The original mixture used by Gunning had the following composition;
_viz._, one part of potassium sulfate and two parts of strong sulfuric
acid. The substances are united by heat and, on cooling, are in a
semi-solid state, melting, however, easily on the application of heat
and assuming a condition to be easily poured from vessel to vessel.
The quantity of the sample taken should vary in proportion to its
nitrogenous content from half a gram to a gram. The combustion takes
place in flasks entirely similar to those used in the ordinary kjeldahl
process. In the case of liquids, they should be previously evaporated
to dryness before the addition of the oxidizing mixture. At the
beginning of the combustion there is a violent foaming attended with
evolution of some acid and much water, and afterwards of stronger acid.
This loss of acid should not be allowed to go far enough to produce
too great concentration of the material in the flask. One of the best
ways to avoid it is to place a funnel in the flask covered with a
watch-glass which will permit of the condensation and return of the
escaping acid. As soon as the foaming ceases, the flame should be so
regulated as to permit of the volatilized acid being condensed upon the
sides of the flask. In the end a colorless mass is obtained in which no
metallic oxids are present, and this mass can at once be diluted with
water, treated with alkali, and distilled. According to the nature of
the substance from half an hour to an hour and a half are required for
the complete combustion.
_Modifications of the Gunning Method._—As in the case of the kjeldahl
method, numerous minor modifications of the gunning method have
been made, the most important of which relate to its application to
substances containing nitrates. In general the same processes are
employed in this case as with the kjeldahl method. One of the best
modifications consists in the use of the mixture of salicylic and
sulfuric acids followed by the addition of sodium thiosulfate or of
potassium sulfate or sulfid. These modifications will be given in
detail under the official methods.
=195. Reactions of the Gunning Process.=—The various reactions which
take place during the combustion according to the gunning method have
been tabulated by Van Slyke.[166]
The first reaction to take place is the union of sulfuric acid and
potassium sulfate to form potassium acid sulfate in accordance with the
following equation:
(1) K₂SO₄ + H₂SO₄ = 2KHSO₄.
When heated, the potassium acid sulfate decomposes, forming potassium
disulfate and water, thus:
(2) 2KHSO₄ = K₂S₂O₇ + H₂O.
The potassium disulfate at a higher temperature decomposes, forming
normal potassium sulfate and sulfur trioxid, thus:
(3) K₂S₂O₇ = K₂SO₄ + SO₃.
At a sufficiently high temperature the two preceding reactions may take
place in one, thus:
2KHSO₄ = K₂SO₄ + H₂O + SO₃.
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