Such precautions are still more important in the case of precipitates which are somewhat more soluble than is barium sulphate, and in such cases the question must be considered, whether as a washing fluid, some solution may not be used, which contains an ion in common with the precipitate, and which has, therefore, according to the principle of the solubility-product, a very much smaller dissolving power for the precipitate in question than pure water. That is a resource of the analyst to which recourse is occasionally taken. Lead sulphate, for instance, is washed with a very dilute solution of sulphuric acid, rather than with pure water;[312] potassium cobaltinitrite, K3Co(NO2)6, which is used in the separation of cobalt from nickel, is washed[313] with a ten per cent solution of potassium acetate, containing a little potassium nitrite. Ammonium phosphomolybdate, used in determinations of phosphates, is washed with a solution of ammonium nitrate. [p149]
The use of such solutions for washing precipitates is limited by the necessity, first, of avoiding salts which interfere with subsequent operations (e.g. which would leave nonvolatile residues in the subsequent ignition of a precipitate, that is to be weighed after ignition) and, second, of avoiding the loss of precipitate by the formation of complex ions between an ion of the precipitate and a component of the washing mixture (see p. [148]). But wherever such complications can be excluded, the method is a desirable one.
It has sometimes been recommended to wash a precipitate with a saturated aqueous solution of the precipitate itself, in place of with pure water. It was reasoned that the solution, being already saturated with the salt, would not be able to dissolve any of the precipitate obtained. That is true; but if a saturated solution of a salt, MeX, is placed on a filter still holding an excess of the precipitant, i.e. one of the ions, say X, of the precipitate, then this excess may cause supersaturation of the saturated washing fluid and some of the salt may be precipitated out of the washing fluid. The method, as commonly employed, has therefore the inherent fault, theoretically at least, of being liable to give too high results. If it is to be employed without error, precautions must be taken first to remove, from the precipitate and filter, the mother liquor (containing the excess of precipitant) as completely as possible. If in a given case this can be accomplished, then the danger of precipitating any of the salt (MeX) from the saturated solution is avoided, and the precipitate (MeX ↓) may then be further washed with a saturated solution of the same salt (MeX), with advantage, in certain cases. Thus, in the Lindo-Gladding method[314] of determining potassium in the form of potassium chloroplatinate, the source of error, just discussed, has been avoided in the following way: the excess of precipitant, chloroplatinic acid H2PtCl6, which has the ion PtCl62− in common with the precipitate, is first removed from the precipitate by thorough washing of the precipitate with alcohol; subsequently, other impurities, e.g. sulphates, soluble in water but not in alcohol, are washed out with an aqueous solution of ammonium chloride[315] that has been saturated with potassium chloroplatinate. The method gives good results.
The Solubility-Product in Volumetric Analysis.
Effect of Electrolytes with No Ion in Common with the Precipitate.
Since the concentrations of both the silver and the acetate ions are reduced, they will not combine as rapidly as before to form nonionized silver acetate, and the conditions of equilibrium between the latter and its ions must be disturbed. The nonionized salt ionizes, for a moment, more rapidly than it is formed and its concentration will thus be reduced. We, therefore, might expect the solution to become unsaturated in respect to the nonionized form, and the solid salt, if present, should go into solution. In other words, the addition of a salt with two foreign ions should increase the solubility of a difficultly soluble salt (it is understood that no salt is used which would precipitate a new, less soluble salt). This expectation has also been fully confirmed by careful quantitative determinations, especially by A. A. Noyes and his collaborators. The effect may be demonstrated more easily by the addition to silver acetate of an electrolyte which will very thoroughly suppress one of its ions. Nitric acid is such an agent. The hydrogen-ion will very decidedly reduce the concentration of the acetate-ion, acetic acid being a weak acid (table, p. [104]). There is no difficulty in recognizing the anticipated effect (exp.).
Solution of Precipitates.
Summary.
Further Considerations Concerning Precipitation and Solution.
On the other hand, solution of an ionogen is evidently favored and its precipitation rendered more difficult, if we suppress one (or both) of its ions. Thus barium phosphate, calcium carbonate, silver borate, and many salts of weak acids, that are very difficultly soluble in water, are quite easily soluble in strong acids, which suppress the anions by converting them into little ionized acids. When a precipitate is dissolved by the addition of a reagent, such as an acid, an alkali, ammonia, ammonium sulphide—chemical solvents most frequently used in analytical work—we may, as a general principle, consider that the reagent must affect one or both of the ions of the precipitate in question, suppressing it (or them) and thereby making solution possible. The problem of determining in what way the suppression of the ion is effected, must then be faced. Many occasions to determine such questions[318] will arise. [p153]