The results show satisfactory material balances and agreement between solubility products calculated from free-energy relationships and those calculated from concentrations and activity coefficients. Precipitates show slightly higher solubilities when the solutions are regarded as nonideal than when considered ideal, agreeing with theory. When a substance may precipitate from a solution dilute in the precipitating substance, a code may or may not predict precipitation, depending on the database or activity-coefficient relationship used. In a problem involving a two-component precipitation, there are only small differences in the precipitate mass and composition between the ideal and nonideal solution calculations. Analysis of this result indicates that this may be a frequent occurrence. An analytical approach is derived for judging whether this phenomenon will occur in any real or postulated precipitation situation. The discussion looks at applications of this approach. In the solutes remaining after the precipitations, there seems to be little consistency in the calculated concentrations and activity coefficients. They do not appear to depend in any coherent manner on the database or activity-coefficient relationship used. These results reinforce warnings in the literature about perfunctory or mechanical use of numerical speciation codes.