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Discovering Diverse Content Through
Random Scribd Documents
 Ni =
59(Cu)
Copper. Zinc. Gallium. Germanium. Arsenic. Selenium. Bromine.
5 — —
Cu = 63.6 Zn = 65.4 Ga = 70.0 Ge = 72.3 As = 75.0 Se = 79.0 Br = 79.95
Ruthenium.
Ru = 101.7

{
Rhodium.
Krypton. Rubidium. Strontium. Yttrium. Zirconium. Niobium. Molybdenum.
6 — Rh = 103.0
Kr=81.8 Rb = 85.4 Sr = 87.6 Y = 89.0 Zr = 90.6 Nb = 94.0 Mo = 96.0
Palladium.
Pd =
106.5(Ag)
Silver.
Cadmium. Indium. Tin. Antimony. Tellurium. Iodine.
7 — Ag = —
Cd = 112.4 In = 114.0 Sn = 119.0 Sb = 120.0 Te = 127 I = 127
107.9
Xenon. Cæsium.
Barium. Lanthanum. Cerium.
8 Xe = Cs = — — — —
Ba = 137.4 La = 139 Ce = 140
128 132.2
9 — — — — — — — — —
Osmium.
Os = 191

{
Iridium.
Ytterbium. Tantalum. Tungsten.
10 — — — — — Ir = 193
Yb = 173 Ta = 183.0 W = 184
Platinum.
Pt =
194.9(Au)
Gold.
Mercury. Thallium. Lead. Bismuth.
11 — Au = — — —
Hg = 200.0 Tl = 204.1 Pb = 206.9 Bi = 208
197.2
Radium. Thorium. Uranium.
12 — — — — — —
Rd = 224 Th = 232 U = 239

The periodic law, in the words of its author, is the “direct outcome of the stock of
generalisations of established facts which had been accumulated by the end of the
decade 1860–1870.” It is founded wholly on experiment, and is as much the embodiment
of fact as are the laws of chemical combination. It was based upon the adoption of the
definite numerical values of the atomic weights, as indicated by Cannizzaro, as a
consequence of the hypothesis of Avogadro, and upon the assumption that the relations
between the atomic weights of analogous elements must be governed by a general law.
The application of the periodic law immediately led to the re-determination of certain
atomic weights and to the correction of their assumed atomic values. At the time of its
enunciation the determination of the valency of an element was purely empirical, with no
apparent necessary relation to that of other elements. We find now that the valency is a
matter of a priori knowledge, just as much as any other property of the element. The
amended values for the atomic weight and valency of a number of elements thus
demanded by the law have been confirmed by all the experimental criteria employed by
chemists. The generalisation further indicated the existence of new elements; it pointed
out their probable sources, and foretold their properties. Instances of this power of
divination in the law are to be seen, as already mentioned, in the discovery of gallium by
Lecoq de Boisbaudran, of scandium by Nilson, and of germanium by Winkler, the
existence and main properties of which were severally foretold by Mendeléeff in 1871.
 The promulgation of the law was heralded as a proof of the validity of the conception
of a primordial matter. It was held that it can find a rational explanation only in the idea
of unity in the formative material. But its author would not admit that his generalisation
had any relation to the Pythagorean hypothesis:

The periodic law, based as it is on the solid and wholesome ground of

experimental research, has been evolved independently of any conception as to
the nature of the elements. It does not in the least originate in the idea of an
unique matter, and it has no historical connection with that relic of the torments
of classical thought; and therefore it affords no more indication of the unity of
matter or of the compound nature of the elements than do the laws of
Avogadro, and Gerhardt, or the law of specific heats, or even the conclusions of
spectrum analysis. None of the advocates of a unique matter has ever tried to
explain the law from the standpoint of ideas taken from a remote antiquity,
when it was found convenient to admit the existence of many gods—and of a
unique matter.

The reader who desires a fuller exposition of the principles of the periodic law must
be referred to special treatises on the subject, or to the larger manuals on general
chemistry. It must, however, be stated that, while many facts discovered since the
original promulgation of the principle and since its development by Lothar Meyer,
Carnelley, Thomsen, and others, are consistent with the law, other facts, some of which
were known before 1870, are apparently out of harmony with it, or at all events await a
fuller interpretation. For example, tellurium is not in its proper place in the scheme if its
atomic weight, 127.5, has been correctly ascertained. Cobalt (58.97) and nickel (58.68)
have atomic weights so closely accordant that their properties and those of their
corresponding compounds should be very similar, and, in fact, almost identical; but such
is not the case. Indeed, it has been said, no prevision of the periodic law would have led
to the discovery of nickel. Similar considerations apply to manganese, chromium, and
iron; the atomic weights of these elements are less widely different than the differences
in their properties and the divergence in their chemical relationships would seem to
require. The relative positions of argon and potassium are also not consistent with the
law. There are difficulties, too, connected with what we know at present concerning the
atomic weights of the so-called rare earth metals. In spite, however, of these seeming
anomalies, it can hardly be doubted that the periodic law is as much the expression of a
natural law as is the law of gravitation; although it is possible, and indeed probable, that,
as we now define it, it is only the first approximation to the truth, and that, as our
knowledge becomes more precise, Mendeléeff’s classification, in its present form, will
require modification and extension, just as Mendeléeff’s own scheme may be said to be a
modification and extension of the attempts at the rational classification of the chemical
elements made by his predecessors.
 Dmitri Ivanowitsch Mendeléeff.

