The Principles of Chemistry, Volume IIMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume II
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
_Phosphorous acid_, PH_{3}O_{3}, is generally obtained from phosphorus
trichloride, PCl_{3}, by the action of water: PCl_{3} + 3H_{2}O = 3HCl +
PH_{3}O_{3}. Both acids formed are soluble in water, but are easily
separated, because hydrochloric acid is volatile whilst phosphorous acid
volatilises with difficulty, and if a small amount of water be originally
taken the hydrochloric acid nearly all passes off directly. Concentrated
solutions of phosphorous acid give crystals of H_{3}PO_{3}, which fuse at
70°, attract moisture from the air, and deliquesce when ignited, giving
phosphine and phosphoric acid,[22] and are oxidised into orthophosphoric
acid by many oxidising agents. In its salts only two hydrogen atoms are
replaced by metals (Würtz); the salts of the alkaline metals are soluble,
and give precipitates with salts of the majority of other metals.
[22] Phosphorous acid, when subjected to the action of nascent hydrogen
(zinc and sulphuric acid), evolves phosphine, and when boiled with
an excess of alkali it evolves hydrogen (PH_{3}O_{3} + 3KHO =
PK_{3}O_{4} + 2H_{2}O + H_{2}); owing to its liability to
oxidation, it is a reducing agent--for instance, it reduces cupric
chloride to cuprous chloride, and precipitates silver from the
nitrate and mercury from its salts.
These reactions are perhaps connected with the fact that in this
acid one atom of hydrogen should be considered as in the same
condition as in phosphuretted hydrogen, which is expressed by the
formula PHO(OH)_{2}, if we represent it as PH_{4}X, with the
substitution of two of the hydrogen atoms by oxygen and of HX by
two of hydroxyl. The direct passage of phosphorous chloride into
phosphorous acid would, however, indicate that all the three atoms
of hydrogen in it occur in the form of hydroxyl, because no
difference is known between the three atoms of chlorine in
PCl_{3}--they all react alike, as a rule. However, Menschutkin, by
acting on alcohol, C_{2}H_{5}OH, with phosphorous chloride,
obtained hydrochloric acid and a substance P(C_{2}H_{5}O)Cl_{2},
and from it by the action of bromine he obtained ethyl bromide,
C_{2}H_{5}Br, and a compound PBrOCl_{2}, which proves, to a
certain extent, the existence of a difference between the three
atoms of chlorine in phosphorous chloride. If we turn our
attention to the formation of phosphine by the ignition of
phosphorous acid, we see that 4PH_{3}O_{3} only evolve 3H in the
form of PH_{3}, and therefore the residue--that is,
3PH_{3}O_{4}--will still contain one hydrogen of the same nature
as in phosphine, because in 4PH_{3}O_{3} we should recognise four
such hydrogens as in phosphine. We arrive at the same conclusion
by examining the decomposition of hypophosphorous acid,
2PH_{3}O_{2} = PH_{3} + PH_{3}O_{4}.
Public-domain text, read in full here on John Shaqi.
Reviews
Reviews
No reviews yet
Be the first to share your thoughts on this work.
Elsewhere in the archive
Join the Discussion
Join the discussion
Sign in to leave a comment or review.
Sign InorCreate an account