_The Manipulation._—Place from seven-tenths to three and five-tenths
grams of the substance to be analyzed in a kjeldahl digesting flask,
add sixty cubic centimeters of sulfuric acid containing one gram of
salicylic acid, and shake until thoroughly mixed, then add five grams
of crystallized sodium thiosulfate; or add to the substance thirty
cubic centimeters of sulfuric acid containing two grams of salicylic
acid, then add gradually two grams of zinc dust, shaking the contents
of the flask at the same time. Finally place the flask on the stand
for holding the digestion flasks, where it is heated over a low flame
until all danger from frothing has passed. The heat is then raised
until the acid boils briskly and the boiling continued until white
fumes no longer pour out of the flask. This requires about five or ten
minutes. Add now approximately seven-tenths gram of mercuric oxid or
its equivalent in metallic mercury, and continue the boiling until the
liquid in the flask is colorless or nearly so. In case the contents of
the flask are likely to become solid before this point is reached add
ten cubic centimeters more of sulfuric acid. Complete the oxidation
with a little potassium permanganate in the usual way, and proceed with
the distillation as described in the kjeldahl method. The reagents
should be tested by blank experiments.
=194. The Gunning Moist Combustion Process.=—The modification proposed
by Gunning was based upon the observation that in the ordinary kjeldahl
process the excess of sulfur trioxid in the beginning of the operation
soon escapes or unites with water in a form not easily decomposed.[165]
During the progress of the combustion the acid diminishes in strength
until it is below the concentration represented by the formula H₂SO₄,
and in this diluted condition the oxidation takes place more slowly.
Gunning proposes to avoid this difficulty by mixing potassium sulfate
with the sulfuric acid. This salt forms with the sulfuric acid, acid
salts which, by heating, lose water easier than acid and as is well
known, they not only act as decomposing and oxidizing media as well as
sulfuric acid, but even in a higher degree, resembling the action of
sulfuric acid at high temperatures and under pressure.
By heating this mixture of sulfuric acid and potassium sulfate with
organic matters in an open vessel, not only the water originally
present, but that which is formed during the oxidation is driven off
without loss of acid. For this reason instead of the oxidizing mixture
becoming weaker, the acid becomes stronger, the boiling-point rises and
this, combined with the fluidity of the mass favors the decomposition
and oxidation of the organic matter in a constantly increasing ratio.
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