An Introductory Course of Quantitative Chemical Analysis by Henry P. Talbot (good short books .TXT) 📖

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.]

PART IV STOICHIOMETRY

The problems with which the analytical chemist has to deal are not, as a matter of actual fact, difficult either to solve or to understand. That they appear difficult to many students is due to the fact that, instead of understanding the principles which underlie each of the small number of types into which these problems may be grouped, each problem is approached as an individual puzzle, unrelated to others already solved or explained. This attitude of mind should be carefully avoided.

It is obvious that ability to make the calculations necessary for the interpretation of analytical data is no less important than the manipulative skill required to obtain them, and that a moderate time spent in the careful study of the solutions of the typical problems which follow may save much later embarrassment.

1. It is often necessary to calculate what is known as a "chemical factor," or its equivalent logarithmic value called a "log factor," for the conversion of the weight of a given chemical substance into an equivalent weight of another substance. This is, in reality, a very simple problem in proportion, making use of the atomic or molecular weights of the substances in question which are chemically equivalent to each other. One of the simplest cases of this sort is the following: What is the factor for the conversion of a given weight of barium sulphate (BaSO_{4}) into an equivalent weight of sulphur (S)? The molecular weight of BaSO_{4} is 233.5. There is one atom of S in the molecule and the atomic weight of S is 32.1. The chemical factor is, therefore, 32.1/233.5, or 0.1375 and the weight of S corresponding to a given weight of BaSO_{4} is found by multiplying the weight of BaSO_{4} by this factor. If the problem takes the form, "What is the factor for the conversion of a given weight of ferric oxide (Fe_{2}O_{3}) into ferrous oxide (FeO), or of a given weight of mangano-manganic oxide (Mn_{3}O_{4}) into manganese (Mn)?" the principle involved is the same, but it must then be noted that, in the first instance, each molecule of Fe_{2}O_{3} will be equivalent to two molecules of FeO, and in the second instance that each molecule of Mn_{3}O_{4} is equivalent to three atoms of Mn. The respective factors then become

(2FeO/Fe_{2}O_{3}) or (143.6/159.6) and (3Mn/Mn_{3}O_{4}) or (164.7/228.7).

It is obvious that the arithmetical processes involved in this type of problem are extremely simple. It is only necessary to observe carefully the chemical equivalents. It is plainly incorrect to express the ratio of ferrous to ferric oxide as (FeO/Fe_{2}O_{3}), since each molecule of the ferric oxide will yield two molecules of the ferrous oxide. Mistakes of this sort are easily made and constitute one of the most frequent sources of error.

2. A type of problem which is slightly more complicated in appearance, but exactly comparable in principle, is the following: "What