An examination of some methods employed in determining the atomic weight of CadmiumBucher, John Emery
History
An examination of some methods employed in determining the atomic weight of Cadmium
Bucher, John Emery
Cadmium; Thesis (Ph. D.)
The fact that sulphide of cadmium was always too light after the first
hour’s heating in hydrogen sulphide proves that it must have contained
some oxide of cadmium even after this heating. Oxide of cadmium is
readily absorbed by the glaze on porcelain, and some error must have
been introduced in this way because it would not be converted into
sulphide after forming a silicate.
The effect of this would be to give a low result for the atomic weight
of cadmium. To get some idea of the magnitude of this error, the
sulphide was poured out of the boats used in the first and second
determinations. They were then warmed with nitric acid for a few
moments, washed in water, and heated over the blast lamp for a few
minutes. The boats used as tares were treated in exactly the same
manner. On weighing, the boats in which the oxalate in determinations I
and II had been decomposed, were found to be 1.12 milligrammes and .82
milligrammes heavier respectively than at the beginning of the
determinations. This would only introduce an error of .03 of a unit in
the atomic weight on account of the small difference in weight between
these amounts of oxide and equivalent amounts of sulphide. The boats
were warmed, as above mentioned, with nitric acid to remove any adhering
sulphide. This might have decomposed some cadmium silicate at the same
time, and the error due to cadmium oxide thus be found smaller than it
really is.
The following experiment was made in the hope of avoiding the formation
of cadmium silicate. The glaze was removed from the inside of a
porcelain boat by hydrofluoric acid followed by a thorough scouring with
sand and water. The boat was then heated in the flame of a blast lamp
for several minutes, tared against another boat which was not treated
with hydrofluoric acid. Both were heated to redness in a current of
hydrogen sulphide for an hour, cooled, weighed, and then heated in
hydrogen sulphide for another hour, and weighed again. The boat gained
1.7 milligrammes during this second heating, showing that a boat whose
glaze has been removed by hydrofluoric acid could not be used in this
method. Throughout this work, great care was taken to exclude the oxygen
of the air from the cadmium sulphide, while hot. The current of hydrogen
sulphide in which the cadmium sulphide is heated must not be too slow,
otherwise the sulphur in the dissociated gas will diffuse to the colder
parts of the tube and condense, the residual gas becoming very rich in
hydrogen. The hydrogen will then reduce some of the sulphide to metal,
causing loss by volatilization. One determination was lost in this way,
over two milligrammes of the sulphide being sublimed out, and it could
easily be detected on the side of the tube. It is believed that the
cause of the variations in the four determinations made by this method,
is due to imperfect dehydration of the oxalate. It did not seem
advisable to continue this part of the work any farther; therefore the
Public-domain text, read in full here on John Shaqi.
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