Dmitri Ivanowitsch Mendeléeff, with whose name this fruitful generalisation is

indissolubly connected, was born February 7, 1834 (N.S.), at Tobolsk, in Siberia, and was
the fourteenth and youngest child of Ivan Mendeléeff, the Director of the gymnasium at
that place. Soon after the birth of Dmitri his father became blind, and the family were
practically dependent upon the mother, Maria Dmitrievna Mendeleeva, who established a
glass works near Tobolsk, on the profits of which she brought up and educated her large
family. At the age of fifteen Mendeléeff was taken by his mother to St. Petersburg, and
began the study of natural science at the Physico-Mathematical Faculty of the Institute.
After serving as a science master at Simferopol in the Crimea and at Odessa, in 1856 he
became a privat-docent in the University; then, following a short period of study in
France and Germany, he returned to St. Petersburg, and in 1866 he was made Professor
of General Chemistry in the University. His reputation mainly rests upon his contributions
to chemical philosophy and physical chemistry, notably on specific volumes, on critical
temperatures, on the thermal expansion of liquids, on the nature of solutions, on the
elasticity of gases, and the origin and nature of petroleum. He died on January 31, 1907.
 CHAPTER VII

Valency

C
hemical formulæ, from the time of Berzelius onwards, have
been regarded as rational expressions—that is, they serve
to represent the relations and analogies of the substance
they are employed to designate, and indicate in the simplest and at
the same time the most comprehensive manner the chemical
changes in which the substances take part. In the words of
Gerhardt, those formulæ are “the best that make evident the
greatest number of such relations and analogies,” and that serve to
express the greatest number of the chemical changes in which they
are concerned.

In such concrete expressions of chemical change it was

frequently observed that a definite group of some or all of the
constituent elements of the substance hung together, as it were, and
passed, apparently unchanged, into the products of its
transformation. These groups were not necessarily radicals in the
sense in which Liebig and Wöhler used the term; to Gerhardt and to
Kekulé they were simply residues, remaining unattacked in a
chemical metamorphosis, and passing as such into the products of
the change. They might or might not be capable of isolation as
definite entities. Thus, for example, we may represent the
composition of the following sulphur compounds so as to show that
they all contain the group SO2, or sulphuryl:
 Sulphuryl chloride. Chlorosulphonic acid.

Sulphuryl Leaden chamber Sulphuric acid.

nitryl chloride. crystals.

These formulæ serve to show how the several substances are

mutually related, and that they may be derived from one another by
the substitution of atoms of chlorine for hydroxyl (OH), or nitryl
(NO2), or vice versa.
It was pointed out in 1851 by Williamson, and subsequently by
Gerhardt, that these groups are characterised by differences in their
power of combining with or replacing atoms of hydrogen, or of
groups or elements which, like chlorine, are chemically equivalent to
hydrogen. Such a radical or residue as ethyl (C2H5) is chemically
equivalent to one atom of hydrogen, as is shown when we compare
the formula for ether, as established by Williamson, with that of
ordinary alcohol:

Alcohol. Ether.

Sulphuryl, SO2, is chemically equivalento two atoms of hydrogen;

