NICOTINE yields half its nitrogen as
Ammonia 10·49
IV. Dr Guy, as well as others, have made researches, having for their
object the determination of the exact temperature at which the poisonous
alkaloids melt and sublime. A very minute speck of the substance is placed
on a porcelain plate or copper disc, and a square or oval of
microscope-covering glass is placed over it, supported by a thin ring of
glass or any other convenient substance.
Heat is then applied to the plate or copper, and the temperature, as
indicated by a thermometer at which the substance fuses or volatilises, is
carefully noted.
CANTHARIDINE sublimes as a white Fahr. Cent.
vapour without change of form or colour. 212° 100°
Sublime. Melt.
/----------\ /----------\
Sublime, melt and Fahr. Cent. Fahr. Cent.
MORPHINE } yield carbonaceous { 330° 165° 340° 171°
STRYCHNINE} residue. { 345° 174° 430° 224°
Melt. Sublime.
/----------\ /----------\
Fahr. Cent. Fahr. Cent.
ACONITINE } { 140° 60° 400° 204°
ATROPINE } Melt, change { 150° 66° 280° 138°
VERATRINE } colour, sublime, { 200° 93° 360° 182°
BRUCINE } and { 240° 116° 400° 204°
DIGITALIN } deposit carbon. { 310° 154° 310° 154°
PICROTOXIN} { 320° 160° 320° 160°
SOLANINE } { 420° 215° 420° 216°
_Selmi's method of extracting poisonous alkaloids in forensic
investigations._ The alcoholic extract of the viscera, acidified and
filtered, is evaporated at 65° C., the residue taken up with water,
filtered to separate fatty matters, and decoloured by means of basic
acetate of lead, leaving the solution in contact with the air for 24
hours. It is then filtered, the lead precipitated by means of sulphuretted
hydrogen, and the solution after concentration repeatedly extracted with
ether. The ethereal solution is then saturated with dry carbonic
anhydride, which generally causes a precipitate of minute drops adhering
to the sides of the vessel, and containing some of the alkaloids. The
ethereal solution is then poured into a clean vessel, mixed with about
half its volume of water, and a current of carbonic anhydride passed for
about twenty minutes, which may cause the precipitation of other alkaloids
not precipitated by dry carbonic anhydride. Usually the whole of the
alkaloids present in the ether are thrown down by these means, but if not,
the solution is dehydrated by agitation with Barium oxide, and then a
solution of tartaric acid in ether added to the clear liquid, taking great
care not to employ excess of acid. This throws down any alkaloid that may
remain. In order to extract any alkaloids that may still remain in the
viscera, they are mixed with Barium hydrate and a little water, and then
agitated with purified amylic alcohol; the alkaloids may subsequently be
extracted from the alcohol by agitation with very dilute sulphuric acid.
A knowledge of the different solubilities of the alkaloids will be found
an important auxiliary in their analysis. The following is a summary of
the relative solubility of the most important of them. The figures denote
the number of parts of the liquid required for their solution:--
_Absolute alcohol._--Strychnine insoluble; brucine soluble.
_Amylic alcohol._--Solanine (1061); digitalin sparingly soluble; morphine
(133); strychnine (122); veratrine, brucine, atropine, aconitine, and
picrotoxin, freely soluble.
_Benzol._--All the poisonous alkaloids, except solanine, are soluble in
benzol.
_Chloroform._--Solanine (50,000); morphine (6550); strychnine (8); the
rest freely soluble.
_Ether._--Solanine (9000); morphine (7725); strychnine (1400); aconitine
(777); brucine (440); veratrine (108); atropine, picrotoxin,[26] and
digitalin, very soluble.
[Footnote 26: Digitalin and picrotoxin, although not alkaloids, are
inserted in the above list, because they have a general similarity in
chemical properties to them; and for the convenience of the toxicologist.]
_Water_ (_cold_).--Strychnine (8333); veratrine (7860); morphine (4166);
aconitine (1783); solanine (1750); brucine (900); atropine (414);
picrotoxin (150); digitalin very soluble.
