Chapter XXI: Part V: More or Less Volatile Poisonous Substances Capable of Being (1)

SEPARATED BY DISTILLATION FROM NEUTRAL OR ACID LIQUIDS.

HYDROCARBONS--CAMPHOR--ALCOHOL--AMYL NITRITE--ETHER--CHLOROFORM AND
OTHER ANÆSTHETICS--CHLORAL--CARBON DISULPHIDE--CARBOLIC
ACID--NITRO-BENZENE--PRUSSIC ACID--PHOSPHORUS.

I.--Hydrocarbons.

1. PETROLEUM.

§ 137. Petroleum is a general term for a mixture of hydrocarbons of
the paraffin series, which are found naturally in certain parts of
the world, and are in commerce under liquid and solid forms of
various density. Crude petroleum is not imported into England, the
original substance having previously undergone more or less
rectification. The lighter and more volatile portions are known
under the name of cymogene, rhigolene, gasolene, and naphtha.

§ 138. =Cymogene= has a specific gravity of ·590, and boils at 0°.
It has been employed in refrigerating machines. It appears to
consist chiefly of butane (C₄H₁₀).

§ 139. =Rhigolene= is now used in medicine in the form of spray to
produce local anæsthesia. It boils at 18°, and has a density of
·650.

§ 140. =Gasolene= has a density of ·680-·688; it has received
technical applications in the “naphthalising” of air and gas.

§ 141. =Benzoline= (=mineral naphtha=, =petroleum naphtha=,
=petroleum spirit=, =petroleum ether=) is a mixture of the lighter
series of hydro-carbons; the greater part consists of heptane, and
there is also a considerable quantity of pentane (C₇H₁₆) present.
The specific gravity varies from ·69 to ·74. It is very inflammable,
and is used in sponge lamps, and also as a solvent for gutta-percha,
naphthalene, paraffin, wax, and many other bodies. By the practical
chemist it is much employed.

The similarity of the terms _benzoline_ and _benzene_ has caused
benzoline to be often confused with _benzol_ or _benzene_, the
leading constituent of coal-tar naphtha (C₆H₆). Mr Allen[132] gives
in the following table a summary of the chief points of distinction,
both between petroleum naphtha, shale naphtha, and coal-tar naphtha.
The table is founded upon the examination of particular samples, and
commercial samples may present a few minor deviations.

[132] _Commercial Organic Analysis_, vol. ii. p. 31.

TABLE OF THE VARIETIES OF NAPHTHA.

+---------------------+----------------------+----------------------+
| Petroleum Naphtha. | Shale Naphtha. | Coal-tar Naphtha. |
+---------------------+----------------------+----------------------+
|Contains at least 75 |Contains at least 60 |Consists almost wholly|
|per cent. of heptane,|to 70 per cent. of |of benzene, C₆H₆, and |
|C₇H₁₆, and other |heptylene, C₇H₁₄, and |other homologous |
|hydrocarbons of the |other hydrocarbons of |hydrocarbons, with a |
|marsh gas or paraffin|the olefin series; the|small percentage of |
|series; the remainder|remainder paraffins. |light hydrocarbons in |
|apparently olefins, |No trace of benzene or|some samples. |
|C_{n}H_{2n}, with |its homologues. | |
|distinct traces of | | |
|benzene and its | | |
|homologues. | | |
| | | |
|Specific gravity at |Specific gravity at |Specific gravity ·876.|
|15°, ·600. |15°, ·718. | |
| | | |
|Distils between 65° |Distils between 65° |Distils between 80° |
|and 100°. |and 100°. |and 120°. |
| | | |
|Dissolves coal-tar |Behaves similarly to |Readily dissolves |
|pitch, but slightly; |petroleum naphtha with|pitch, forming a deep |
|liquid, but little |regard to the solution|brown solution. |
|coloured even after |of pitch. | |
|prolonged contact. | | |
| | | |
|On shaking three |When treated with |The liquids form a |
|measures of the |fused carbolic acid |homogeneous mixture |
|sample with one |crystals, the liquids |when treated with |
|measure of fused |mix perfectly. |fused carbolic acid |
|crystals of absolute | |crystals. |
|carbolic acid, no | | |
|solution. Liquids not| | |
|miscible. | | |
| | | |
|Combines with 10 per |Combines with upwards |Combines slowly with |
|cent. of its weight |of 90 per cent. of its|30-40 per cent. of its|
|of bromine in the |weight of bromine. |weight of bromine. |
|cold. | | |
+---------------------+----------------------+----------------------+

§ 142. =Paraffin Oil= (or =kerosine, mineral oil, photogen=, &c.) is
the chief product resulting from the distillation of American
petroleum--the usual specific gravity is about ·802--it is a mixture
of hydrocarbons of the paraffin series. It should be free from the
more volatile constituents, and hence should not take fire when a
flame is applied near the surface of the cold liquid.

