By M. Carey Lea.
In the first part of this paper were described certain forms of silver; among them a lilac blue substance, very soluble in water, with a deep red color. After undergoing purification, it was shown to be nearly pure silver. During the purification by washing it seemed to change somewhat, and, consequently, some uncertainty existed as to whether or not the purified substance was essentially the same as the first product; it seemed possible that the extreme solubility of the product in its first condition might be due to a combination in some way with citric acid, the acid separating during the washing. Many attempts were made to get a decisive indication, and two series of analyses, one a long one, to determine the ratio between the silver and the citric acid present, without obtaining a wholly satisfactory result, inasmuch as even these determinations of mere ratio involved a certain degree of previous purification which might have caused a separation.
This question has since been settled in an extremely simple way, and the fact established that the soluble blue substance contains not a trace of combined citric acid.
The precipitated lilac blue substance (obtained by reducing silver citrate by ferrous citrate) was thrown on a filter and cleared of mother water as far as possible with a filter pump. Pure water was then poured on in successive portions until more than half the substance was dissolved. The residue, evidently quite unchanged, was, of course, tolerably free from mother water. It was found that by evaporating it to dryness over a water bath, most of the silver separated out as bright white normal silver; by adding water and evaporating a second time, the separation was complete, and water added dissolved no silver. The solution thus obtained was neutral. It must have been acid had any citric acid been combined originally with the silver. This experiment, repeated with every precaution, seems conclusive. The ferrous solution, used for reducing the silver citrate, had been brought to exact neutrality with sodium hydroxide. After the reduction had been effected, the mother water over the lilac blue precipitate was neutral or faintly acid.
A corroborating indication is the following: The portions of the lilac blue substance which were dissolved on the filter (see above) were received into a dilute solution of magnesium sulphate, which throws down insoluble allotropic silver of the form I have called B (see previous paper). This form has already been shown to be nearly pure silver. The magnesia solution, neutral before use, was also neutral after it had effected the precipitation, indicating that no citric acid had been set free in the precipitation of the silver.
It seems, therefore, clear that the lilac blue substance contains no combined citric acid. Had the solubility of the silver been due to combination with either acid or alkali, the liquid from which it was separated by digestion at or below 100° C. must have been acid or alkaline; it could not have been neutral.
We have, therefore, this alternative: In the lilac blue substance we have either pure silver in a soluble form or else a compound of silver, with a perfectly neutral substance generated from citric acid in the reaction which leads to the formation of the lilac blue substance. If this last should prove the true explanation, then we have to do with a combination of silver of a quite different nature from any silver compounds hitherto known. A neutral substance generated from citric acid must have one or more atoms of hydrogen replaced by silver. This possibility recalls the recent observations of Ballo, who, by acting with a ferrous salt on tartaric acid, obtained a neutral colloid substance having the constitution of arabin, CHO.
To appreciate the difficulty of arriving at a correct conclusion, it must be remembered that the silver precipitate is obtained saturated with strong solutions of ferric and ferrous citrate, sodium citrate, sulphate, etc. These cannot be removed by washing with pure water, in which the substance itself is very soluble, but must be got rid of by washing with saline solutions, under the influence of which the substance itself slowly but continually changes. Next, the saline solution used for washing must be removed by alcohol. During this treatment, the substance, at first very soluble, gradually loses its solubility, and, when ready for analysis, has become wholly insoluble. It is impossible at present to say whether it may not have undergone other change; this is a matter as to which I hope to speak more positively later. It is to be remarked, however, that these allotropic forms of silver acquire and lose solubility from very slight causes, as an instance of which may be mentioned the ease with which the insoluble form B recovers its solubility under the influence of sodium sulphate and borate, and other salts, as described in the previous part of this paper.
The two insoluble forms of allotropic silver which I have described as B and C - B, bluish green; C, rich golden color - show the following curious reaction. A film of B, spread on glass and heated in a water stove to 100° C. for a few minutes becomes superficially bright yellow. A similar film of the gold colored substance, C, treated in the same way, acquires a blue bloom. In both cases it is the surface only that changes.
All these forms of silver are acted upon by light. A and B acquire a brownish tinge by some hours' exposure to sunlight. With C the case is quite different, the color changes from that of red gold to that of pure yellow gold. The experiment is an interesting one. The exposed portion retains its full metallic brilliancy, giving an additional proof that the color depends upon molecular arrangement, and this with the allotropic forms of silver is subject to change from almost any influence.
These substances vary greatly in stability under influences difficult to appreciate. I have two specimens of the gold yellow substance, C, both made in December, 1886, with the same proportions, under the same conditions. One has passed to dazzling white, normal silver, without falling to powder, or undergoing disaggregation of any sort; the fragments have retained their shape, simply changing to a pure frosted white, remaining apparently as solid as before; the other is unchanged, and still shows its deep yellow color and golden luster. Another specimen made within a few months and supposed to be permanent has changed to brown. Complete exclusion of air and light is certainly favorable to permanence.
The brittleness of the substances B and C, the facility with which they can be reduced to the finest powder, makes a striking point of difference between allotropic and normal silver. It is probable that normal silver, precipitated in fine powder and set aside moist to dry gradually, may cohere into brittle lumps, but these would be mere aggregations of discontinuous material. With allotropic silver the case is very different, the particles dry in optical contact with each other, the surfaces are brilliant, and the material evidently continuous. That this should be brittle indicates a totally different state of molecular constitution from that of normal silver.
The allotropic forms of silver show a lower specific gravity than that of normal silver.
In determining the specific gravities it was found essential to keep the sp. gr. bottle after placing the material in it for some hours under the bell of an air pump. Films of air attach themselves obstinately to the surfaces, and escape but slowly even in vacuo.
Taken with this precaution, the blue substance, B, gave specific gravity 9.58, and the yellow substance, C, specific gravity 8.51. The specific gravity of normal silver, after melting, was found by G. Rose to be 10.5. That of finely divided silver obtained by precipitation is stated to be 10.62.1
I believe these determinations to be exact for the specimens employed. But the condition of aggregation may not improbably vary somewhat in different specimens. It seems, however, clear that these forms of silver have a lower specific gravity than the normal, and this is what would be expected.
Chestnut Hill, Philadelphia, May, 1889
Amer. Jour. of Science.
Watts' Dict., orig. ed., v. 277.