The principal Alkaloids and their Salts, in the state of powder, or with
'conia' and 'nicotia,' in the state of an oily looking liquid, may be thus
distinguished:--
1. _a._ The powder is treated with nitric acid:--It is coloured red;
probable presence of Brucia, Delphia, Morphia, or commercial Strychnia. If
the reddened acid becomes violet on the addition of 'protochloride of
tin,' it is BRUCIA; if it becomes black and carbonaceous, it is DELPHIA.
If the powder is fusible without decomposition, and strongly decomposes
iodic acid, it is MORPHIA; if it is not fusible without decomposition, and
does not decompose iodic acid, it is STRYCHNIA.
_b._ If instead of a red, the powder strikes a green colour with nitric
acid, it is SOLANIA; if it is insoluble in 'ether,' and not reddened by
'nitric acid,' it is EMETIA; if soluble in ether, not reddened by 'nitric
acid,' but melts and volatilises when heated, it is ATROPIA; if it is thus
affected by ether or nitric acid, but does not volatilise, it is VERATRIA.
(See 2, _below_.)
2. _a._ The powder, or (with 'conia and nicotia') concentrated liquor, is
treated with a drop or two of concentrated sulphuric acid:--A red colour
is produced; probable presence of Brucia, Nicotina, Salicine, or Veratria.
If the reddened mixture has at first a roseate hue, turning deep red on
the addition of nitric acid, it is BRUCIA; if the original substance
moistened with solution of potassa evolves the odour of tobacco, it
contains NICOTINE; if the red colour produced by the acid is permanent and
of an intense blood-hue, and the powder agglutinates into lumps like
resin, it is SALICINE; if the colour is at first yellowish, changing to
blood-red, and ultimately to crimson and violet, it is VERATRIA.
_b._ If instead of the substance being 'reddened' by strong sulphuric
acid, no particular action ensues in the cold, it contains either Conia or
Strychnia; if a small fragment of bichromate of potassa being now dropped
in, produces a rich violet colour, it is STRYCHNIA; if the original matter
on being heated, or treated with solution of potassa, evolves a
penetrating, disagreeable odour, somewhat analogous to that from
'hemlock,' or to a mixture of those from tobacco and mice, it is CONIA.
"_Reactions with ceroso-ceric oxide._ This oxide exhibits characteristic
colours with several alkaloids, especially with STRYCHNINE. When strong
sulphuric acid is poured upon strychnine, and then a small quantity of
ceroso-ceric oxide added, a fine blue colour is produced, similar to that
which strychnine exhibits with potassium bichromate, but much more
permanent. The blue colour gradually changes to cherry-red, and then
remains unaltered for several days. This reaction is capable of detecting
one part of strychnine in a million parts of liquid. BRUCINE similarly
treated acquires an orange-colour, gradually changing to yellow; MORPHINE,
olive-brown, finally brown; NARCOTINE, brown cherry red, finally wine-red;
CODEINE, olive-green, finally brown; QUININE, pale-yellow; CINCHONINE and
THEINE remain colourless; VERATRINE becomes reddish-brown; ATROPINE, dingy
yellowish-brown; SOLANINE, yellow at first, finally brownish; EMETINE,
brown; COLCHICINE, first green, then dirty brown; ANILINE, after a long
time, acquires a blue colour extending from the edges inwards; CONINE
becomes light-yellow. PIPERINE colours the sulphuric acid blood-red, and
is turned dark-brown, almost black by the cerium oxide" (Sonnenschein).
"_Reactions with picric acid._ This acid is a very good precipitant for
alkaloids, affording a very delicate test for many of them, and may
perhaps also serve for separating them one from another. The precipitation
takes place even in solutions containing a large excess of sulphuric
acid, and is sometimes complete. _Precipitated_ are, BRUCINE, STRYCHNINE,
VERATRINE, QUINIDINE, CINCHONINE, and most of the opium alkaloids; _not
precipitated_, MORPHINE, ATROPINE (English), PSEUDO-MORPHINE, CAFFEINE,
and all glucosides" (Hager).
