A more detailed description of the method of making the titration
follows: After the distillation is finished the condensing-tube is
rinsed with a little water, after which the sulfuric acid unneutralized
in the receiver is determined. It is advisable first to test the
reaction of the distillate with litmus paper before going any further;
for if at any time all the acid should be found neutralized it will
be necessary to add a sufficient quantity of one-twentieth normal
sulfuric acid before adding the potassium iodid, etc., otherwise the
determination will be irreparably lost. Add to the contents of the
flask ten cubic centimeters of the potassium iodid and two cubic
centimeters of the potassium iodate solutions, described further on,
and the sodium thiosulfate is then run in from a burette till the
fluid, which is constantly kept agitated by shaking the flask, shows
only a bare trace of yellow coloration from the iodin still present.
Starch solution is then added, and the blue color obtained is at once
removed by additional thiosulfate solution. When some experience has
been gained, the eye is able to discern, with great certainty, even the
slight coloration caused by only a small trace of free iodin.
In regard to the sensitiveness of the end reaction and the accuracy
of the result, this method of titration leaves nothing to be wished
for. The strength of the thiosulfate solution is determined in exactly
the same manner, and with starch as an indicator. For this purpose,
measure ten cubic centimeters of one-twentieth normal sulfuric acid
into an erlenmeyer, add 120 cubic centimeters of ammonia-free water,
ten cubic centimeters of potassium iodid solution, and two cubic
centimeters of iodate solution; add thiosulfate solution till the fluid
shows only the above-mentioned light yellow tint, then add starch,
and finally thiosulfate. In this way the strength of the thiosulfate
is ascertained, which of course must be occasionally re-determined,
under exactly the same conditions as with the nitrogen determinations
themselves, and every possible error is thereby excluded. That the
solution once decolorized within a short time again assumes a deep blue
color, is a matter of no concern, inasmuch as both solutions are added
in such a manner that the end reaction lies exactly at the point when
the starch iodid reaction distinctly disappears.
=180. Theory of the Reactions.=—As has been seen above the final
product of heating a nitrogenous organic compound with sulfuric acid
and an oxidizing body is ammonium sulfate. The various steps by which
this is obtained have been traced by Dafert:[150]
(1) The sulfuric acid abstracts from the organic matter the elements of
water:
(2) The sulfur dioxid produced by the action of the residual carbon on
sulfuric acid exercises a reducing effect on the nitrogenous bodies
present:
(3) From the nitrogenous bodies produced by the above reduction ammonia
is formed by the action of an oxidizing body:
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