History of Chemistry, Volume 2 (of 2): From 1850 to 1910Thorpe, T. E. (Thomas Edward)
History
History of Chemistry, Volume 2 (of 2): From 1850 to 1910
Thorpe, T. E. (Thomas Edward)
Chemistry -- History
The true significance of the hypotheses of Avogadro and Ampère was
long obscured, first on account of their imperfect appreciation by
the great leaders of chemical thought during the first half of the
nineteenth century—Berzelius, Gay Lussac, Wollaston, and Gmelin—and,
secondly, on account of the almost universal practice of deducing
atomic weights from purely chemical considerations of equivalence.
At the same time, it must be admitted that the recognition of the
value of these hypotheses was still further retarded by the seeming
anomalies which resulted from a more extended knowledge of the vapour
densities of elements and compounds. Thus the vapour densities of
mercury, sulphur, phosphorus, and arsenic, as ascertained by Dumas and
Mitscherlich, were plainly inconsistent with chemical analogies and
the law of Dulong and Petit. So, too, what appeared to be the vapour
densities of sal-ammoniac, phosphorus pentachloride, sulphuric acid,
calomel, and of other substances that might be mentioned, were not in
accordance with the values demanded by other well-ascertained facts.
By the middle of the nineteenth century the hypothesis of Avogadro
was practically forgotten and the law of volumes ignored. The atomic
weights of the elements, and the system of notation universally
employed in England and Germany, were based wholly upon equivalents.
The anomalies thus created were clearly pointed out by Gerhardt, and
subsequently by Laurent who showed how a consistent and harmonious
explanation of the facts could be reached by regarding as true
equivalents equal volumes—for example, of steam, ammonia, hydrogen
chloride, carbon dioxide, marsh gas, etc.; by assuming, in other words,
that equal numbers of the molecules of these various substances are
contained in equal volumes of the gases, as contended by Avogadro and
Ampère. The simplicity and consistency of the new notation gradually
won for it the adhesion of chemists. This adhesion was facilitated by
the memorable researches of Williamson on etherification, of Gerhardt
on the anhydrides, and by the work of Frankland on the radicals; and
it reached its logical conclusion when │Cannizzaro│—on the basis of
Avogadro’s hypothesis—discussed, in 1858, the true atomic weights of
the metallic elements as distinguished from their equivalent values.
In certain of its aspects the new table of atomic weights drawn up by
Cannizzaro resembled that originally proposed by Berzelius; but the
numbers adopted by the Swedish chemist were founded on no uniform or
rational basis, and were frequently inconsistent.
[Illustration: STANISLAO CANNIZZARO.]
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