The presence of one or more of the alkaloids being shown by any of the
preceding methods, a portion of the original clear solution or powder, or
of the precipitates or filtrates above referred to, must be treated with
their characteristic tests, as given under the individual notices of these
articles, so as to set at rest all doubt as to their identity. No single
test must ever be relied on as a positive proof. The presence of Brucia,
Morphia and Strychnia may be determined in substances which after being
mixed with the salts of these alkaloids have undergone the acetous,
vinous, or putrefactive fermentation, as shown by Orfila, MM. Larocque and
Thibierge, and many other eminent chemists and toxicologists, and
confirmed, in numerous cases, by our own experiments. Opium and morphia
may thus be readily detected in beer, wine, soup, and milk. A paper by
Professor DRAGENDORF in the 'American Chemist' for April, 1876, may be
consulted with advantage.
_Concluding Remarks._ It is a singular fact that none of the organic bases
found in plants have yet been formed artificially, although several
analogous substances have been thus produced. Closely allied to the
alkaloids there also exists an extensive series of neutral proximate
principles, which differ from those substances chiefly in the absence of
basic properties, and in most of them being destitute of nitrogen. They
are usually bitter, and, like the alkaloids, generally represent the
active properties of the plants in which they are found; whilst some of
them possess considerable medicinal energy. Of this kind are asparagin,
elaterin, gentianin, picrotoxin, salicin, &c. These two classes of bodies,
though actually distinct, are frequently confounded. See ALKALI, ORGANIC
BASES, POISONS, PROXIMATE PRINCIPLES, VEGETABLES, NOMENCLATURE, &c.; also
the individual alkaloids under their respective heads.
=ALKALOIDS OF ACONITE=. The nature of the active principle of aconite root
does not appear to have been satisfactorily determined. Messrs Groves,
Wright, and Williams contend that the _Aconitum napellus_ yields an active
crystalline alkaloid, which they distinguish as _Aconitine_, and to which
they assign the formula C_{33}H_{43}NO_{12}; they add that additionally
the root contains more or less of another active alkaloid, which they term
_Pseudaconitine_, and which is represented by the formula
C_{36}H_{49}NO_{11}; they also assert that the extract of the roots
contains varying quantities of certain decomposition products resulting
from the saponification of the above bases by the acids, which are
produced by the breaking up of part of the aconitine. The name of these
decomposition products is _Aconine_ and _Pseudaconine_. Of _Aconitum
ferox_ they report that it yields a comparatively large quantity of
_Pseudaconitine_ and a small quantity of _Aconitine_. They further affirm
that the so-called aconitine of commerce is a mixture of true aconitine
and pseudaconitine with variable quantities of their alteration products,
aconine and pseudaconine, and of certain amorphous unnamed alkaloids.
Messrs Paul and Kingzett contest the accuracy of these deductions, and
dispute the correctness of the formula given to aconitine. Dr Paul doubts
whether the alkaloid to which the active properties of the root are
ascribed has ever yet been obtained in an isolated condition. He thinks it
probable that the substance obtained from aconite root was to a great
extent a salt of an acid, like aconitic acid. For further information the
reader is referred to the 'Pharmaceutical Year Book' for 1873, 1874, 1875,
1876, and 1877.
=AL'KANET.= _Syn._ ANCHU'SA, L.; ORCANETTE, Fr.; ORKANET, Ger.;
OR'CHANET*, DYER'S AL'KANET, D. BU'GLOSS*. The _anchu'sa tincto''ria_
(Willd.; _lithosper'mum tincto''rium_--Linn.), a deciduous herbaceous
plant, with a perennial, dark blood-red root. _Hab._ Asia Minor, Greece,
Hungary, &c. It is also largely cultivated in the neighbourhood of
Montpellier. The dried root (ALKANET ROOT; RADIX ANCHUSÆ, R. A. TINCTORIÆ)
is chiefly imported from the Levant. It contains a beautiful blood-red
colour, which it freely gives out to oils, fats, wax, spirits, essences,
and similar substances, by simply infusing it in them, and is consequently
much employed to colour these articles. Wax tinged with it, and applied on
warm marble, stains it of a rich flesh-colour, which sinks deep into the
stone, and possesses considerable durability. Its spirituous tincture also
imparts a deep red to marble.
