Scientific American Supplement, No. 633, February 18, 1888Various
Science
Scientific American Supplement, No. 633, February 18, 1888
Various
Science -- Periodicals
More than one hypothesis has been proposed to account for these cases of
isomerism, but no one has shown itself to be entirely satisfactory.
Quite recently Johannes Wislicenus, Professor of Chemistry in the
University of Liepsic, has made what has the appearance of being an
important contribution toward the solution of the problem referred to.
The author shows that many of the facts known in regard to the relations
between maleic and fumaric acids, and the other substances which
furnish examples of "abnormal isomerism," may be explained by the aid of
an extension of the Le Bel-Van't Hoff hypothesis. It is difficult
without the aid of models to give a clear idea concerning the hypothesis
of Wislicenus, but some idea of it may be gained from the following. If
we suppose a carbon atom to exert its affinities in the directions of
the solid angles of a tetrahedron, as is done in the Le Bel-Van't Hoff
hypothesis, then, when two carbon atoms unite, as in ethane, the union
will be between two solid angles of two tetrahedrons. If the two carbon
atoms unite by the ethylene kind of union, the union will be along a
line corresponding to one of the edges of each tetrahedron. In the
former case, in which single union exists, the two parts of the molecule
represented by the two tetrahedrons can be supposed to be capable of
revolving around an axis either in the same direction or in opposite
directions. This axis corresponds to the straight line joining the two
carbon atoms. In the case in which double union exists no such
revolution is possible. Again, if, by addition to an unsaturated
compound like ethylene, a saturated compound is formed, the kind of
union between the carbon atoms is changed, and the possibility of
revolution of the two parts of the compound is given. Whether such
revolution take place or not will be determined largely by the structure
of the compound. The tendency will be for those parts of the molecule
which have the greatest specific affinity for one another to take those
positions in which they are nearest to one another. Thus, suppose that
chlorine is added to ethylene. By following the change on the model, it
is seen that in the resulting figure the two chlorine atoms in ethylene
chloride are situated at angles of the two tetrahedrons which are
nearest each other. But chlorine has a stronger affinity for hydrogen
than it has for chlorine, and therefore each chlorine atom would tend to
get as near a hydrogen atom as possible. This involves a partial
revolution of the two tetrahedrons in opposite directions around their
common axis. So also hydrogen would tend to take a position as near as
possible to hydroxyl and to carboxyl, while hydroxyl would avoid
hydroxyl, and carboxyl would avoid carboxyl. These views are suggested
as a result of a careful application of the original Le Bel-Van't Hoff
hypothesis, and are, of course, of little value unless they can be shown
to be in accordance with the facts.
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