§ 143. =Effects of Petroleum.=--Since we have here to deal with a
commercial substance of such different degrees of purity, and
various samples of which are composed of such various proportions of
different hydrocarbons, its action can only be stated in very
general terms. Eulenberg[133] has experimented with the lighter
products obtained from the distillation of Canadian petroleum. This
contained sulphur products, and was extremely poisonous, the vapour
killing a rabbit in a short time, with previous insensibility and
convulsions. The autopsy showed a thin extravasation of blood on the
surface of each of the bulbi, much coagulated blood in the heart,
congested lungs, and a bloody mucus covering the tracheal mucous
membrane. An experiment made on a cat with the lighter petroleum
(which had no excess of sulphur) in the state of vapour, showed that
it was an anæsthetic, the anæsthesia being accompanied by
convulsions, which towards the end were tetanic and violent. The
evaporation of 1·5 grm. in a close chamber killed the animal in
three hours. The lungs were found congested, but little else was
remarkable. Much petroleum vapour is breathed in certain factories,
especially those in which petroleum is refined.[134] From this cause
there have been rather frequent toxic symptoms among the workmen.
Eulenberg[135] describes the symptoms as follows:--A person, after
breathing an overdose of the vapour, becomes very pale, the lips are
livid, the respiration slow, the heart’s action weak and scarcely to
be felt. If he does not immediately go into the open air away from
the poisonous vapour, these symptoms may pass on to insensibility,
convulsions, and death. It often occasions a condition of the
voluntary muscles similar to that induced by drunkenness, and on
recovery the patient is troubled by singing in the ears and noises
in the head. The smell and taste of the poison may remain for a long
time.

[133] _Gewerbe-Hygiene._

[134] The vapour most likely to rise at the ordinary temperature, and mix with the atmosphere, is that of the lighter series, from cymogene to benzoline.

[135] _Op. cit._

§ 144. Poisoning by taking light petroleum into the stomach is not
common. In a case recorded by Taylor,[136] a woman, for the purpose
of suicide, swallowed a pint of petroleum, There followed a slight
pain in the stomach, and a little febrile disturbance, and a
powerful smell of petroleum remained about the body for six days;
but she completely recovered. In August 1870 a sea-captain drank a
quantity of paraffin, that is, lighting petroleum, and died in a few
hours in an unconscious state. A child, 2 years old, was brought to
King’s College Hospital within ten minutes after taking a
teaspoonful of paraffin. It was semi-comatose and pale, with
contracted pupils; there was no vomiting or purging. Emetics of
sulphate of zinc were administered, and the child recovered in
twenty-four hours. In another case treated at the same hospital, a
child had swallowed an unknown quantity of paraffin. It fell into a
comatose state, which simulated tubercular meningitis, and lasted
for nearly three weeks.[137] In a case recorded by Mr Robert
Smith,[138] a child, 4 years of age, had swallowed an unknown
quantity of paraffin. A few minutes afterwards, the symptoms
commenced; they were those of suffocation, with a constant cough;
there was no expectoration; the tongue, gums, and cheeks were
blanched and swollen where the fluid touched them; recovery
followed. A woman, aged 32, who had taken a quarter of a pint of
paraffin, was found unconscious and very cold; the stomach-pump was
used, and she recovered.[139] Hence it is tolerably certain, from
the above instances, that should a case of petroleum poisoning
occur, the expert will not have to deal with infinitesimal
quantities; but while the odour of the oil will probably be
distinctly perceptible, there will be also a sufficient amount
obtained either from matters vomited, or the contents of the
stomach, &c., so that no difficulty will be experienced in
identifying it.

[136] _Poisons_, p. 656

[137] _Brit. Med. Journ._, Sept. 16, 1876, p. 365.

[138] _Brit. Med. Journ._, Oct. 14, 1876.

[139] _Pharm. Journ._, Feb. 12, 1875; also for other cases see _Brit. Med. Journ._, Nov. 4, 1876; and Köhler’s _Physiol. Therap._, p. 437.

