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

After cooling the electrodes in a desiccator, weigh them and from the weight of copper on the cathode and of lead dioxide (PbO_{2}) on the anode, calculate the percentage of copper (Cu) and of lead (Pb) in the brass.

[Note 1: It is obvious that the brass taken for analysis should be untarnished, which can be easily assured, when wire is used, by scouring with emery. If chips or borings are used, they should be well mixed, and the sample for analysis taken from different parts of the mixture.]

[Note 2: If a white residue remains upon treatment of the alloy with nitric acid, it indicates the presence of tin. The material is not, therefore, a true brass. This may be treated as follows: Evaporate the solution to dryness, moisten the residue with 5 cc. of dilute nitric acid (sp. gr. 1.2) and add 50 cc. of hot water. Filter off the meta-stannic acid, wash, ignite in porcelain and weigh as SnO_{2}. This oxide is never wholly free from copper and must be purified for an exact determination. If it does not exceed 2 per cent of the alloy, the quantity of copper which it contains may usually be neglected.]

[Note 3: The electrodes should be freed from all greasy matter before using, and those portions upon which the metal will deposit should not be touched with the fingers after cleaning.]

[Note 4: Of the ions in solution, the H^{+}, Cu^{++}, Zn^{++}, and Fe^{+++} ions tend to move toward the cathode. The NO_{3}^{-} ions and the lead, probably in the form of PbO_{2}^{—} ions, move toward the anode. At the cathode the Cu^{++} ions are discharged and plate out as metallic copper. This alone occurs while the solution is relatively concentrated. Later on, H^{+} ions are also discharged. In the presence of considerable quantities of H^{+} ions, as in this acid solution, no Zn^{++} or Fe^{+++} ions are discharged because of their greater deposition potentials. At the anode the lead is deposited as PbO_{2} and oxygen is evolved.

For the reasons stated on page 141 care must be taken that the solution does not become alkaline if the electrolysis is long continued.]

[Note 5: Urea reacts with nitrous acid, which may be formed in the solution as a result of the reducing action of the liberated hydrogen. Its removal promotes the complete precipitation of the copper. The reaction is

CO(NH_{2}){2} + 2HNO{2} —> CO_{2} + 2N_{2} + 3H_{2}O.]

[Note 6: The electrodes must be washed nearly or quite free from the nitric acid solution before the circuit is broken to prevent re-solution of the copper.

If several solutions are connected in the same circuit it is obvious that some device must be used to close the circuit as soon as the beaker is removed.]

[Note 7: The electrodes upon which the copper has been deposited may be cleaned by immersion in warm nitric acid. To remove the lead dioxide, add a few crystals of oxalic acid to the nitric acid.]

Most brasses contain small percentages of iron (usually not over 0.1 per cent) which, unless removed, is precipitated as phosphate and weighed with the zinc.

PROCEDURE.—To the solution from the precipitation of copper and lead by electrolysis, add dilute ammonia (sp. gr. 0.96) until the precipitate of zinc hydroxide which first forms re-dissolves, leaving only a slight red precipitate of ferric hydroxide. Filter off the iron precipitate, using a washed filter, and wash five times with hot water. Test a portion of the last washing with a dilute solution of ammonium sulphide to assure complete removal of the zinc.

The precipitate may then be ignited and weighed as ferric oxide, as described on page 110.

Calculate the percentage of iron (Fe) in the brass.

PROCEDURE.—Acidify the filtrate from the iron determination with dilute nitric acid. Concentrate it to 150 cc. Add to the cold solution dilute ammonia (sp. gr. 0.96) cautiously until it barely smells of ammonia; then add !one drop! of a dilute solution of litmus (Note 1), and drop in, with the aid of a dropper, dilute nitric acid until the blue of the litmus just changes to red. It is important that this point should not be overstepped. Heat the solution nearly to boiling and pour into it slowly a filtered solution of di-ammonium hydrogen phosphate[1] containing a weight of the phosphate about equal to twelve times that of the zinc to be precipitated. (For this calculation the approximate percentage of zinc is that found by subtracting the sum of the percentages of the copper, lead and iron from 100 per cent.) Keep the solution just below boiling for fifteen minutes, stirring frequently (Note 2). If at the end of this time the amorphous precipitate has become crystalline, allow the solution to cool for about four hours, although a longer time does no harm (Note 3), and filter upon an asbestos filter in a porcelain Gooch crucible. The filter is prepared as described on page 103, and should be dried to constant weight at 105°C.

[Footnote 1: The ammonium phosphate which is commonly obtainable contains some mono-ammonium salt, and this is not satisfactory as a precipitant. It is advisable, therefore, to weigh out the amount of the salt required, dissolve it in a small volume of water, add a drop of phenolphthalein solution, and finally add dilute ammonium hydroxide solution cautiously until the solution just becomes pink, but do not add an excess.]

Wash the precipitate until free from sulphates with a warm 1 per cent solution of the di-ammonium phosphate, and then five times with 50 per cent alcohol (Note 4). Dry the crucible and precipitate for an hour at 105°C., and finally to constant weight (Note 5). The filtrate should be made alkaline with ammonia and tested for zinc with a few drops of ammonium sulphide, allowing it to stand (Notes 6, 7 and 8).

From the weight of the zinc ammonium phosphate (ZnNH_{4}PO_{4}) calculate the percentage of the zinc (Zn) in the brass.

[Note 1: The zinc ammonium phosphate is soluble both in acids and in ammonia. It is, therefore, necessary to precipitate the zinc in a nearly neutral solution, which is more accurately obtained by adding a drop of a litmus solution to the liquid than by the use of litmus paper.]