phosphoryl, PO, as suggested by Odling, to three atoms of
hydrogen. Gerhardt therefore proposed to designate these and
similar groups as monatomic, diatomic, triatomic, according to their
respective hydrogen-replacing power.
This conception of the definite atom-fixing or replacing power of
groups or compound radicals was extended by Frankland, in 1852,
so as to include the simple radical—that is, the elements. In the
memoir in which he announced the existence of the organometallic
compounds he pointed out that the elements may be classified
according to their combining power, or, as he expressed it, according
as “their affinities are best satisfied.” This idea was independently
developed by Couper and Kekulé in 1858; it is from that period that
the definite introduction of the conception of atomicity, atomic-value,
or valency, into chemical doctrine may be said to date.
The memoir in Liebig’s Annalen der Chemie und Pharmacie, in
which Kekulé announced his views, deals particularly with the
tetravalency of carbon and the doctrine of linking of atoms in terms
of their valency. As formulated by Kekulé and as subsequently
developed in his famous text-book, this doctrine exercised an
immediate effect on the progress of the chemistry of carbon
compounds. Like every fruitful hypothesis, it stimulated inquiry, and
brought out analogies; and the more it was applied the more
apparent became its suggestiveness and utility. The scope of
chemical formulæ was greatly extended. Rational formulæ grew into
dissected or constitutional formulæ; and on the system of
constitutional formulæ have been grafted successive attempts to
elucidate the manner in which the constituents of a molecule are
grouped and held together. It is interesting to note that the
proximate effect of the theory of chemical structure which grew out
of Kekulé’s doctrine was to assimilate what was sound in the
seemingly antagonistic theories of types and radicals. As a mode of
exposition, Kekulé used models to illustrate the manner in which the
affinity-values of compounds are satisfied; these were not intended
to represent the actual spatial distribution of the atoms in a
molecule, but they nevertheless familiarised the mind with the idea
first clearly recognised by Wollaston and Berzelius that this is the
ultimate aim of chemistry. It was probably their use, either actually
or by visualisation, that led Kekulé in 1865 to his theory of the
constitution of benzene, as developed in his paper on the
constitution of the aromatic compounds—a theory no less fruitful in
its consequences than that of the tetravalency of carbon and of the
linkage of atoms. Such models, too, in the hands of Van ’t Hoff,
subsequently served to elucidate the connection between optical
characters and crystalline form, and to explain the isomerism of
certain organic substances.
Kekulé was of opinion that the valency, or affinity-value, of an
element was a definite and invariable quantity—a fundamental
property of the atom as immutable as its atomic weight. Many facts
appear to show that such is not the case. Thus phosphorus and
nitrogen are sometimes trivalent and at other times pentavalent; tin,
in certain of its compounds, is divalent; in others, tetravalent.
Sulphur may be a dyad, a tetrad, or a hexad. It will be seen that the
valency of these particular elements varies by two units: this was at
one time held to be a natural law, and the various elements were
divided by Frankland into the two main groups of (1) perissads, or
elements of odd atomic value, and (2) artiads, or elements of even
atomic value. Experience has demonstrated that a rigid classification
on this basis is not possible. Many instances are known of elements
not only varying in valency by two units, but even by one unit. Thus
nitrogen, which is usually a perissad, is apparently an artiad in nitric
oxide and in gaseous nitrogen peroxide. Roscoe has shown that
uranium and tungsten, originally regarded as artiads, form
pentachlorides.
To what the difference in the affinity-value of an element is due,
and why different elements should manifest different values, is at
present unknown. Valency, like other properties, appears to be a
periodic function of atomic weight; from the behaviour of such
analogous compounds as phosphorus pentafluoride, phosphorus
pentachloride, phosphorus pentabromide, it seems, too, to be
related to the weights of the atoms in combination. Further, it would
appear that the mutual affinities of substances vary with
temperature—i.e., with the energy imparted to their molecules;
numerous instances appear to indicate that the atom-fixing power of
an element decreases when it is strongly heated—that is, when the
internal energy imparted to its combinations exceeds a certain
limiting value. Van ’t Hoff has attempted a mechanical explanation of
valency depending on the shape of the atoms, as affected by
variation in their vibratory motions resulting from differences of
temperature. Helmholtz suggested that the different charges of
electricity associated with the atoms may determine their affinity-
values—that, for example, a monad carries a single charge, a dyad
two, a triad three charges. Many considerations go to show that the
affinity-value of an element is not capable of definite numerical
expression in the sense which the doctrine of valency as generally
understood implies, and that the variations are not of the per saltum
character assumed by saying that the affinity-value is sometimes 1,
sometimes 2, at other times 3, and so on. When we have apparently
satisfied the accepted atomic value of an element by allocating to it
what we regard as the necessary complement of atoms of other
bodies, it is frequently evident that the capacity for combination of
the whole molecule is not satisfied. Many apparently saturated
molecules have the power of combining with other equally saturated
molecules. Sulphur trioxide (SO3) and barium monoxide (BaO) would
appear each to have their affinity-values satisfied; nevertheless they
combine with great readiness to form barium sulphate, BaSO4.
 CHAPTER VIII

The Chemistry of Aromatic Compounds

T
he suggestions of Couper and Kekulé that an explanation of the
properties of chemical compounds should be sought in the
nature and mutual affinities of their constituent elements
rather than of their radicals were not wholly accepted at the time
they were first made. Speculative ideas have to justify themselves by
facts. The value of an hypothesis depends upon its usefulness and
expediency, and on its power of indicating the lines of future inquiry.
How far it is inductively sound and deductively useful is a matter for
individual judgment. Consequently the tendency to pass from purely
rational and constitutional formulæ to formulæ which sought to
symbolise the inner structure—the very skeleton, as it were—of a
molecule, was resisted for a time, and by no one more strongly than
by Kolbe.