_Prop._, _&c._ The colouring matter of alkanet was regarded by Pelletier
as a fatty acid (ANCHUSIC ACID); but it has since been shown to be a
species of resin (ANCHUSINE, PSEUDO-ALKANNINE, P.-ALKANIUM). According to
Dr John, good alkanet root contains 5-1/2 per cent. of this substance.
Anchusine melts at 140° Fahr.; is scarcely soluble in water, to which it
only imparts a dirty red colour, but is very soluble in alcohol, oils, and
acetic acid. Alkalies turn it blue. It is found wholly in the root-bark.
In selecting this article, the smaller roots should therefore be chosen,
as they possess more bark than the larger ones, in proportion to their
weight. Exposure to ammoniacal fumes, or even handling it much with the
fingers, changes its red to a crimson or purplish hue.
_Uses_, _&c._ It is much employed by druggists and perfumers to colour
oils, lip-salves, plasters, pomatums, &c.; by varnish-makers, to tinge
their varnishes and lacquers; by statuaries to stain marble; by
dairy-farmers, to colour cheese; by wine-merchants and bottlers (in the
form of tincture), to stain beforehand the corks of their port-wine
bottles, in order to imitate the effects of age, and as colouring and
flavouring for factitious port wine; and by dyers, and others. A species
of crimson rouge was formerly prepared from it (hence its name).
=ALLANTO'IC ACID.= See ALLANTOIN.
=ALLAN'TOIN.= C_{8}H_{6}O_{6}N_{4}. _Syn._ ALLANTO'IC ACID*, AMNIOT'IC
A.[dagger] AM'NIC A.[dagger]; ALLANTOÏ'NA, L. A substance discovered by
Vauquelin and Buniva in what they imagined to be the liquor amnii of the
cow, and hence named by them amniotic acid. It was afterwards shown by
Dzondi and Lassaigne to exist in the fluid of the allantoïs, and not of
the amnios. It has since been produced artificially by Wöhler and Liebig.
_Prep._ 1. The allantoïc fluid of the f[oe]tal calf is evaporated to 1-4th
or 1-5th of its volume, and then set aside for some time. The crystals
thus obtained are purified by re-solution, digestion with animal charcoal,
and re-crystallisation.
2. (Wöhler and Liebig.) Uric acid, 1 part; is dissolved in water, 20
parts; and freshly precipitated and well-washed binoxide of lead is added
to the solution until the colour ceases to change; the liquid is next
filtered while hot, evaporated until a pellicle forms on the surface, and
then set aside to crystallise; the crystals being purified as before.
_Prop., &c._ Small, but very brilliant prismatic, transparent, colourless
crystals; tasteless; neutral; soluble in 160 parts of cold water, and in
much less at 212°; nitric acid converts it into ALLANTURIC ACID; oil of
vitriol resolves it into ammonia, carbonic acid, and carbonic oxide; hot
concentrated solutions of the caustic alkalies change it into ammonia and
oxalic acid.
=ALLANTOX'ICUM.= [L.] _Syn._ ALLANTOX'ICUM, L. (prim., Gr.). The poison
developed, during putrefaction, in sausages made of blood, liver, &c. "It
often proves speedily fatal." (Kraus.)
=ALLGEMEINE FLUSSTINCTUR= (Sulzberger, Salzungen). For the relief of a
number of diseases, among which are cholera and sea-sickness. Aloes, 1
part; spirit of wine, 2 parts. (Spau.)
=ALLIA'CEOUS= (-sh'us). _Syn._ ALLIA'CEUS, L.; ALLIACÉ, AILIACÉ, Fr.;
KNOBLAUCHARTIG, &c., Ger. Garlick-like; an epithet applied to substances
having the odour or properties of garlic or onions.
=Alliaceous Plants.= Chives, garlic, leeks, onions, rocambole, shallots,
&c.
