[Note 1: The precipitation of the magnesium should be made in as small volume as possible, and the ratio of ammonia to the total volume of solution should be carefully provided for, on account of the relative solubility of the magnesium ammonium phosphate. This matter has been fully discussed in connection with the phosphoric anhydride determination.]
[Note 2: The first magnesium ammonium phosphate precipitate is rarely wholly crystalline, as it should be, and is not always of the proper composition when precipitated in the presence of such large amounts of ammonium salts. The difficulty can best be remedied by filtering the precipitate and (without washing it) redissolving in a small quantity of hydrochloric acid, from which it may be again thrown down by ammonia after adding a little disodium phosphate solution. If the flocculent character was occasioned by the presence of magnesium hydroxide, the second precipitation, in a smaller volume containing fewer salts, will often result more favorably.
The removal of iron or alumina from a contaminated precipitate is a matter involving a long procedure, and a redetermination of the magnesium from a new sample, with additional precautions, is usually to be preferred.]
DETERMINATION OF CARBON DIOXIDE
!Absorption Apparatus!
[Illustration: Fig. 3]
The apparatus required for the determination of the carbon dioxide should be arranged as shown in the cut (Fig. 3). The flask (A) is an ordinary wash bottle, which should be nearly filled with dilute hydrochloric acid (100 cc. acid (sp. gr. 1.12) and 200 cc. of water). The flask is connected by rubber tubing (a) with the glass tube (b) leading nearly to the bottom of the evolution flask (B) and having its lower end bent upward and drawn out to small bore, so that the carbon dioxide evolved from the limestone cannot bubble back into (b). The evolution flask should preferably be a wide-mouthed Soxhlet extraction flask of about 150 cc. capacity because of the ease with which tubes and stoppers may be fitted into the neck of a flask of this type. The flask should be fitted with a two-hole rubber stopper. The condenser (C) may consist of a tube with two or three large bulbs blown in it, for use as an air-cooled condenser, or it may be a small water-jacketed condenser. The latter is to be preferred if a number of determinations are to be made in succession.
A glass delivery tube (c) leads from the condenser to the small U-tube (D) containing some glass beads or small pieces of glass rod and 3 cc. of a saturated solution of silver sulphate, with 3 cc. of concentrated sulphuric acid (sp. gr. 1.84). The short rubber tubing (d) connects the first U-tube to a second U-tube (E) which is filled with small dust-free lumps of dry calcium chloride, with a small, loose plug of cotton at the top of each arm. Both tubes should be closed by cork stoppers, the tops of which are cut off level with, or preferably forced a little below, the top of the U-tube, and then neatly sealed with sealing wax.
The carbon dioxide may be absorbed in a tube containing soda lime (F) or in a Geissler bulb (F') containing a concentrated solution of potassium hydroxide (Note 2). The tube (F) is a glass-stoppered side-arm U-tube in which the side toward the evolution flask and one half of the other side are filled with small, dust-free lumps of soda lime of good quality (Note 3). Since soda lime contains considerable moisture, the other half of the right side of the tube is filled with small lumps of dry, dust-free calcium chloride to retain the moisture from the soda lime. Loose plugs of cotton are placed at the top of each arm and between the soda lime and the calcium chloride.
The Geissler bulb (F'), if used, should be filled with potassium hydroxide solution (1 part of solid potassium hydroxide dissolved in two parts of water) until each small bulb is about two thirds full (Note 4). A small tube containing calcium chloride is connected with the Geissler bulb proper by a ground joint and should be wired to the bulb for safety. This is designed to retain any moisture from the hydroxide solution. A piece of clean, fine copper wire is so attached to the bulb that it can be hung from the hook above a balance pan, or other support.