“PREPARATION OF ETHYLARSENOUS OXIDE—The compound was prepared by
treating sodium arsenite with ethyl chloride under pressure. The
resulting sodium salt of ethylarsenic acid was converted into the free
acid and reduced by sulfur dioxide. The ethylarsenous acid formed in
this way lost water and was thereby transformed into ethylarsenous
oxide. The reactions involved are as follows:
C₂H₅Cl + Na₃AsO₃ = C₂H₅AsO₃Na₂ + NaCl
C₂H₅AsO₃Na₂ + 2 HCl = C₂H₅AsO₃H₂ + 2 NaCl
C₂H₅AsO₃H₂ + SO₂ + H₂O = C₂H₅AsO₂H₂ + H₂SO₄
2C₂H₅AsO₂H₂ = (C₂H₅As)₂O + H₂O.
“The ethyl chloride used in the preparation was in part made in this
factory, and in part received from other sources. As ethyl chloride
is an important product used in peace time, it is not, therefore,
essentially a war product and its preparation was not described.
“In preparing the solution of sodium arsenite, one molecular weight
of arsenous oxide was dissolved in a solution containing 8 molecular
weights of sodium hydroxide. The solution of the base was prepared from
a 50 per cent solution of sodium hydroxide to which enough solid alkali
was added to make the solution a 55 per cent one. In one operation 660
kg. of arsenous oxide were used. For 100 parts of arsenous oxide, 130
parts of ethyl chloride were used, this being the theoretical amount of
the latter.
“The reaction was carried out in a steel autoclave of about 300 liters
capacity. The temperature was maintained at between 90° and 95°. The
ethyl chloride was pumped in, in 3 or 4 portions, and the pressure
in the autoclave was kept at from 10 to 15 atmospheres. The several
portions of ethyl chloride were introduced at intervals of about 1½
hrs. During the entire reaction, the contents of the autoclave were
vigorously stirred. After all the ethyl chloride had been added, the
material was stirred from 12 to 16 hrs., at the end of which time
the pressure had fallen to about 6 atmospheres. The excess of ethyl
chloride and the alcohol formed in the reaction were next distilled
off. At this point a sample of the solution was drawn off for testing.
This was done by determining the amount of arsenite present in the
solution. If not more than 20 per cent of sodium arsenite had not
reacted, the preparation was considered satisfactory. Water was then
added to the contents of the autoclave in sufficient amount to dissolve
the solid material. The product was next drawn over into a tank and
neutralized with sulfuric acid. It was then treated with sulfur dioxide
gas until there was an excess of the latter present. The mixture was
then heated to about 70° when the ethylarsenous oxide precipitated as
a heavy oil. This was readily separated and shipped without further
purification. The yield of ethylarsenous oxide, from arsenic oxide, was
from 80 to 82 per cent of a product which contained about 93 per cent
of pure ethylarsenous oxide.
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