After cooling, the contents of the flask are diluted with water, the
green color giving place to a brown with a rise of temperature. After
cooling a second time the whole is brought into a distillation flask of
about three-quarters of a liter capacity and attached to a condenser
which ends in a vessel containing titrated sulfuric acid. About forty
cubic centimeters of sodium hydroxid solution of one and three-tenths
specific gravity are added and the stopper at once inserted to prevent
any loss of ammonia. To prevent bumping during the distillation some
zinc dust is added securing an evolution of hydrogen during the
progress of the distillation. In this case the bumping is prevented
until near the end of the operation when it begins anew, probably by
reason of the separation of solid sodium sulfate. After the end of
the distillation, the excess of acid remaining in the receiver is
determined by a set alkali solution and thus the quantity of ammonia
obtained easily calculated. Kjeldahl, however, preferred to titrate the
solution after adding potassium iodate and iodid, a mixture which in
the presence of a strong acid sets free a quantity of iodin equivalent
to the free acid present. The iodin thus set free is titrated by a set
solution of sodium thiosulfate using starch as an indicator. The merits
of this method are sharpness of the end reaction and the possibility of
using only a small quantity of the nitrogenous body for the combustion.
The sulfuric acid used in the receiver is made of the same strength as
the thiosulfate solution; _viz._, about one-twentieth normal. Thirty
cubic centimeters of this were found to be the proper amount for use
with substances taken in such quantities as to produce ammonia enough
to neutralize about half of it. The titration is carried on as follows:
A few crystals of potassium iodid are dissolved in the acid mixture
obtained after the distillation is completed, then a few drops of the
starch-paste and finally a few drops of a four per cent solution of
potassium iodate. The iodin set free is then oxidized by the addition
of the one-twentieth normal sodium thiosulfate solution until the blue
color disappears.
_Example_: Sulfuric acid used, 30 cc.
Equivalent to sodium thiosulfate, 30 cc.
Blank combustion required, 29.8 cc thiosulfate solution.
Combustion of 0.645 gram of barley 14.5 cc “ “
required, -------
Thiosulfate corresponding to barley, 15.3 cc.
In the computation it is more simple to multiply the corresponding
number of cubic centimeters of thiosulfate by seven, half the atomic
weight of nitrogen, and divide the product by the weight of the
substance taken, which will give the per cent of nitrogen therein.
15.3 × 7
Then ---------- × 100 = 1.66 = per cent of nitrogen in sample taken.
0.645
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