[Note 3: The accurate quant.i.tative separation of calcium and magnesium as oxalates requires considerable care. The calcium precipitate usually carries down with it some magnesium, and this can best be removed by redissolving the precipitate after filtration, and reprecipitation in the presence of only the small amount of magnesium which was included in the first precipitate. When, however, the proportion of magnesium is not very large, the second precipitation of the calcium can usually be avoided by precipitating it from a rather dilute solution (800 cc. or so) and in the presence of a considerable excess of the precipitant, that is, rather more than enough to convert both the magnesium and calcium into oxalates.]
[Note 4: The ionic changes involved in the precipitation of calcium as oxalate are exceedingly simple, and the principles discussed in connection with the barium sulphate precipitation on page 113 also apply here. The reaction is
C_{2}O_{4}^{--} + Ca^{++} --> [CaC_{2}O_{4}].
Calcium oxalate is nearly insoluble in water, and only very slightly soluble in acetic acid, but is readily dissolved by the strong mineral acids. This behavior with acids is explained by the fact that oxalic acid is a stronger acid than acetic acid; when, therefore, the oxalate is brought into contact with the latter there is almost no tendency to diminish the concentration of C_{2}O_{4}^{--} ions by the formation of an acid less dissociated than the acetic acid itself, and practically no solvent action ensues. When a strong mineral acid is present, however, the ionization of the oxalic acid is much reduced by the high concentration of the H^{+} ions from the strong acid, the formation of the undissociated acid lessens the concentration of the C_{2}O_{4}^{--} ions in solution, more of the oxalate pa.s.ses into solution to re-establish equilibrium, and this process repeats itself until all is dissolved.
The oxalate is immediately reprecipitated from such a solution on the addition of OH^{-} ions, which, by uniting with the H^{+} ions of the acids (both the mineral acid and the oxalic acid) to form water, leave the Ca^{++} and C_{2}O_{4}^{--} ions in the solution to recombine to form [CaC_{2}O_{4}], which is precipitated in the absence of the H^{+} ions. It is well at this point to add a small excess of C_{2}O_{4}^{--} ions in the form of ammonium oxalate to decrease the solubility of the precipitate.
The oxalate precipitate consists mainly of CaC_{2}O_{4}.H_{2}O when thrown down.]
[Note 5: The small quant.i.ty of ammonium oxalate solution is added before the second precipitation of the calcium oxalate to insure the presence of a slight excess of the reagent, which promotes the separation of the calcium compound.]
[Note 6: On ignition the calcium oxalate loses carbon dioxide and carbon monoxide, leaving calcium oxide:
CaC_{2}O_{4}.H_{2}O --> CaO + CO_{2} + CO + H_{2}O.
For small weights of the oxalate (0.6 gram or less) this reaction may be brought about in a platinum crucible at the highest temperature of a Tirrill burner, but it is well to ignite larger quant.i.ties than this over the blast lamp until the weight is constant.]
[Note 7: The heat required to burn the filter, and that subsequently applied as described, will convert most of the calcium oxalate to calcium carbonate, which is changed to sulphate by the sulphuric acid.
The reactions involved are
CaC_{2}O_{4} --> CaCO_{3} + CO, CaCO_{3} + H_{2}SO_{4} --> CaSO_{4} + H_{2}O + CO_{2}.
If a porcelain crucible is employed for ignition, this conversion to sulphate is to be preferred, as a complete conversion to oxide is difficult to accomplish.]
[Note 8: The determination of the calcium may be completed volumetrically by washing the calcium oxalate precipitate from the filter into dilute sulphuric acid, warming, and t.i.trating the liberated oxalic acid with a standard solution of pota.s.sium permanganate as described on page 72. When a considerable number of a.n.a.lyses are to be made, this procedure will save much of the time otherwise required for ignition and weighing.]
DETERMINATION OF MAGNESIUM
PROCEDURE.--Evaporate the acidified filtrates from the calcium precipitates until the salts begin to crystallize, but do !not!
evaporate to dryness (Note 1). Dilute the solution cautiously until the salts are brought into solution, adding a little acid if the solution has evaporated to very small volume. The solution should be carefully examined at this point and must be filtered if a precipitate has appeared. Heat the clear solution to boiling; remove the burner and add 25 cc. of a solution of disodium phosphate. Then add slowly dilute ammonia (1 volume strong ammonia (sp. gr. 0.90) and 9 volumes water) as long as a precipitate continues to form. Finally, add a volume of concentrated ammonia (sp. gr. 0.90) equal to one third of the volume of the solution, and allow the whole to stand for about twelve hours.
Decant the solution through a filter, wash it with dilute ammonia water, proceeding as prescribed for the determination of phosphoric anhydride on page 122, including; the reprecipitation (Note 2), except that 3 cc. of disodium phosphate solution are added before the reprecipitation of the magnesium ammonium phosphate instead of the magnesia mixture there prescribed. From the weight of the pyrophosphate, calculate the percentage of magnesium oxide (MgO) in the sample of limestone. Remember that the pyrophosphate finally obtained is from one fifth of the original sample.
[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 quant.i.ty 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!
[Ill.u.s.tration: 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 gla.s.s 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 gla.s.s delivery tube (c) leads from the condenser to the small U-tube (D) containing some gla.s.s beads or small pieces of gla.s.s 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 pota.s.sium hydroxide (Note 2). The tube (F) is a gla.s.s-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 pota.s.sium hydroxide solution (1 part of solid pota.s.sium 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 pa.s.s 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 a.n.a.lytical 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 ma.s.s of soda lime.
It is essential that soda lime of good quality for a.n.a.lytical 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 pa.s.ses through the bulbs. The small quant.i.ty 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 gla.s.s joint.
After the pota.s.sium hydroxide is approximately half consumed in the first bulb of the absorption apparatus, pota.s.sium 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 a.n.a.lysis!
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 gla.s.s stopc.o.c.ks 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 pinchc.o.c.ks (a) and (k) and open (h). No bubbles should pa.s.s through (D) or (G) after a few seconds. When a.s.sured 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 pinchc.o.c.ks (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 pa.s.s 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 pa.s.s 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 stopc.o.c.ks 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 stopc.o.c.ks (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 a.n.a.lysis.
[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 a.s.sured. The stopc.o.c.ks 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 pa.s.ses 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 a.s.sumed 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.]