Kolbe’s attitude to the new doctrine may be said to have had its
justification in his own work. His remarkable prediction, based on
considerations which had nothing in common with Kekulé’s doctrine,
of the existence of the secondary and tertiary alcohols, so soon to
be confirmed by Friedel’s discovery of secondary propyl alcohol, and
by Butlerow’s isolation of tertiary butyl alcohol, served to retard the
general adoption of Kekulé’s views by showing that apparently they
were no more fruitful in suggestiveness than those they were
intended to supplant. But it was exactly in their suggestiveness with
regard to the development of isomerism that structural formulæ
based upon valency were gradually found to be most useful. It was
perceived that it was now possible not only to foretell the existence
of isomers, but to determine their number, and to some extent to
forecast their properties and modes of decomposition. Cayley, for
example, calculated the number of possible isomers of the
hydrocarbons of the generic formula CnH2n+2 up to C6H14 all those
that theory predicted have been discovered. In no single case have
more been obtained than the number indicated by theory. The
accumulated weight of this and similar testimony ultimately
established the doctrine of chemical structure on a firm basis.
This conception received a great extension as the result of
Kekulé’s application of his ideas to the explanation of the chemical
constitution of the group of substances of vegetable origin—
consisting of essential oils, balsams, resins, and their products,
which, on account of their characteristic odours, were collectively
known to the older chemists as the aromatic compounds. Some of
these, like oil of bitter almonds, gum benzoin, coumarin, oil of
wintergreen, oil of anise, oil of cinnamon, oil of cumin, balsam of
tolu, phenol, and certain of their derivatives, such as benzene,
aniline, salicylic acid, cinnamic acid, toluene, cymene, had already
been investigated with important theoretical results; but as a class
they had received far less attention than the derivatives of the great
group of homologous radicals of which methyl is the initial member.
Of course it was part of the doctrine of Liebig—the discoverer of
benzoyl—that the aromatic compounds also contained specific
radicals; but the relation of these compounds to those we now call
aliphatic (fatty) compounds was not understood, although certain
analogies were recognised.
In 1866 Kekulé drew attention to the following significant
peculiarities of the aromatic compounds: (1) All aromatic
compounds, even the simplest, are comparatively richer in carbon
than the corresponding class of fatty (aliphatic) compounds; (2)
among the aromatic substances, as among fatty compounds,
numerous homologous compounds exist; (3) the simplest aromatic
substances contain at least six atoms of carbon; (4) all
decomposition products of aromatic substances show a certain
family resemblance; the main product of the decomposition contains
at least six atoms of carbon—e.g., benzene C6H6, phenol C6H6O,
etc., which would seem to indicate that all aromatic substances
contain a nucleus or atomic grouping containing six carbon atoms.
Within this nucleus the carbon atoms are in closer connection or
denser combination, from which it follows that all aromatic
compounds are comparatively rich in carbon. More carbon atoms can
then be added to this nucleus according to the same laws that
govern the fatty compounds. In this way the existence of
homologous compounds may be explained.
On the assumption that carbon is tetravalent and that its valency
is constant, Kekulé showed how, by linking together six carbon
atoms by alternate single and double bonds, six affinity units may be
left free. If we assume that six carbon atoms are attached to one
another according to this law of symmetry, we obtain a group which,
regarded as an open chain, contains eight unsaturated units of
affinity:

By making the further assumption that the two carbon atoms at

the ends of the chain are linked together by one unit of affinity each,
a closed chain (a symmetrical ring) is obtained which now contains
six unsaturated units of affinity:

From this closed chain all the substances usually designated as

“aromatic compounds” are derived. In these a common nucleus may
be assumed: it is the closed chain C6A6, where A denotes an
unsaturated affinity. The six affinities of this nucleus may be satisfied
by six monovalent elements. They may also, wholly or in part, be
satisfied by one affinity of polyvalent elements, the latter necessarily
bringing with them other atoms into the compound, thus producing
one or more side chains, which in their turn may be lengthened by
the addition of other atoms.
If each of the free units is satisfied by an atom of hydrogen, we
obtain benzene, which, as Kekulé demonstrated, becomes the centre
round which the great group of aromatic compounds might be said
to revolve. Benzene was discovered by Faraday in 1825 among the
volatile liquids condensed from the oil-gas made by the Portable Gas
Company. It had already played a notable part in the development of
chemical theory in connection with the discovery of isomerism. It
was now to play a far more important rôle: to become, in fact, the
progenitor of a great family of substances, not only of theoretical
value, but of great economic importance.
The limits of this work preclude any attempt to trace in detail the
development of the conception with which Kekulé enriched science,
or to dilate upon the great extension of benzenoid or cyclic
chemistry which has resulted from it during the past forty years. It
has been said that Kekulé’s memoir on the benzene theory is the
most brilliant piece of scientific prediction to be found in the whole
range of organic chemistry. Of course, on its promulgation it had to
run the gauntlet of criticism; and an army of eager, active workers
was soon engaged in testing its sufficiency and in developing the
rich province which it first made known. As the facts multiplied,
other statical formulæ were suggested by Dewar, Ladenburg, and
Claus, but they have not proved more adequate to explain the facts
as these have become better understood. Observations which
seemed to contradict Kekulé’s theory, or which seemed to be
imperfectly explained by it, have, in the light of fuller knowledge,
been shown to be in harmony with it; and such additional proofs of
agreement have thereby served to strengthen its position. Its
capacity for development is, indeed, as in the case of every other
hypothesis of the first rank, one of its cardinal qualities. It
adequately explains the constitution of great numbers of derivatives
whose analogies and relations, apart from it, would have remained
obscure and in many cases unintelligible. The symmetrical
distribution of the carbon and hydrogen atoms in the benzene
molecule, assumed by Kekulé on indirect grounds, has been
established by the independent investigations of Ladenburg and
others, and its ring structure has been demonstrated by Baeyer and
Perkin. Purely physical evidence, based upon its thermo-chemical
and optical characters can be adduced in its support. Determinations
of the molecular volume and magnetic rotation of its compounds
further serve to substantiate it.
 August Kekulé von Stradonitz.