§ 145. In order to separate petroleum from any liquid, the
substances under examination must be carefully distilled in the
manner recommended under “_Ether_.” The lighter petroleums will
distil by the aid of a water-bath; but the heavier require a
stronger heat; redistillation of the distillate may be necessary.
The odour of the liquid, its inflammable character, and its other
properties, will be sufficient for identification.

2. COAL-TAR-NAPHTHA--BENZENE.

§ 146. Coal-tar-naphtha in its crude state, is an extremely complex
liquid, of a most disagreeable smell. Much benzene (C₆H₆) is present
with higher homologues of the benzene series. Toluene (C₇H₈),
naphthalene (C₁₀H₈), hydrocarbons of the paraffin series,
especially hexane (C₆H₁₄), and hydrocarbons of the olefin series,
especially pentylene, hexylene, and heptylene (C₅H₁₀, C₆H₁₂ and
C₇H₁₄). Besides these, there are nitrogenised bases, such as
aniline, picoline, and pyridine; phenols, especially carbolic acid;
ammonia, ammonium sulphide, carbon disulphide, and probably other
sulphur compounds; acetylene and aceto-nitrile. By distillation and
fractional distillation are produced what are technically known
”_once run_” _naphtha_, _90 per cent. benzol_, _50 and 90 per cent.
benzol_,[140] _30 per cent. benzol_, _solvent naphtha_, and residue
known as “_last runnings_.”

[140] Or 50/90 benzol, this indicates that 50 per cent. distils over below 100°; and 40, making in all 90, below 120°.

§ 147. Taylor[141] records a case in which a boy, aged 12, swallowed
about 3 ozs. of naphtha, the kind usually sold for burning in lamps,
and died with symptoms of narcotic poisoning. The child, after
taking it, ran about in wild delirium, he then sank into a state of
collapse, breathing stertorously, and the skin became cold and
clammy. On vomiting being excited, he rejected about two
tablespoonfuls of the naphtha, and recovered somewhat, but again
fell into collapse with great muscular relaxation. The breathing was
difficult; there were no convulsions; the eyes were fixed and
glassy, the pupils contracted; there was frothing at the mouth. In
spite of every effort to save him, he died in less than three hours
after taking the poison. The body, examined three days after death,
smelt strongly of naphtha, but the _post-mortem_ appearances were in
no way peculiar, save that the stomach contained a pint of
semi-fluid matter, from which a fluid, having the characteristics of
impure benzene, was separated.

[141] _Op. cit._, p. 657.

§ 148. The effects of the vapour of benzene have been studied by
Eulenberg in experiments on cats and rabbits, and there are also
available observations on men[142] who have been accidentally
exposed to its influence. From these sources of information, it is
evident that the vapour of benzene has a distinctly narcotic effect,
while influencing also in a marked degree the spinal cord. There
are, as symptoms, noises in the head, convulsive trembling and
twitchings of the muscles, with difficulty of breathing.

[142] Dr. Stone, _Med. Gaz._, 1848, vol. xii. p. 1077.

DETECTION AND SEPARATION OF BENZENE.

§ 149. Benzene is separated from liquids by distillation, and may be
recognised by its odour, and by the properties described at p. 130.
The best process of identification, perhaps, is to purify and
convert it into nitro-benzene, and then into aniline, in the
following manner:--

1. =Purification.=--The liquid is agitated with a solution of
caustic soda; this dissolves out of the benzene any bodies of an
acid character, such as phenol, &c. The purified liquid should again
be distilled, collecting that portion of the distillate which passes
over between 65° and 100°; directly the thermometer attains nearly
the 100°, the distillation should be stopped. The distillate, which
contains all the benzene present, is next shaken with concentrated
sulphuric acid in the cold; this will dissolve out all the
hydrocarbons of the ethylene and acetylene series. On removing the
layer of benzene from the acid, it must be again shaken up with
dilute soda, so as to remove any trace of acid. The benzene is, by
this rather complicated series of operations, obtained in a very
fair state of purity, and may be converted into nitro-benzene, as
follows:--

2. =Conversion into Nitro-Benzene.=--The oily liquid is placed in a
flask, and treated with four times its volume of fuming nitric acid.
The flask must be furnished with an upright condenser; a vigorous
action mostly takes place without the application of heat, but if
this does not occur, the flask may be warmed for a few minutes.

