A century of science in America : $b with special reference to the American Journal of Science, 1818-1918
History
A century of science in America : $b with special reference to the American Journal of Science, 1818-1918
American journal of science; Science -- United States -- History
In some cases isomorphism takes place to a greater or less extent
between substances which are not chemically similar, and this brings
about a variation in composition which at times has caused confusion.
For instance, the mineral pyrrhotite has a composition which usually
varies between Fe_{7}S_{8} and Fe_{11}S_{12}, and both these formulas
have been assigned to it. It was recently shown by Allen, Crenshaw and
Johnston in the Journal (=33=, 169, 1912) that this is a case where the
compound FeS is capable of taking up various amounts of sulphur
isomorphously.
The idea of solid solution was advanced by van’t Hoff to explain the
crystallization of mixtures, including cases of evident isomorphism.
This view has been widely accepted, and it has been particularly useful
in cases where isomorphism is not evident. Solid solution between metals
has been found to be exceedingly common, many alloys being of this
character. A case of this kind was observed by Cooke and described in
the Journal (=20=, 222, 1855). He prepared two well-crystallized
compounds of zinc and antimony to which he gave the formulas Zn_{3}Sb
and Zn_{2}Sb, but he observed that excellent crystals of each could be
obtained which varied largely in composition from these formulas. As the
two compounds were dissimilar in their formulas and crystalline forms,
Cooke assumed that isomorphism was impossible and concluded “that it is
due to an actual perturbation of the law of definite proportions,
produced by the influence of mass.” We should now regard this as a case
of solid solution.
_A Lack of Confidence in Avogadro’s Principle._—One reason why chemists
were so slow in arriving at the correct atomic weights and formulas was
a partial loss of confidence in Avogadro’s principle. About 1826 the
young French chemist Dumas devised an excellent method for the
determination of vapor densities at high temperatures, and his results
and those of others showed some discrepancies in the expected densities.
For example, the vapor density of sulphur was found to be about three
times too great, that of phosphorus twice too great, that of mercury
vapor and that of ammonium chloride only about half large enough to
correspond to the values expected from analogy and other considerations.
Thus, one volume of oxygen with two volumes of hydrogen make two volumes
of steam, but only one third of a volume of sulphur vapor was found to
unite with two volumes of hydrogen to make two volumes of hydrogen
sulphide. Berzelius saw clearly that the results pointed to the
existence of such molecules as S_{6}, P_{4}, and Hg_{1}, but it was not
generally realized in those days that Avogadro’s rule is fundamentally
reliable, and Berzelius himself appears to have lost confidence in it on
account of these complications, for he did not apply Avogadro’s
principle to decisions about atomic weights, except in the cases of
substances gaseous at ordinary temperatures.
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