History, Modern -- 19th century; Nineteenth century
considered essential; Graham, however, showed that there exist three
series of salts—one set derived from P2O5,3H2O, one from P2O5,2H2O,
and a third from P2O5,H2O. His way of stating the fact was that water
could play the part of a base; for example, the ordinary phosphate
of commerce possessed, according to him, the formula P2O5,2Na2O,H2O,
two-thirds of the “water of constitution” being replaced by oxide of
sodium. Liebig, then professor at Giessen (1803–1873), founded on these
and on similar observations of his own the doctrine of poly-basic
acids—acids in which one, two, three, or more atoms of hydrogen
were replaceable by metals. Thus, instead of writing, as Graham did,
P2O5,2Na2O,H2O, he wrote, PO4Na2H; and for orthophosphoric acid
PO4H3. The group of atoms (PO4), therefore, existed throughout the
whole series of orthophosphates, and could exist in combination with
hydrogen, with hydrogen and metals, or with metals alone. Similarly
the group (P2O7) was characteristic of pyrophosphates and (PO3) of
metaphosphates, for P2O5,2H2O=(P2O7)H4; and P2O5,H2O=2(PO3)H.
The first clear ideas of the structure of the molecule were, however,
gained from the study of the compounds of carbon. It was difficult to
apply the dualistic theory to them. For few of them are electrolytes,
and therefore their products of electrolysis, being non-existent,
could not be classified. Nevertheless, Gay-Lussac regarded alcohol,
C2H6O, as a compound of C2H4, ethylene, and H2O, water; and oxalic
acid (anhydrous), C2O3, as one of CO2 with CO. The discovery of
“isomeric compounds,” _i.e._, of compounds which possess the same
ultimate formula and yet differ entirely in their properties,
forced upon chemists the necessity of attending to the structure of
the molecule; for only by such a supposition could the difference
between two isomeric bodies be explained. In 1823 Liebig discovered
that silver fulminate and silver cyanate both possessed the empirical
formula AgCNO; in 1825 this was followed by the discovery by Faraday
that oil gas contains a hydrocarbon identical in composition with
ethylene, C2H4, yet differing from it in properties; and in 1829
Wöhler, professor in Göttingen (1800–1882), discovered that urea, a
constituent of urine, could be produced by heating ammonium cyanate,
NH4CNO, a substance of the same formula. It therefore became clear that
the identity of a compound must depend on some other cause than its
ultimate composition.
Public-domain text, read in full here on John Shaqi.
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