=256. The Oxidation Method.=—The removal of the reducing sugars may
be accomplished by oxidation instead of fermentation. The process
of analysis is in all respects similar to that described in the
foregoing paragraph, substituting oxidation for fermentation.[212]
For the oxidizing agent mercuric cyanid is preferred, and it is
conveniently prepared by dissolving 120 grams of mercuric cyanid and
an equal quantity of sodium hydroxid in water mixing the solutions
and completing the volume to one liter. If a precipitate be formed
in mixing the solutions it should be removed by filtering through
asbestos. For the polarization, ten grams of the sugars in 100 cubic
centimeters is a convenient quantity. Ten cubic centimeters of
this solution are placed in a flask of water marked at fifty cubic
centimeters, a sufficient quantity of the mercuric cyanid added to
remain in slight excess after the oxidation is finished (from twenty to
twenty-five cubic centimeters) and the mixture heated to the boiling
point for three minutes. The alkali, after cooling, is neutralized with
strong hydrochloric acid and the passing from alkalinity to acidity
will be indicated by a discharge of the brown color which is produced
by heating with the alkaline mercuric cyanid. The heating with the
mercury salt should be conducted in a well ventilated fume chamber.
The calculation of the results is conducted by means of the formulas
given in the preceding paragraph. In the original paper describing
this method, it was stated that its accuracy depended on the complete
oxidation of the reducing sugar in a manner leaving no optically active
products, and on the inactivity of the reagents used in respect to the
dextrin present. These two conditions are not rigidly fulfilled, as is
shown by Wilson.[213] According to his data maltose leaves an optically
active residue, which gives a somewhat greater right hand rotation than
is compensated for by the diminished rotation of the dextrin. Wilson,
however, confesses that the dextrin used contained reducing sugars,
which would not be the case had it been prepared by the process of
treating it with alkaline mercuric cyanid as above indicated. Upon the
whole, the oxidation of the reducing sugar by a mercury salt gives
results which, while not strictly accurate, are probably as reliable as
those afforded by fermentation. The author has attempted to supplant
both the oxidation and fermentation methods by removing the reducing
sugars with a precipitating reagent, such as phenylhydrazin, but the
methods are not sufficiently developed for publication.
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