[Note 2: The precipitate which first forms is amorphous, and may have a variable composition. On standing it becomes crystalline and then has the composition ZnNH_{4}PO_{4}. The precipitate then settles rapidly and is apt to occasion "bumping" if the solution is heated to boiling. Stirring promotes the crystallization.]

[Note 3: In a carefully neutralized solution containing a considerable excess of the precipitant, and also ammonium salts, the separation of the zinc is complete after standing four hours. The ionic changes connected with the precipitation of the zinc as zinc ammonium phosphate are similar to those described for magnesium ammonium phosphate, except that the zinc precipitate is soluble in an excess of ammonium hydroxide, probably as a result of the formation of complex ions of the general character Zn(NH_{3})_{4}^{++}.]

[Note 4: The precipitate is washed first with a dilute solution of the phosphate to prevent a slight decomposition of the precipitate (as a result of hydrolysis) if hot water alone is used. The alcohol is added to the final wash-water to promote the subsequent drying.]

[Note 5: The precipitate may be ignited and weighed as Zn_{2}P_{2}O_{7}, by cautiously heating the porcelain Gooch crucible within a nickel or iron crucible, used as a radiator. The heating must be very slow at first, as the escaping ammonia may reduce the precipitate if it is heated too quickly.]

[Note 6: If the ammonium sulphide produced a distinct precipitate, this should be collected on a small filter, dissolved in a few cubic centimeters of dilute nitric acid, and the zinc reprecipitated as phosphate, filtered off, dried, and weighed, and the weight added to that of the main precipitate.]

[Note 7: It has been found that some samples of asbestos are acted upon by the phosphate solution and lose weight. An error from this source may be avoided by determining the weight of the crucible and filter after weighing the precipitate. For this purpose the precipitate may be dissolved in dilute nitric acid, the asbestos washed thoroughly, and the crucible reweighed.]

[Note 8. The details of this method of precipitation of zinc are fully discussed in an article by Dakin, !Ztschr. Anal. Chem.!, 39 (1900), 273.]

Of the natural silicates, or artificial silicates such as slags and some of the cements, a comparatively few can be completely decomposed by treatment with acids, but by far the larger number require fusion with an alkaline flux to effect decomposition and solution for analysis. The procedure given below applies to silicates undecomposable by acids, of which the mineral feldspar is taken as a typical example. Modifications of the procedure, which are applicable to silicates which are completely or partially decomposable by acids, are given in the Notes on page 155.

Grind about 3 grams of the mineral in an agate mortar (Note 1) until no grittiness is to be detected, or, better, until it will entirely pass through a sieve made of fine silk bolting cloth. The sieve may be made by placing a piece of the bolting cloth over the top of a small beaker in which the ground mineral is placed, holding the cloth in place by means of a rubber band below the lip of the beaker. By inverting the beaker over clean paper and gently tapping it, the fine particles pass through the sieve, leaving the coarser particles within the beaker. These must be returned to the mortar and ground, and the process of sifting and grinding repeated until the entire sample passes through the sieve.

[Note 1: If the sample of feldspar for analysis is in the massive or crystalline form, it should be crushed in an iron mortar until the pieces are about half the size of a pea, and then transferred to a steel mortar, in which they are reduced to a coarse powder. A wooden mallet should always be used to strike the pestle of the steel mortar, and the blows should not be sharp.

It is plain that final grinding in an agate mortar must be continued until the whole of the portion of the mineral originally taken has been ground so that it will pass the bolting cloth, otherwise the sifted portion does not represent an average sample, the softer ingredients, if foreign matter is present, being first reduced to powder. For this reason it is best to start with not more than the quantity of the feldspar needed for analysis. The mineral must be thoroughly mixed after the grinding.]

PROCEDURE.—Weigh into platinum crucibles two portions of the ground feldspar of about 0.8 gram each. Weigh on rough balances two portions of anhydrous sodium carbonate, each amounting to about six times the weight of the feldspar taken for analysis (Note 1). Pour about three fourths of the sodium carbonate into the crucible, place the latter on a piece of clean, glazed paper, and thoroughly mix the substance and the flux by carefully stirring for several minutes with a dry glass rod, the end of which has been recently heated and rounded in a flame and slowly cooled. The rod may be wiped off with a small fragment of filter paper, which may be placed in the crucible. Place the remaining fourth of the carbonate on the top of the mixture. Cover the crucible, heat it to dull redness for five minutes, and then gradually increase the heat to the full capacity of a Bunsen or Tirrill burner for twenty minutes, or until a quiet, liquid fusion is obtained (Note 2). Finally, heat the sides and cover strongly until any material which may have collected upon them is also brought to fusion.

Allow the crucible to cool, and remove the fused mass as directed on page 116. Disintegrate the mass by placing it in a previously prepared mixture of 100 cc. of water and 50 cc. of dilute hydrochloric acid (sp. gr. 1.12) in a covered casserole (Note 3). Clean the crucible and lid by means of a little hydrochloric acid, adding this acid to the main solution (Notes 4 and 5).

[Note 1: Quartz, and minerals containing very high percentages of silica, may require eight or ten parts by weight of the flux to insure a satisfactory decomposition.]

[Note 2: During the fusion the feldspar, which, when pure, is a silicate of aluminium and either sodium or potassium, but usually contains some iron, calcium, and magnesium, is decomposed by the alkaline flux. The sodium of the latter combines with the silicic acid of the silicate, with the