Friedrich August Kekulé was born at Darmstadt on

September 7, 1829. After passing through the gymnasium of his
native town, he entered, in 1847, the University of Giessen, with the
intention of becoming an architect. Attracted by Liebig’s teaching, he
turned to chemistry, and worked with Will on amyl sulphuric acid and
its salts. In 1851 he went to Paris, heard Dumas’s lectures, and
formed a friendship with Gerhardt, whose Traité de Chimie
Organique largely moulded his views. He became an assistant to Von
Planta, occupying himself with the chemistry of the alkaloids.
Subsequently he came to London, worked under Stenhouse, and
made the acquaintance of Williamson, then in the full vigour of his
scientific activity. Here he discovered thioacetic acid. It was at this
time, also, that his ideas with regard to structural chemistry began
to take shape. Returning to Germany, he attached himself to the
University of Heidelberg as a privat-docent, and had for a pupil
Baeyer, who took up the study of the organo-arsenic compounds. In
1858 he published his memorable paper “On the Constitution and
Metamorphoses of Chemical Compounds and on the Chemical
Nature of Carbon,” in which he developed his views on the linking of
atoms, out of which has grown our system of constitutional
formulæ. The immediate result of this celebrated memoir was a call
to the chemical chair of the University of Ghent, where Kekulé had
among other students Baeyer, Hübner, Körner, Ladenburg,
Linnemann, and Dewar. Here he remained nine years, and here he
published his classical Lehrbuch der Organischen Chemie. The years
he spent in Ghent were the most productive time of his career, and it
was there that he developed his benzene theory—a conception as
fruitful as that of his doctrine of atom-linking. In 1867 Kekulé was
called to Bonn to take charge of the newly erected laboratory which
Hofmann had designed. Although he continued to work, mostly in
collaboration with his pupils, among whom may be named Anschütz,
Bernthsen, Thorpe, Carnelley, Claisen, Dittmar, Franchimont, Van ’t
Hoff, Japp, Schultz, Wallach, and Zincke, his health after 1876 began
to fail. He died on July 13, 1896.

* * * * *
Of course no statical formula can be the ultimate representation
of the constitution of benzene. However convenient and suggestive
such a formula may be, it can be only a transitional phase in its
complete chemical and physical history. Kekulé was early conscious
of this fact, and suggested a dynamical hypothesis based upon a
mechanical conception of valency. This he imagined might represent
the number of contacts with other atoms which a vibrating atom
experienced in the unit of time. Two atoms of tetravalent carbon,
each linked by one combining unit, will experience four oscillations,
striking each other and three other atoms in the unit of time, while
the monovalent hydrogen atom makes only one oscillation. The
doubly linked carbon will collide with its neighbouring atom twice,
and also with two other atoms within the same period. The
assumption that the carbon atom has a more rapid motion than the
hydrogen atom is, however, not warranted by the kinetic theory.
Other dynamic formulæ have been proposed by Knorr and by Collie.
Collie and Baly have further suggested that the absorption bands of
benzene observed in the ultra violet of its spectrum point to
synchronous oscillations of its molecule, due to dynamic changes in
the making and breaking of the links between the several pairs of
the carbon atoms, setting up vibrations in the benzene ring
comparable with those of an elastic ring in the act of expanding and
contracting.

