It is known that platinum heated in a forge fire, in contact with
carbon, becomes fusible. Boussingault has shown that this is due to the
formation of a silicide of platinum by means of the reduction of the
silica of the carbon by the metal. MM. P. Schuetzenberger and A. Colson
have produced the same phenomenon by heating to white heat a slip of
platinum in the center of a thick layer of lampblack free from silica.
The increase in weight of the metal and the augmentation of its
fusibility were found to be due, in this case also, to a combination
with silicon. As the silicon could not come directly from the carbon
which surrounded the platinum, MM. Schuetzenberger and Colson have
endeavored to discover under what form it could pass from the walls of
the crucible through a layer of lampblack several centimeters in
thickness, in spite of a volatility amounting to almost nothing under
the conditions of the experiment. They describe the following
experiments as serving to throw some light upon the question:
1. A thin slip of platinum rolled in a spiral is placed in a small
crucible of retort carbon closed by a turned cover of the same material.
This is placed in a second larger crucible of refractory clay, and the
intervening space filled with lampblack tightly packed. The whole is
then heated to white heat for an hour and a half in a good wind furnace.
After cooling, the platinum is generally found to have been fused into a
button, with a marked increase in weight due to taking up silicon, which
has penetrated in the form of vapor through the walls of the interior
crucible.
2. If, in the preceding experiment, the lampblack be replaced by a
mixture of lampblack and rutile in fine powder, the slip of platinum
remains absolutely intact, and does not change in weight. Thus the
titaniferous packing recommended by Sainte-Claire Deville for preventing
the access of nitrogen in experiments at high temperatures also prevents
the passage of silicon. A mixture of carbon and finely divided iron is,
on the contrary, ineffectual. These facts seem to indicate that nitrogen
plays a part in the transportation of the silicon, as this is only
prevented by the same means made use of in order to prevent the passage
of nitrogen.
3. The volatility of free silicon at a high temperature is too slight to
account for the alteration of the platinum at a distance. This can be
shown by placing several decigrammes of crystallized silicon on the
bottom of a small crucible of retort carbon, covering the silicon with a
small flat disk of retort carbon upon which is placed the slip of
platinum. The crucible, closed by its turned cover, is then enveloped in
a titaniferous packing and kept at a brilliant white heat for an hour
and a half. The metal is found to have only very slightly increased in
weight, and its properties remain unaltered. This experiment was
repeated several times with the same result. If, however, the
crystallized silicon be replaced by powdered calcined silica, the
platinum, placed upon the carbon disk, fuses and increases in weight,
while the silica loses weight. The theory of these curious phenomena is
very difficult to establish on account of the high temperatures which
are necessary for their manifestation, but it may be concluded, at
present, that nitrogen and probably oxygen also play some part in the
transportation of the silicon across the intervening space, and that the
carbosilicious compounds recently described by MM. Schuetzenberger and
Colson also take part in the phenomenon.--_Comptes Rendus_, xciv.,
1,710.--_Amer. Chem. Journal._
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