=ALLIGA'TION.= _Syn._ ALLIGA'TIO, L. In _commercial arithmetic_, a rule
for ascertaining the price or value of mixtures, and for determining the
proportions of the ingredients that must be taken to produce mixtures of
any given price, value, or strength. The first is called ALLIGATION
ME'DIAL; the second, ALLIGATION ALTERN'ATE. Its principles and
applications are explained under MIXTURES (Arithmetic of).
=ALLOP'ATHY.= _Syn._ ALLOPA'THIA, L. (from [Greek: allos], _other_,
_different_, and [Greek: pathos], _affection_ or _disease_, Gr.);
ALLOPATHIE, Fr. In _medicine_, the method of curing disease by the use of
remedies which tend to produce a condition of the system, either differing
from, opposed to, or incompatible with the condition believed to be
essential to the disease it is sought to cure. It is commonly employed to
distinguish the ordinary system of medical practice from hom[oe]opathy
(which see). Hence (an) ALLOP'ATHIST, and the corresponding adjective
ALLOPATH'IC (_allopath'icus_, L.).
=ALLOT'ROPY.= _Syn._ ALLOT'ROPISM; ALLOTRO'PIA, ALLOTROPIS'MUS, L.
Literally, a difference in character; another form of the same substance.
In _chemistry_, a term invented, by Berzelius, to express the state or
condition, or the change of character, assumed by certain substances at
different temperatures, or under different treatment, whilst their nature
and composition continue the same. It more particularly relates to colour,
hardness, solubility, texture, &c. Boron, carbon, silicon, iron, sulphur,
and phosphorus, afford striking examples of the changes here referred to.
=ALLOX'ANTIN.= C_{8}H_{4}N_{4}O_{7}.3H_{2}O. A crystallisable substance,
first obtained by Dr Prout from uric acid.
_Prep._ 1. Uric acid, 1 part; is boiled in water, 32 parts; dilute nitric
acid being added until solution is complete; the resulting liquid is
evaporated to 2/3rds its volume, and then set aside for 10 or 12 hours;
the crystals, which are deposited, are purified by re-solution and
crystallisation.
2. Sulphuretted hydrogen gas is passed, in a full stream, through a
moderately strong aqueous solution of alloxan, in the cold. The
alloxantin, which is deposited as a crystalline mass, is purified by
draining, cautious washing with cold water, re-solution in boiling water,
and re-crystallisation. The impure mother-liquor from which crystals of
alloxan have separated, if diluted with water, may be used for this
purpose.
_Prop., &c._ Crystals, small colourless, transparent, four-sided, oblique
rhombic prisms; scarcely soluble in cold water; solution reddens litmus;
with baryta water it gives a characteristic violet-coloured precipitate,
which disappears on heating; and with nitrate of silver a black
precipitate of that metal; the crystals are reddened by ammoniacal
vapours.
=ALLOY'.= _Syn._ ALLIAGE, Fr.; LEGIRUNG, VERMISCHUNG DURCH SCHMELZEN, Ger.
In _coinage_, a compound of the precious metals with another, or others,
of less value; also the least valuable metal, or metals, in such
compounds. In _chemistry_ and _metallurgy_, combinations of the metals
with each other usually obtained by fusion. When mercury is one of
the component metals, the compound is termed an AMALGAM.
_Prep., &c._ No General rules can be given for this purpose. Alloys of
metals differing greatly in fusibility, are commonly made by adding the
more fusible one, either in the melted state, or in small portions at a
time, to the other melted, or heated to the lowest possible temperature at
which a perfect union will take place between them. The mixture is usually
affected under a flux, or some material that will promote liquefaction,
and prevent volatilisation and unnecessary exposure to the air. Thus, in
melting lead and tin together, for solder, resin, or tallow is thrown upon
the surface; in tinning copper, the surface is rubbed with sal ammoniac;
and in combining some metals, powdered charcoal is used for the same
purpose. Quicksilver combines with many metals in the cold, forming
AMALGAMS.
_Comp._ The following _Table_ exhibits the composition of the more
important compounds of this class:--
_Table of the principal Alloys._[27]