* * * * *
The large group of the essential oils, containing hydrocarbons
similar to oil of turpentine, and classed under the generic term of
terpenes, might, from their origin and mode of occurrence, be
expected to be allied in constitution to the aromatic compounds; and
such is found to be the case. The terpenes are isomeric
hydrocarbons of the formula C10H16. They are found sometimes
singly, at other times mixed, in a great variety of plants, associated
with sesquiterpenes C15H24, and oxygenated substances, such as
camphor, borneol, menthol, etc., some of which have long been
known and valued for their medicinal properties and technical
applications. The elucidation of their constitution has taxed the skill
of many workers during the past thirty years; but, thanks to the
labours of Wallach, Baeyer, Perkin, Tiemann, Bredt, Komppa, and
others, an insight has been gained into their nature and analogies.
They are apparently all cyclic compounds with certain attributes
which connect them with hydrocarbons of the aliphatic series.
Pinene, the characteristic constituent of oil of turpentine, obtained
by distilling the resinous exudations of many species of pines, exists
in two modifications, distinguished by differences in optical activity,
known respectively as australene, found in American, Russian, and
Swedish turpentine, and terebenthene, found mainly in French
turpentine. It would seem from their empirical formulæ, as well as
from their association in nature, that the terpenes and camphor,
which Dumas first showed to have the composition C10H16O, should
be closely allied in constitution, and that it ought to be readily
possible to effect their mutual transformation. The constitution of
camphor was long one of the standing problems of organic
chemistry, and dozens of formulæ have been suggested at various
times during the last twenty years in explanation of its structure.
That it contained a benzene nucleus seemed to be proved by the
ease with which it yielded toluene, cymene, and other benzene
homologues. The first real insight into its structure was gained when
Bredt ascertained the constitution of camphoronic acid, C6H11
(CO2H)4—a product, together with camphoric acid, of the oxidation
of camphor—which he found broke up into trimethylsuccinic acid and
isobutyric acid, and the structure of which was established by Perkin
and J. F. Thorpe.
The result of the Japanese monopoly has been to greatly
enhance the price of natural camphor; during the last ten years it
has practically trebled. This has naturally stimulated endeavours to
prepare this substance by synthetical means. Artificial camphor is
now made from pinene by transforming the hydrocarbon into bornyl
chloride by the action of hydrochloric acid. From this camphene is
prepared; by treatment with glacial acetic acid it forms isobornyl
acetate. On hydrolysis this is transformed into isoborneol, which by
oxidation yields camphor, differing from the naturally occurring
variety only in the fact that it is optically inactive. All so-called
aromatic compounds are not necessarily cyclic systems, for it has
been recognised within the past few years that some of the most
valuable natural perfumes, such as that of the rose, lavender, and
orange blossom, lemon-grass, geranium, ylang-ylang, neroli, etc.,
owe their characteristic aroma to the presence of terpenes and
camphors, which are not strictly benzenoid or cyclic compounds, but
“ruptured rings” behaving like open-chain or aliphatic substances. To
judge from past experience, it may confidently be stated that, now
the constitution of these substances is understood, their synthetical
preparation on an industrial scale is practicable. The discovery by
Cahours in 1844 that oil of wintergreen is substantially methyl
salicylate led to its artificial production from synthetically prepared
salicylic acid. Sir William Perkin in 1868 effected the synthesis of
coumarin, the aromatic principle in woodruff and hay. Fittig and
Mielck in 1869 synthesised heliotropin, and in 1871 Tiemann and
Haarmann obtained vanillin, the characteristic aromatic body in the
vanilla pod, by synthetic means, and established its manufacture on
a commercial scale. The chemical nature of the characteristic
odoriferous substances in oil of cumin, anise, rue, cinnamon,
heliotrope, jasmine, violet, parsley, etc., has now been established
and some of them are made industrially. The artificial essence of
violets known as ionone, prepared by Tiemann in 1893, and now
made commercially, is similar but not identical in structure with the
true perfume—irone. What is known as artificial musk is a trinitro-
butyl toluol. Artificial orange-flower oil is a methyl ester of anthranilic
acid.
In Vol. I. a short account has been given of the early history of
the large and important group of vegetable products known as the
alkaloids. Many of these have long been valued on account of their
powerful physiological action. As they all contain nitrogen and are
generally basic, they were regarded by Berzelius, and subsequently
by Liebig and Hofmann, as akin to ammonia in constitution, and
were classed as amines. The first experimental evidence of their
nature was obtained by Gerhardt, who found that, when strychnine
and certain of the alkaloids belonging to the quinine group are
treated with potash, an oil was obtained which he termed quinoline,
and which was recognised by Hofmann as identical with a substance
obtained in 1834 from coal-tar by Runge, and at that time known as
leucol. By other modes of treatment certain alkaloids—e.g., nicotine
and conine—are found to yield pyridine, a basic substance found by
Anderson, in 1846, in the fœtid liquor obtained by distilling bones,
and since found in coal-tar. Others of them—e.g., papaverine,
narcotine, etc.—yield isoquinoline, an oil also discovered in coal-tar,
by Hoogewerff, and Van Dorp, in 1885. These three substances—
quinoline, isoquinoline, and pyridine—constitute so many nuclei in
the constitution of a large number of alkaloids. Pyridine resembles
benzene in being a cyclic compound, consisting of five carbon atoms
and one nitrogen atom. Quinoline stands to pyridine in much the
same relation that naphthalene stands to benzene. It can be
obtained synthetically, as first shown by Koenigs and Skraup, and
subsequently by Doebner and Von Miller, from benzene derivatives.
Isoquinoline, isomeric with quinoline, differs from that substance
in the position of the nitrogen atom. It, too, has been synthetically
prepared from benzene derivatives in a number of ways.
Among the naturally occurring pyridine alkaloids may be named
piperine, found in black pepper, and conine, the poisonous principle
of hemlock (conium maculatum). The latter alkaloid was prepared
synthetically by Ladenburg in 1886; as first obtained it differed from
the naturally occurring product, which is dextro-rotatory, in being
optically inactive. Ladenburg surmised that the synthetic preparation
stood to the naturally occurring compound in the same relation that
racemic acid stood to tartaric acid, and that, by treatment in the
manner employed by Pasteur, the racemic modification of conine
might be separated into its dextro- and lævo-constituents. This was
found to be the case; but the separated dextro component was now
found to be distinctly more optically active than the pure, natural
variety. It was, in fact, an isomeric modification—iso-conine. By
heating this to 300° it was transformed into ordinary conine,
identical in all respects with the natural alkaloid. Ladenburg has also
effected the synthesis of piperine by condensing piperidine and
piperinic acid.
Nicotine, the alkaloid of tobacco, was discovered by Posselt and
Reimann in 1828. Its constitution was first ascertained by Pinner,
and it was synthetically obtained by Amé Pictet, in 1904, as an
inactive substance, capable of being resolved by the crystallisation of
its tartrates into a dextro- and lævo-modification, the latter of which
was identical with that found in the tobacco leaf.
Atropine and hyoscyamine—the poisonous principles of
belladonna and henbane—are isomeric alkaloids, the former of which
is optically inactive, and the latter is lævo-rotatory. Atropine is, in
fact, the racemic modification. The constitution of both alkaloids is
known, and their synthesis is now possible.
The successive steps may be thus indicated:
1. Synthesis of glycerin (Faraday, Kolbe, Melsens, Boerhave,
Friedel, and Silva).
2. Glycerin to glutaric acid (Berthelot and De Luca, Cahours and
Hofmann, Erlenmeyer, Lermantoff, and Markownikoff).
3. Glutaric acid to suberone (Brown and Walker, Boussingault).
4. Suberone to tropidine (Willstätter).
5. Tropidine to tropine (Willstätter, Ladenburg).
6. Synthesis of tropic acid (Berthelot, Fittig and Tollens, Friedel,
Ladenburg, and Rügheimer).
7. Tropine and tropic acid: atropine (Ladenburg).
The alkaloid cocaïne, contained in the leaves of erythroxylon
coca and now employed as a local anæsthetic, was discovered by
Niemann in 1860. It has been shown to be closely related to
atropine in constitution, and has now been synthetically prepared in
the dextro-modification.
The alkaloids papaverine, narcotine, narceïne, contained in
opium, are derivatives of isoquinoline, as also is berberine, found in
the common barberry (berberis vulgaris). Papaverine, which occurs
in opium to the extent of about one per cent., was first isolated by
Merck in 1848. Its constitution has been established by Goldschmidt.
Narcotine is, next to morphine, the most abundant constituent of
opium. The study of the products of its hydrolysis and oxidation—
viz., opianic acid and cotarnine, both of which substances have long
been known—has indicated its probable structure. Narceïne is closely
allied to narcotine, and can, indeed, be obtained from it by
combining the latter alkaloid with methyl iodide and treating the
compound with caustic potash. The constitution of berberine, which
is one of the few coloured vegeto-alkaloids known, has been worked
out by Perkin. As yet nothing definite is known concerning the
structure of the most important and largest constituent of opium—
viz., morphine; or of its congeners codeïne and thebaine. Grimaux,
however, in 1881 converted morphine into codeïne by treatment with
methyl iodide and potash; hence the two alkaloids stand in a relation
somewhat similar to that in which narceïne stands to narcotine.
There is very little doubt that the three alkaloids are very closely
related, and that a knowledge of the constitution of one of them
would immediately elucidate the structure of the others. They are
probably phenanthrene derivatives.
Quinine and cinchonine, the most important of the cinchona
alkaloids, are quinoline compounds, and are closely related in
constitution. But the many attempts to unravel their structure have
yielded no definite results up to the present.
 CHAPTER IX

