An Introductory Course of Quantitative Chemical Analysis by Henry P. Talbot (superbooks4u txt) 📕

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.

The small bottle (G) with concentrated sulphuric acid (sp. gr. 1.84) is so arranged that the tube (f) barely dips below the surface. This will prevent the absorption of water vapor by (F) or (F') and serves as an aid in regulating the flow of air through the apparatus. (H) is an aspirator bottle of about four liters capacity, filled with water; (k) is a safety tube and a means of refilling (H); (h) is a screw clamp, and (K) a U-tube filled with soda lime.

[Note 1: The air current, which is subsequently drawn through the apparatus, to sweep all of the carbon dioxide into the absorption apparatus, is likely to carry with it some hydrochloric acid from the evolution flask. This acid is retained by the silver sulphate solution. The addition of concentrated sulphuric acid to this solution reduces its vapor pressure so far that very little water is carried on by the air current, and this slight amount is absorbed by the calcium chloride in (E). As the calcium chloride frequently contains a small amount of a basic material which would absorb carbon dioxide, it is necessary to pass carbon dioxide through (E) for a short time and then drive all the gas out with a dry air current for thirty minutes before use.]

[Note 2: Soda-lime absorption tubes are to be preferred if a satisfactory quality of soda lime is available and the number of determinations to be made successively is small. The potash bulbs will usually permit of a larger number of successive determinations without refilling, but they require greater care in handling and in the analytical procedure.]

[Note 3: Soda lime is a mixture of sodium and calcium hydroxides. Both combine with carbon dioxide to form carbonates, with the evolution of water. Considerable heat is generated by the reaction, and the temperature of the tube during absorption serves as a rough index of the progress of the reaction through the mass of soda lime.

It is essential that soda lime of good quality for analytical purposes should be used. The tube should not contain dust, as this is likely to be swept away.]

[Note 4: The solution of the hydroxide for use in the Geissler bulb must be highly concentrated to insure complete absorption of the carbon dioxide and also to reduce the vapor pressure of the solution, thus lessening the danger of loss of water with the air which passes through the bulbs. The small quantity of moisture which is then carried out of the bulbs is held by the calcium chloride in the prolong tube. The best form of absorption bulb is that to which the prolong tube is attached by a ground glass joint.

After the potassium hydroxide is approximately half consumed in the first bulb of the absorption apparatus, potassium bicarbonate is formed, and as it is much less soluble than the carbonate, it often precipitates. Its formation is a warning that the absorbing power of the hydroxide is much diminished.]

!The Analysis!

PROCEDURE.— Weigh out into the flask (B) about 1 gram of limestone. Cover it with 15 cc. of water. Weigh the absorption apparatus (F) or (F') accurately after allowing it to stand for 30 minutes in the balance case, and wiping it carefully with a lintless cloth, taking care to handle it as little as possible after wiping (Note 1). Connect the absorption apparatus with (e) and (f). If a soda-lime tube is used, be sure that the arm containing the soda lime is next the tube (E) and that the glass stopcocks are open.

To be sure that the whole apparatus is airtight, disconnect the rubber tube from the flask (A), making sure that the tubes (a) and (b) do not contain any hydrochloric acid, close the pinchcocks (a) and (k) and open (h). No bubbles should pass through (D) or (G) after a few seconds. When assured that the fittings are tight, close (h) and open (a) cautiously to admit air to restore atmospheric pressure. This precaution is essential, as a sudden inrush of air will project liquid from (D) or (F'). Reconnect the rubber tube with the flask (A). Open the pinchcocks (a) and (k) and blow over about 10 cc. of the hydrochloric acid from (A) into (B). When the action of the acid slackens, blow over (slowly) another 10 cc.

The rate of gas evolution should not exceed for more than a few seconds that at which about two bubbles per second pass through (G) (Note 2). Repeat the addition of acid in small portions until the action upon the limestone seems to be at an end, taking care to close (a) after each addition of acid (Note 3). Disconnect (A) and connect the rubber tubing with the soda-lime tube (K) and open (a). Then close (k) and open (h), regulating the flow of water from (H) in such a way that about two bubbles per second pass through (G). Place a small flame under (B) and !slowly! raise the contents to boiling and boil for three minutes. Then remove the burner from under (B) and continue to draw air through the apparatus for 20-30 minutes, or until (H) is emptied (Note 4). Remove the absorption apparatus, closing the stopcocks on (F) or stoppering the open ends of (F'), leave the apparatus in the balance case for at least thirty minutes, wipe it carefully and weigh, after opening the stopcocks (or removing plugs). The increase in weight is due to absorption of CO_{2}, from which its percentage in the sample may be calculated.

After cleaning (B) and refilling (H), the apparatus is ready for the duplicate analysis.

[Note 1: The absorption tubes or bulbs have large surfaces on which moisture may collect. By allowing them to remain in the balance case for some time before weighing, the amount of moisture absorbed on the surface is as nearly constant as practicable during two weighings, and a uniform temperature is also assured. The stopcocks of the U-tube should be opened, or the plugs used to close the openings of the Geissler bulb should be removed before weighing in order that the air contents shall always be at atmospheric pressure.]

[Note 2: If the gas passes too rapidly into the absorption apparatus, some carbon dioxide may be carried through, not being completely retained by the absorbents.]

[Note 3: The essential ionic changes involved in this procedure are the following: It is assumed that the limestone, which is typified by calcium carbonate, is very slightly soluble in water, and the ions resulting are Ca^{++} and CO_{3}^{—}. In the presence of H^{+} ions of the mineral acid, the CO_{3}^{—} ions form [H_{2}CO_{3}]. This is not only a weak acid which, by its formation, diminishes the concentration of the CO_{3}^{—} ions, thus causing more of the carbonate to dissolve to re-establish equilibrium, but it is also an unstable compound and breaks down into carbon dioxide and water.]

[Note 4: Carbon dioxide is dissolved by cold water, but the gas is expelled by boiling, and, together with that which is distributed through the apparatus, is swept out into the absorption bulb by the current of air. This air is purified by drawing it through the tube (K) containing soda lime, which removes any carbon dioxide which may be in it.]

DETERMINATION OF LEAD, COPPER, IRON, AND ZINC IN BRASS ELECTROLYTIC SEPARATIONS

!General Discussion!

When a direct current of electricity passes from one electrode to another through solutions of electrolytes, the individual ions present in these solutions tend to move toward the electrode of opposite electrical charge to that which each ion bears, and to be discharged by that electrode. Whether or not such discharge actually occurs in the case of any particular ion depends upon the potential (voltage) of the current which is passing through the solution, since for each ion there is, under definite conditions, a minimum potential below which the discharge of the ion cannot be effected. By taking advantage of differences in discharge-potentials, it is possible to effect separations of a number of the metallic ions by electrolysis, and at the same time to deposit the metals in forms which admit of direct weighing. In this way the slower procedures of precipitation and filtration may frequently be avoided. The following paragraphs present a brief statement of the fundamental principles and conditions underlying electro-analysis.

The total energy of an electric current as it passes through a solution is distributed among three factors, first, its potential, which is measured in volts, and corresponds to what is called