The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
If a piece of phosphorus be dropped into a flask containing chlorine, it
burns when touched with a red-hot wire, and combines with the chlorine.
If the phosphorus be in excess, liquid _phosphorus trichloride_, PCl_{3},
is always formed, but if the chlorine be in excess the solid
pentachloride is obtained. The trichloride is generally prepared in the
following manner. Dry chlorine (passed through a series of Woulfe's
bottles containing sulphuric acid) is led into a retort containing sand
and phosphorus. The retort is heated, the phosphorus melts, spreads
through the sand, and gradually forms the trichloride, which distils over
into a receiver, where it condenses. _Phosphoric chloride_ or _phosphorus
pentachloride_, PCl_{5}, is prepared by passing dry chlorine into a
vessel containing phosphorus trichloride (purified by distillation).
Phosphorous chloride combines directly with oxygen, but more rapidly with
ozone or with the oxygen of potassium chlorate (3PCl_{3} + KClO_{3} =
3POCl_{3} + KCl), forming _phosphorus oxychloride_, POCl_{3} (Brodie).
This compound is also formed by the first action of water on phosphoric
chloride; for example, if two vessels, one containing phosphoric chloride
and the other water, are placed under a bell jar, after a certain time
the crystals of the chloride disappear and hydrochloric acid passes into
the water. The aqueous vapour acts on the pentachloride, and the
following reaction occurs: PCl_{5} + H_{2}O = POCl_{3} + 2HCl, the result
being that liquid phosphorus oxychloride is found in one vessel, and a
solution of hydrochloric acid in the other. However, an excess of water
directly transforms phosphoric chloride into orthophosphoric acid,
PCl_{5} + 4H_{2}O = PH_{3}O_{4} + 5HCl,[26] since POCl_{3} reacts with
water (3H_{2}O), forming 3HCl and phosphoric acid PO(OH)_{3}.
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