A chemist when conducting a laboratory experiment dropped a glass flask
containing about 40 c.c. of diethyl sulphate, thereby spilling some over
his clothes. He went on working, and noticed burns after some time,
quickly followed by hoarseness and pain in the throat. He died of severe
inflammation of the lungs. A worker in another factory was dropping
diethyl sulphate and stirring it into an at first solid, and later
semi-liquid, mass for the purpose of ethylating a dye stuff. In doing
so he was exposed to fumes, and at the end of the work complained of
hoarseness and smarting of the eyes. He died of double pneumonia two days
later. Post mortem very severe corrosive action on the respiratory tract
was found, showing that the diethyl sulphuric acid had decomposed inside
the body and that nascent sulphuric acid had given rise to the severe
burns. The principal chemist who had superintended the process suffered
severely from hoarseness at night, but no serious consequences followed.
It is stated also that workmen in chemical factories coming into contact
with the fumes of diethyl sulphate ester suffer from eye affections.[3]
CHLORINE, CHLORIDE OF CALCIUM, AND CHLORATES
MANUFACTURE.—The older processes depend on the preparation of chlorine
and hydrochloric acid by an oxidation process in which the oxidising
agent is either a compound rich in oxygen—usually common manganese
dioxide (pyrolusite)—or the oxygen of the air in the presence of heated
copper chloride (as catalytic agent). The former (Weldon process) is
less used now than either the latter (Deacon process) or the electrolytic
manufacture of chlorine.
In the _Weldon process_ from the still liquors containing manganous
chloride the manganese peroxide is regenerated, and this so regenerated
Weldon mud, when mixed with fresh manganese dioxide, is used to initiate
the process. This is carried out according to the equations:
MnO₂ + 4HCl = MnCl₄ + 2H₂O
MnCl₄ = MnCl₂ + Cl₂.
[Illustration: FIG. 6.—Preparation of Chlorine—Diaphragm Method (_after
Ost_)]
Hydrochloric acid is first introduced into the chlorine still (vessels
about 3 m. in height, of Yorkshire flag or fireclay), next the Weldon
mud gradually, and finally steam to bring the whole to boiling; chlorine
comes off in a uniform stream. The manganous chloride still liquor is run
into settling tanks. The regeneration of the manganous chloride liquor
takes place in an oxidiser which consists of a vertical iron cylinder in
which air is blown into the heated mixture of manganous chloride and milk
of lime. The dark precipitate so formed, ‘Weldon mud,’ as described, is
used over again, while the calcium chloride liquor runs away.
The _Deacon process_ depends mainly on leading the stream of hydrochloric
acid gas evolved from a saltcake pot mixed with air and heated into a
tower containing broken bricks of the size of a nut saturated with
copper chloride. Chlorine is evolved according to the equation:
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