Stereo-Isomerism: Stereo-Chemistry

T
he first gropings in the search for light on the inner structure of
molecular groupings may be said to date from Biot’s work
on polarisation. In 1815 Biot, a pupil of Malus, made the
remarkable discovery that a number of naturally occurring organic
compounds—e.g., sugar, tartaric acid, oil of turpentine, camphor,
etc., are optically active—that is, rotate the plane of polarisation in
one direction or the other. The property had previously been
observed in quartz, and was assumed to be connected with the
crystalline character of that substance. Biot, however, pointed out
that the case of oil of turpentine which is a liquid, and the cases of
the other substances when in solution, showed that crystalline
character had no necessary connection with the phenomenon, but
that it must be dependent upon the internal or molecular
arrangement of the optically active substance.

In 1844 Mitscherlich, who first demonstrated the relation

between atomic constitution and crystalline form, drew attention to
the fact that the salts of the isomeric modifications of tartaric acid,
studied by Berzelius, although possessing the same chemical
composition, the same crystalline form, with the same angles, the
same double refraction, and therefore the same angles between
their optical axes, nevertheless behave quite differently as regards
their optical activity, solutions of the tartrates rotating the plane of
polarisation, whereas those of the racemates are inactive. In 1848
this remarkable circumstance engaged the attention of Louis Pasteur,
a young man who had just completed his course at the École
Normale in Paris, and was acting as assistant to Balard, the
discoverer of the element bromine. Pasteur, on examining the
crystals of the two forms of tartaric acid, and of some of their salts,
detected the presence, on some of them, of certain facets—so-called
hemihedral faces—which had hitherto been unrecognised, but were
similar to facets which Haüy had observed on quartz. Haüy had, in
fact, divided quartz crystals into two classes—right-handed and left-
handed, depending upon the side on which these facets occurred.
The forms were, as it is termed, enantiomorphous. Biot, moreover,
found that some quartz crystals, cut parallel to the axis, turned the
plane of polarisation to the right, whereas others turned it to the
left; and Herschel suggested that the phenomena were probably
connected, and such was found to be the case.
Mindful of Herschel’s observation, Pasteur found that the crystals
of certain of the optically active tartrates showed hemihedral faces,
whereas those of the corresponding racemates showed no trace of
them. On recrystallising the racemates, however, it was noticed that
two sets of crystals were formed—enantiomorphic forms—the first
set of crystals having hemihedral forms on the right-hand side, and
the second set on the left-hand side. The forms, in fact, were so
related that one appeared, as if it were the image, as seen in a
mirror, of the other. When solutions of these crystals were examined,
one set was found to rotate to the right, the other to an equal
degree to the left. The dextro-rotatory salt yielded ordinary tartaric
acid; the corresponding lævo-rotatory acid was a hitherto unknown
modification: the two together, in equal proportions, constituted
racemic acid.
In 1863 Wislicenus published a remarkable memoir on the
synthesis of lactic acid. The acid in sour milk was discovered by
Scheele in 1780. In 1807 Berzelius discovered a similar acid, called
sarcolactic acid, in muscle juice; this was erroneously pronounced by
Liebig to be identical with that of sour milk. Other forms of lactic
acid were made known, the structural character of which was not to
be explained by current hypotheses. Wislicenus concluded that their
differences could be due only to different arrangements of their
atoms in space.
In 1874 the conception of atomic grouping received a
remarkable development by the publication of two memoirs—one by
Van ’t Hoff, and the other by Le Bel—which served to connect
molecular structure with optical activity. Confining their attention to
carbon compounds, they inferred that all optically active substances
contained at least one multivalent atom, united to other atoms or
groups, so as to form in space an unsymmetrical arrangement.
Van ’t Hoff regarded the carbon atom as occupying the centre of a
tetrahedron, to the summits of which its valencies were directed. If
different groupings are attached to these summits, the structure is
asymmetrical, and is optically active. The two forms of lactic acid, for
example, may be represented by the following space formulæ:

