The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
In order to show the general method for the preparation of acid
chloranhydrides, we will take that of acetic acid, CH_{3}·COOH, as an
example. Phosphorus pentachloride is placed in a glass retort, and acetic
acid poured over it; hydrochloric acid is then evolved, and the substance
distilling over directly after is a very volatile liquid, boiling at 50°,
and having all the properties of the chloranhydrides. With water it forms
hydrochloric and acetic acids. The reaction here taking place may be
explained thus: the substitution of the oxygen taken from the acetic acid
(from its carboxyl) by two atoms of chlorine from the PCl_{5} should be
as follows: CH_{3}·COOH + PCl_{5} = CH_{3}·COHCl_{2} + POCl_{3}. But the
compound CH_{3}·COHCl_{2} does not exist in a free state (because it
would indicate the possibility of the formation of compounds of the type
CX_{6}, and carbon only gives those of the type CX_{4}); it therefore
splits up into HCl and the chloranhydride CH_{3}·COCl. The general scheme
for the reaction of phosphorus pentachloride with hydrates ROH is exactly
the same as with water; namely, ROH with PCl_{5}, gives POCl_{3} + HCl +
RCl--that is a chloranhydride.[28 bis]
[28 bis] This reaction indeed proceeds very easily and completely with
a number of hydroxides, if they do not react on hydrochloric acid
and phosphorus oxychloride, which is the case when they have
alkaline properties. When the hydroxide is bibasic and is present
in excess, it not unfrequently happens that the elements of water
are taken up: R(OH)_{2} + PCl_{5} = RO + 2HCl + POCl_{3}. The
anhydride RO may then be converted into chloranhydride, RO +
PCl_{5} = RCl_{2} + POCl_{3}--that is, phosphorus pentachloride
brings about the substitution of O by Cl_{2}. Thus carbonyl
chloride, COCl_{2}, boron chloride, 2BCl_{3}, and succinic
chloride, C_{4}H_{4}O_{2}Cl_{2}, &c., are respectively obtained by
the action of phosphoric chloride on carbonic, boric, and succinic
anhydrides. Phosphorus pentachloride reacts in a similar manner on
the aldehydes, RCHO, forming RCHCl_{2}, and on the chloranhydrides
themselves--for example, with acetic chloride, CH_{3}.COCl (when
heated in a closed tube), it forms a substance having the
composition CH_{3}CCl_{3}.
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