Since the date mentioned the principal improvements in the process
have been in changing the composition of the copper solution in order
to render it more stable, which has been accomplished by varying the
proportions of copper sulfate, alkali and tartaric acid. For the better
keeping of the solution the method of preserving the copper sulfate
and the alkaline tartrates in separate flasks and only mixing them
at the time of use has been found very efficacious.[76] For testing
for the end of the reaction by means of an acetic acid solution of
potassium ferrocyanid the filtering tube suggested by the author, the
use of which will be described further on, has proved quite useful.
Pavy has suggested that by the addition of ammonia to the copper
solution the precipitated suboxid may be kept in solution and the end
of the reaction thus easily distinguished by the disappearance of the
blue color.[77] Allen has improved on this method by covering the hot
mixture with a layer of paraffin oil whereby any oxidation of the
suboxid is prevented.[78]
The introduction and development of the gravimetric process depending
on securing the reduced copper oxid in a metallic state as developed by
Allihn, Soxhlet, and others, completes the resumé of this brief sketch
of the rise and development of the process.
=114. Action of Alkaline Copper Solution on Dextrose.=—The action to
which dextrose and other reducing sugars are subjected in the presence
of a hot alkaline copper solution is two-fold in its nature. In the
first place there is an oxidation of the sugar which is transformed
into tartronic, formic and oxalic acids, the two latter in very small
quantities. At the same time another part of the sugar is attacked
directly by the alkali and changed to complex products among which
have been detected lactic, oxyphenic and oxalic acids, also two bodies
isomeric with dioxyphenolpropionic acid. When the sugar is in large
excess melassic and glucic acids have also been detected. The glucic
acid may be regarded as being formed by simple dehydration but becomes
at once resolved into pyrocatechin and gluconic acid according to
the reaction C₁₂H₁₈O₉ = C₆H₆O₂ + C₅H₁₂O₇. The gluconic acid also is
decomposed and gives birth to lactic and glyceric acids according to
the formula C₆H₁₂O₇ = C₃H₆O₃ + C₃H₆O₄. The glyceric acid also in the
presence of a base is changed into lactic and oxalic acids. Between
lactic acid and pyrocatechin, existing in a free state, there is
produced a double reciprocal etherification in virtue of which there
arise two ethers isomeric with hydrocaffeic acid, C₉H₁₀O₄. One of these
bodies is an acid and corresponds to the constitution
CH₃
/
O ── CH
/ \
C₆H₄ CO₂H (2)
\
OH (2)
and the other is of an alcoholic nature corresponding to the formula
CO₂ ── CHOH ── CH₃ (1)
/
C₆H₄
\
OH₂ (2)
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