Chapter IX: Part III: Gravimetric Analysis (3)

Test the solution in the beaker for copper as follows, remembering that it is to be used for subsequent determinations of iron and zinc: Remove about 5 cc. and add a slight excess of ammonia. Compare the mixture with some distilled water, holding both above a white surface. The solution should not show any tinge of blue. If the presence of copper is indicated, add the test portion to the main solution, evaporate the whole to a volume of about 100 cc., and again electrolyze with clean electrodes (Note 7).

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.]

DETERMINATION OF IRON

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.

DETERMINATION OF ZINC

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.]

DETERMINATION OF SILICA IN SILICATES

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.

PREPARATION OF THE SAMPLE

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.]

FUSION AND SOLUTION

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 evolution of carbon dioxide, while about two thirds of the aluminium forms sodium aluminate and the remainder is converted into basic carbonate, or the oxide. The calcium and magnesium, if present, are changed to carbonates or oxides.

The heat is applied gently to prevent a too violent reaction when fusion first takes place.]

[Note 3: The solution of a silicate by a strong acid is the result of the combination of the H^{+} ions of the acid and the silicate ions of the silicate to form a slightly ionized silicic acid. As a consequence, the concentration of the silicate ions in the solution is reduced nearly to zero, and more silicate dissolves to re-establish the disturbed equilibrium. This process repeats itself until all of the silicate is brought into solution.

Whether the resulting solution of the silicate contains ortho-silicic acid (H_{4}SiO_{4}) or whether it is a colloidal solution of some other less hydrated acid, such as meta-silicic acid (H_{2}SiO_{3}), is a matter that is still debatable. It is certain, however, that the gelatinous material which readily separates from such solutions is of the nature of a hydrogel, that is, a colloid which is insoluble in water. This substance when heated to 100°C., or higher, is completely dehydrated, leaving only the anhydride, SiO_{2}. The changes may be represented by the equation:

SiO_{3}^{--} + 2H^{+} --> [H_{2}SiO_{3}] --> H_{2}O + SiO_{2}.]

[Note 4: A portion of the fused mass is usually projected upward by the escaping carbon dioxide during the fusion. The crucible must therefore be kept covered as much as possible and the lid carefully cleaned.]

[Note 5: A gritty residue remaining after the disintegration of the fused mass by acid indicates that the substance has been but imperfectly decomposed. Such a residue should be filtered, washed, dried, ignited, and again fused with the alkaline flux; or, if the quantity of material at hand will permit, it is better to reject the analysis, and to use increased care in grinding the mineral and in mixing it with the flux.]

DEHYDRATION AND FILTRATION

PROCEDURE.--Evaporate the solution of the fusion to dryness, stirring frequently until the residue is a dry powder. Moisten the residue with 5 cc. of strong hydrochloric acid (sp. gr. 1.20) and evaporate again to dryness. Heat the residue for at least one hour at a temperature of 110°C. (Note 1). Again moisten the residue with concentrated hydrochloric acid, warm gently, making sure that the acid comes into contact with the whole of the residue, dilute to about 200 cc. and bring to boiling. Filter off the silica without much delay (Note 2), and wash five times with warm dilute hydrochloric acid (one part dilute acid (1.12 sp. gr.) to three parts of water). Allow the filter to drain for a few moments, then place a clean beaker below the funnel and wash with water until free from chlorides, discarding these washings. Evaporate the original filtrate to dryness, dehydrate at 110°C. for one hour (Note 3), and proceed as before, using a second filter to collect the silica after the second dehydration. Wash this filter with warm, dilute hydrochloric acid (Note 4), and finally with hot water until free from chlorides.

[Note 1: The silicic acid must be freed from its combination with a base (sodium, in this instance) before it can be dehydrated. The excess of hydrochloric acid accomplishes this liberation. By disintegrating the fused mass with a considerable volume of dilute acid the silicic acid is at first held in solution to a large extent. Immediate treatment of the fused mass with strong acid is likely to cause a semi-gelatinous silicic acid to separate at once and to inclose alkali salts or alumina.

A flocculent residue will often remain after the decomposition of the fused mass is effected. This is usually partially dehydrated silicic acid and does not require further treatment at this point. The progress of the dehydration is indicated by the behavior of the solution, which as evaporation proceeds usually gelatinizes. On this account it is necessary to allow the solution to evaporate on a steam bath, or to stir it vigorously, to avoid loss by spattering.]

[Note 2: To obtain an approximately pure silica, the residue after evaporation must be thoroughly extracted by warming with hydrochloric acid, and the solution freely diluted to prevent, as far as possible, the inclosure of the residual salts in the particles of silica. The filtration should take place without delay, as the dehydrated silica slowly dissolves in hydrochloric acid on standing.]

