Procedure.—To the combined filtrates from the double precipitation of the hydroxides just described, add 5 cc. of dilute ammonium hydroxide (sp. gr. 0.96), and transfer the liquid to a 500 cc. graduated flask, washing out the beaker carefully. Cool to laboratory temperature, and fill the flask with distilled water until the lowest point of the meniscus is exactly level with the mark on the neck of the flask. Carefully remove any drops of water which are on the inside of the neck of the flask above the graduation by means of a strip of filter paper, make the solution uniform by pouring it out into a dry beaker and back into the flask several times. Measure off one fifth of this solution as follows (Note 1): Pour into a 100 cc. graduated flask about 10 cc. of the solution, shake the liquid thoroughly over the inner surface of the small flask, and pour it out. Repeat the same operation. Fill the 100 cc. flask until the lowest point of the meniscus is exactly level with the mark on its neck, remove any drops of solution from the upper part of the neck with filter paper, and pour the solution into a beaker (400-500 cc.). Wash out the flask with small quantities of water until it is clean, adding these to the 100 cc. of solution. When the duplicate portion of 100 cc. is measured out from the solution, remember that the flask must be rinsed out twice with that solution, as prescribed above, before the measurement is made. (A 100 cc. pipette may be used to measure out the aliquot portions, if preferred.)
Dilute each of the measured portions to 250 cc. with distilled water, heat the whole to boiling, and add ammonium oxalate solution slowly in moderate excess, stirring well. Boil for two minutes; allow the precipitated calcium oxalate to settle for a half-hour, and decant through a filter. Test the filtrate for complete precipitation by adding a few cubic centimeters of the precipitant, allowing it to stand for fifteen minutes. If no precipitate forms, make the solution slightly acid with hydrochloric acid (Note 2); see that it is properly labeled and reserve it to be combined with the filtrate from the second calcium oxalate precipitation (Notes 3 and 4).
Redissolve the calcium oxalate in the beaker with warm hydrochloric acid, pouring the acid through the filter. Wash the filter five times with water, and finally pour through it aqueous ammonia. Dilute the solution to 250 cc., bring to boiling, and add 1 cc. ammonium oxalate solution (Note 5) and ammonia in slight excess; boil for two minutes, and set aside for a half-hour. Filter off the calcium oxalate upon the filter first used, and wash free from chlorides. The filtrate should be made barely acid with hydrochloric acid and combined with the filtrate from the first precipitation. Begin at once the evaporation of the solutions for the determination of magnesium as described below.