The first is the error which may arise from the consumption of the
small quantity of uranium phosphate which is taken with a stirring rod
when the liquid is tested with potassium ferrocyanid. It is very easy
to be assured that the end of the reaction has really been reached. For
this purpose it is only necessary to note the quantity of the solution
already employed and to add to it afterwards four drops; shake, and
make a new test with a drop of the potassium ferrocyanid placed near
the spot which the last one occupied. If a decidedly reddish tint
does not appear at the moment of removing the glass rod, it is to be
concluded that the first appearance was an illusion, and the addition
of uranium is to be continued. If, on the contrary, the coloration
appear of a decided tint, the preceding number may be taken for exact.
It is then always beneficial to close the titration by this test of
four supplementary drops which will exaggerate the coloration and
confirm the figure found.
The second cause of error, and one moreover which is the most
frequently met with, consists in passing the end of the reaction by
adding the uranium too rapidly. In place of giving then a coloration
scarcely perceptible, the test with the drop of potassium ferrocyanid
gives a very marked coloration. In this case the analysis can still
be saved. For this purpose the analyst has, at his disposal, a tenth
normal solution prepared with 100 cubic centimeters of the standard
solution of phosphoric acid diluted to one liter with distilled water.
Ten cubic centimeters of this tenth normal solution are added, and the
titration continued. At the end, the amount of additional phosphoric
acid used is subtracted from the total.
A third cause of error is found in the foam which is often found in
the liquid, due to the shaking. This foam may retain a portion of the
last drops of the solution of uranium which fall upon its surface and
prevent its mixture with the rest of the liquid. If the glass stirring
rod in being removed from the vessel pass through this froth charged
with uranium, the characteristic coloration is obtained before real
saturation is reached. Consequently it is necessary to avoid, as much
as possible, the formation of the foam, and especially to take care
never to take the drop for test after agitation except in the middle of
the liquid where the foam does not exist.
Suppose the titration has been made upon ten cubic centimeters of the
normal solution of phosphoric acid in the conditions which we have
just indicated, and the figure for the uranium obtained is 10.2 cubic
centimeters; if now the correction, which may be supposed to amount
to two-tenths cubic centimeter, be subtracted there will remain ten
cubic centimeters of the uranium solution which would have precipitated
exactly fifty milligrams of phosphoric acid.
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