3. The third class of changes is even more radical in its nature,
having for its object the adaptation of the moist combustion method
to oxidized or mineral nitrogen. The chief feature of this class
of changes consists in the introduction of a substance rich in
hydrocarbons, and capable of easily forming nitro compounds, for the
purpose of holding the oxids of nitrogen which are formed during the
combustion and helping finally to reduce them to the form of ammonia.
The chief varieties of this class of changes were proposed by Asboth,
Jodlbaur, and Scovell, and will be fully set forth in separate
paragraphs.
=188. Method of Wilfarth.=—The basis of this modification as already
noted rests on the fact that certain metallic oxids have the power
of carrying oxygen, and thus assisting in a katalytic way in the
combustion of organic matter.[156] The copper and mercury oxids
are best adapted for this purpose and experience has shown that
mercuric oxid, or even metallic mercury gives the best results. The
manipulation is carried out as follows: From one to three grams of
the sample, according to its richness in nitrogen, are heated with
a mixture of twenty cubic centimeters of acid containing two-fifths
fuming and three-fifths ordinary sulfuric acid. To this is added
about seven-tenths gram of mercuric oxid prepared in the wet way from
a mercury salt free of nitrogen. The combustion takes place in the
usual kjeldahl flask. If the boiling be continued until the liquid
is entirely colorless, final oxidation with potassium permanganate
is unnecessary. To save time the combustion may be stopped when a
light amber color is reached, and then the oxidation finished with
permanganate. Before distilling, a sufficient quantity of potassium
sulfid is added to precipitate all the mercury as sulfid and thus
prevent the formation of mercurammonium compounds which would produce
a deficit of ammonia. A convenient strength of the sulfid solution is
obtained by dissolving forty grams of potassium sulfid in one liter of
water. Bumping at the end of the distillation is not usual, especially
if potash-lye be used, but should it occur it may be stopped by the
addition of zinc dust.
Only when a large excess of potassium sulfid is used is there an
evolution of hydrogen sulfid, the presence of which, however, does not
influence the accuracy of the results.
The presence of mercuric sulfid in the solution tends to prevent
bumping during the distillation, but it is advisable, nevertheless,
to use a little zinc dust. Other minor modifications consist of
forming the acid mixture with equal volumes of concentrated and
fuming sulfuric acid containing in one liter 100 grams of phosphoric
acid anhydrid,[157] and using metallic mercury instead of mercuric
oxid; or a mixture of half a gram of copper sulfate and one gram of
metallic mercury,[158] or half a gram of copper oxid and a few drops of
platinic chlorid solution containing 0.04 gram of platinum in a cubic
centimeter.[159]
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