Ba^{++} + SO_{4}^{—} —> [BaSO_{4}]
This case affords one of the best illustrations of the effect of an excess of a precipitant in decreasing the solubility of a precipitate. If the conditions are considered which exist at the moment when just enough of the Ba^{++} ions have been added to correspond to the SO_{4}^{—} ions in the solution, it will be seen that nearly all of the barium sulphate has been precipitated, and that the small amount which then remains in the solution which is in contact with the precipitate must represent a saturated solution for the existing temperature, and that this solution is comparable with a solution of sugar to which more sugar has been added than will dissolve. It should be borne in mind that the quantity of barium sulphate in this !saturated solution is a constant quantity! for the existing conditions. The dissolved barium sulphate, like any electrolyte, is dissociated, and the equilibrium conditions may be expressed thus:
(!Conc'n Ba^{++} x Conc'n SO_{4}^{—})/(Conc'n BaSO_{4}) = Const.!,
and since !Conc'n BaSO_{4}! for the saturated solution has a constant value (which is very small), it may be eliminated, when the expression becomes !Conc'n Ba^{++} x Conc'n SO_{4}^{—} = Const.!, which is the "solubility product" of BaSO_{4}. If, now, an excess of the precipitant, a soluble barium salt, is added in the form of a relatively concentrated solution (the slight change of volume of a few cubic centimeters may be disregarded for the present discussion) the concentration of the Ba^{++} ions is much increased, and as a consequence the !Conc'n SO_{4}! must decrease in proportion if the value of the expression is to remain constant, which is a requisite condition if the law of mass action upon which our argument depends holds true. In other words, SO_{4}^{—} ions must combine with some of the added Ba^{++} ions to form [BaSO_{4}]; but it will be recalled that the solution is already saturated with BaSO_{4}, and this freshly formed quantity must, therefore, separate and add itself to the precipitate. This is exactly what is desired in order to insure more complete precipitation and greater accuracy, and leads to the conclusion that the larger the excess of the precipitant added the more successful the analysis; but a practical limit is placed upon the quantity of the precipitant which may be properly added by other conditions, as stated in the following note.]
[Note 3: Barium sulphate, in a larger measure than most compounds, tends to carry down other substances which are present in the solution from which it separates, even when these other substances are relatively soluble, and including the barium chloride used as the precipitant. This is also notably true in the case of nitrates and chlorates of the alkalies, and of ferric compounds; and, since in this analysis ammonium nitrate has resulted from the neutralization of the excess of the nitric acid added to oxidize the iron, it is essential that this should be destroyed by repeated evaporation with a relatively large quantity of hydrochloric acid. During evaporation a mutual decomposition of the two acids takes place, and the nitric acid is finally decomposed and expelled by the excess of hydrochloric acid.
Iron is usually found in the precipitate of barium sulphate when thrown down from hot solutions in the presence of ferric salts. This, according to Kuster and Thiel (!Zeit. anorg. Chem.!, 22, 424), is due to the formation of a complex ion (Fe(SO_{4})_{2}) which precipitates with the Ba^{++} ion, while Richards (!Zeit. anorg. Chem.!, 23, 383) ascribes it to hydrolytic action, which causes the formation of a basic ferric complex which is occluded in the barium precipitate. Whatever the character of the compound may be, it has been shown that it loses sulphuric anhydride upon ignition, causing low results, even though the precipitate contains iron.
The contamination of the barium sulphate by iron is much less in the presence of ferrous than ferric salts. If, therefore, the sulphur alone were to be determined in the ferrous ammonium sulphate, the precipitation by barium might be made directly from an aqueous solution of the salt, which had been made slightly acid with hydrochloric acid.]
[Note 4: The precipitation of the barium sulphate is probably complete at the end of a half-hour, and the solution may safely be filtered at the expiration of that time if it is desired to hasten the analysis.
As already noted, many precipitates of the general character of this sulphate tend to grow more coarsely granular if digested for some time with the liquid from which they have separated. It is therefore well to allow the precipitate to stand in a warm place for several hours, if practicable, to promote ease of filtration. The filtrate and washings should always be carefully examined for minute quantities of the sulphate which may pass through the pores of the filter. This is best accomplished by imparting to the filtrate a gentle rotary motion, when the sulphate, if present, will collect at the center of the bottom of the beaker.]
[Note 5: A reduction of barium sulphate to the sulphide may very readily be caused by the reducing action of the burning carbon of the filter, and much care should be taken to prevent any considerable reduction from this cause. Subsequent ignition, with ready access of air, reconverts the sulphide to sulphate unless a considerable reduction has occurred. In the latter case it is expedient to add one or two drops of sulphuric acid and to heat cautiously until the excess of acid is expelled.]