[Note 3: It has been shown by Hillebrand that silicic acid cannot be completely dehydrated by a single evaporation and heating, nor by several such treatments, unless an intermediate filtration of the silica occurs. If, however, the silica is removed and the filtrates are again evaporated and the residue heated, the amount of silica remaining in solution is usually negligible, although several evaporations and filtrations are required with some silicates to insure absolute accuracy.

It is probable that temperatures above 100°C. are not absolutely necessary to dehydrate the silica; but it is recommended, as tending to leave the silica in a better condition for filtration than when the lower temperature of the water bath is used. This, and many other points in the analysis of silicates, are fully discussed by Dr. Hillebrand in the admirable monograph on "The Analysis of Silicate and Carbonate Rocks," Bulletin No. 700 of the United States Geological Survey.

The double evaporation and filtration spoken of above are essential because of the relatively large amount of alkali salts (sodium chloride) present after evaporation. For the highest accuracy in the determination of silica, or of iron and alumina, it is also necessary to examine for silica the precipitate produced in the filtrate by ammonium hydroxide by fusing it with acid potassium sulphate and solution of the fused mass in water. The insoluble silica is filtered, washed, and weighed, and the weight added to the weight of silica previously obtained.]

[Note 4: Aluminium and iron are likely to be thrown down as basic salts from hot, very dilute solutions of their chlorides, as a result of hydrolysis. If the silica were washed only with hot water, the solution of these chlorides remaining in the filter after the passage of the original filtrate would gradually become so dilute as to throw down basic salts within the pores of the filter, which would remain with the silica. To avoid this, an acid wash-water is used until the aluminium and iron are practically removed. The acid is then removed by water.]

IGNITION AND TESTING OF SILICA

PROCEDURE.--Transfer the two washed filters belonging to each determination to a platinum crucible, which need not be previously weighed, and burn off the filter (Note 1). Ignite for thirty minutes over the blast lamp with the cover on the crucible, and then for periods of ten minutes, until the weight is constant.

When a constant weight has been obtained, pour into the crucible about 3 cc. of water, and then 3 cc. of hydrofluoric acid. !This must be done in a hood with a good draft and great care must be taken not to come into contact with the acid or to inhale its fumes (Note 2!).

If the precipitate has dissolved in this quantity of acid, add two drops of concentrated sulphuric acid, and heat very slowly (always under the hood) until all the liquid has evaporated, finally igniting to redness. Cool in a desiccator, and weigh the crucible and residue. Deduct this weight from the previous weight of crucible and impure silica, and from the difference calculate the percentage of silica in the sample (Note 3).

[Note 1: The silica undergoes no change during the ignition beyond the removal of all traces of water; but Hillebrand (!loc. cit.!) has shown that the silica holds moisture so tenaciously that prolonged ignition over the blast lamp is necessary to remove it entirely. This finely divided, ignited silica tends to absorb moisture, and should be weighed quickly.]

[Note 2: Notwithstanding all precautions, the ignited precipitate of silica is rarely wholly pure. It is tested by volatilisation of the silica as silicon fluoride after solution in hydrofluoric acid, and, if the analysis has been properly conducted, the residue, after treatment with the acids and ignition, should not exceed 1 mg.

The acid produces ulceration if brought into contact with the skin, and its fumes are excessively harmful if inhaled.]

[Note 3: The impurities are probably weighed with the original precipitate in the form of oxides. The addition of the sulphuric acid displaces the hydrofluoric acid, and it may be assumed that the resulting sulphates (usually of iron or aluminium) are converted to oxides by the final ignition.

It is obvious that unless the sulphuric and hydrofluoric acids used are known to leave no residue on evaporation, a quantity equal to that employed in the analysis must be evaporated and a correction applied for any residue found.]

[Note 4: If the silicate to be analyzed is shown by a previous qualitative examination to be completely decomposable, it may be directly treated with hydrochloric acid, the solution evaporated to dryness, and the silica dehydrated and further treated as described in the case of the feldspar after fusion.

A silicate which gelatinizes on treatment with acids should be mixed first with a little water, and the strong acid added in small portions with stirring, otherwise the gelatinous silicic acid incloses particles of the original silicate and prevents decomposition. The water, by separating the particles and slightly lessening the rapidity of action, prevents this difficulty. This procedure is one which applies in general to the solution of fine mineral powders in acids.

If a small residue remains undecomposed by the treatment of the silicate with acid, this may be filtered, washed, ignited and fused with sodium carbonate and a solution of the fused mass added to the original acid solution. This double procedure has an advantage, in that it avoids adding so large a quantity of sodium salts as is required for disintegration of the whole of the silicate by the fusion method.]