It will be seen from an inspection of the figures that the one is the
image-form of the other, and, no matter how they are turned, they
are not superposable; they are right- and left-handed, or, as it is
termed, enantiomorphs.
There is no fundamental distinction between the hypothesis of
Van ’t Hoff and Le Bel as to the effect of asymmetry on optical
behaviour. Le Bel regards the effect of asymmetry simply as a
necessary consequence of the presence of four dissimilar groupings,
and as independent of valency and the geometrical form of the
molecule.
 Jacobus Henricus Van ’t Hoff.

It was surmised by Pasteur that every liquid or solid in solution

showing optical activity, if crystallisable, would be found to manifest
hemihedral faces; but this has not been generally established.
Further, it does not always happen that an optically active substance
in solution is so when solid. Lastly, optical activity may be latent
even in asymmetric carbon compounds if dextro- or lævo-
modifications are present in equal proportions, as in racemic acid.
Such compounds are, in fact, termed “racemic,” or racemoids; and
they may be separated occasionally by crystallisation, as in Pasteur’s
method with the tartrates; or as shown by him by the action of the
racemoid upon another optically active substance; or, lastly, by
taking advantage of the specific action (specific assimilation) of
organisms—Pasteur’s so-called biochemical method.
It is a physiological fact of great interest that the behaviour of
enantiomorphs towards the animal organism is frequently markedly
different. Lævo-tartaric acid administered to guinea-pigs is found to
be twice as poisonous as the dextro-acid; dextro-asparagine
possesses a sweet taste, but lævo-asparagine is tasteless; lævo-
nicotine is more poisonous than the dextro-alkaloid.
The ferments known as enzymes are also found to possess the
power of selection, behaving differently towards the different
optically active modifications of the same substance. It is frequently
observed that an optically active substance may be rendered inactive
by the conversion of half the substance into its enantiomorph. This
operation was first performed by Pasteur, and may be brought about
by heating the substance, either alone or with water, under
pressure. Indeed, it is occasionally observed to take place at the
ordinary temperature (autoracemisation).
By the action of various reagents the derivatives of an optically
active substance are found not unfrequently to change the direction
of their optical activity. Indeed, by such means one enantiomorph
may be changed into another. Thus lævo-menthol may be converted
into the dextro-modification by treatment with sulphuric acid.
The rotatory power of a substance is frequently modified by the
character of its solvent, and varies with the temperature and
concentration of the solution. Landolt and Oudemans found that the
specific rotation of dilute solutions of tartrates and of salts of the
active alkaloids was independent of the nature of the base and acid
respectively present—a fact which finds its explanation in the theory
of electrolytic dissociation. It has been known for some years past
that the specific rotation of solutions of certain sugars changes with
time, being sometimes less and sometimes more than the initial
amount. This phenomenon is now known as multirotation, or
mutarotation. It seems to be connected with an alteration in the
configuration of the molecules.
There is a special case of stereo-isomerism, differing from that
of optical isomerism and of structural isomerism (with which we
have hitherto been alone concerned), which was predicted by Van ’t
Hoff in his remarkable work La Chimie dans l’Espace, published in
1877—noteworthy as being the first serious attempt to grapple with
the problem of spatial molecular grouping, foreshadowed by
Wollaston, Berzelius, and, indeed, all the early philosophic thinkers
who accepted the atomic theory. The special form of stereo-
isomerism now referred to, which has been more particularly
investigated by Wislicenus, is distinguished as geometrical
isomerism; not, perhaps, a sufficiently descriptive term, since,
comprehensively, all forms of isomerism are really cases of
geometrical isomerism. Instances of it are to be met with among the
isomeric acids existing as glycerides in certain fats, in cinnamic acid,
in stilbene and its derivatives, etc. It was first observed in maleic
and fumaric acids—isomeric acids of the empirical formula C2H2
(COOH)2, obtained by the distillation of malic acid, the characteristic
acid met with in the apple and other fruits and in certain other
vegetal products. These acids may be represented by the following
space formulæ:

Maleic acid. Fumaric acid.

which show no asymmetry, and hence no possibility of optical
activity or enantiomorphous modifications.
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