After the conversion is over, the liquid, while still warm, must be
transferred into a burette furnished with a glass tap, or to a
separating funnel, and all, except the top layer, run into cold
water; if benzene was originally present, either oily drops of
nitro-benzene will fall, or if the benzene was only in small
quantity, a fine precipitate will gradually settle down to the
bottom of the vessel, and a distinct bitter-almond smell be
observed; but, if there be no benzene in the original liquid, and,
consequently, no nitro-benzene formed, no such appearance will be
observed.

3. =Conversion into Aniline.=--The nitro-benzene may itself be
identified by collecting it on a wet filter, dissolving it off the
filter by alcohol, acidifying the alcoholic solution by hydrochloric
acid, and then boiling it for some time with metallic zinc. In this
way aniline is formed by reduction. On neutralising and diluting the
liquid, and cautiously adding a little clear solution of
bleaching-powder, a blue or purple colour passing to brown is in a
little time produced.

3. TERPENES--ESSENTIAL OILS--OIL OF TURPENTINE.

§ 150. The terpenes are hydrocarbons of the general formula
C_{n}H_{2n-4}. The natural terpenes are divided into three
classes:--

1. =The true terpenes=, _formula_ (C₁₀H₁₆)--a large number of
essential oils, such as those of turpentine, orange peel, nutmeg,
caraway, anise, thyme, &c., are mainly composed of terpenes.

2. =The cedrenes=, _formula_ (C₁₅H₂₄)--the essential oil of cloves,
rosewood, cubebs, calamus, cascarilla, and patchouli belong to this
class.

3. =The colophene hydrocarbons=, _formula_ (C₂₀H₃₂), represented by
colophony.

Of all these, oil of turpentine alone has any toxicological
significance; it is, however, true that all the essential oils, if
taken in considerable doses, are poisonous, and cause, for the most
part, vascular excitement and complex nervous phenomena, but their
action has not been very completely studied. They may all be
separated by distillation, but a more convenient process for
recovering an essential oil from a liquid is to shake it up with
petroleum ether, separating the petroleum and evaporating
spontaneously; by this means the oil is left in a fair state of
purity.

4. OIL OF TURPENTINE--SPIRIT OF TURPENTINE--“TURPS.”

§ 151. Various species of pine yield a crude turpentine, holding in
solution more or less resin. The turpentine may be obtained from
this exudation by distillation, and when the first portion of the
distillate is treated with alkali, and then redistilled, the final
product is known under the name of “rectified oil of turpentine,”
and is sometimes called “camphene.” It mainly consists of
terebenthene. Terebenthene obtained from French turpentine differs
in some respects from that obtained from English or American
turpentine. They are both mobile, colourless liquids, having the
well-known odour of turpentine and highly refractive; but the French
terebenthene turns a ray of polarised light to the left -40·3° for
the sodium ray, and the English to the right +21·5°; the latter
terebenthene is known scientifically as austra-terebenthene. This
action on polarised light is retained in the various compounds and
polymers of the two turpentine oils.

The specific gravity of turpentine oil is ·864; its boiling point,
when consisting of pure terebenthene, 156°, but impurities may raise
it up to 160°; it is combustible and burns with a smoky flame. Oil
of turpentine is very soluble in ether, petroleum ether, carbon
disulphide, chloroform, benzene, fixed and essential oils, and by
the use of these solvents it is conveniently separated from the
contents of the stomach. It is insoluble in water, glycerin, and
dilute alkaline and acid solutions; and very soluble in absolute
alcohol, from which it may be precipitated by the addition of water.

It is polymerised by the action of strong sulphuric acid, the
polymer, of course, boiling at a higher temperature than the
original oil. With water it forms a crystalline hydrate
(C₁₀H₂₀O₂,H₂O). On passing nitrosyl chloride gas into the oil,
either pure or diluted with chloroform or alcohol, the mixture being
cooled by ice, a white crystalline body is deposited, of the formula
C₁₀H₁₆(NOCl). By treating this compound with alcoholic potash, the
substitution product (C₁₀H₁₆NO) is obtained. By treating turpentine
with an equal bulk of warm water, and shaking it in a large bottle
with air, camphoric acid and peroxide of hydrogen are formed. When
turpentine oil is left in contact with concentrated hydrochloric
acid, there is formed terebenthene dihydrochloride (C₁₀H₁₆2HCl),
which forms rhombic plates, insoluble in water, and decomposable by
boiling alcoholic potash, with formation of terpinol, (C₁₀H₁₇)₂O.
The dihydrochloride gives a colour-reaction with ferric chloride.
This is an excellent test--not, it is true, confined to oil of
turpentine--but common to the dihydrochlorides of all the terpenes.
A few drops of the oil are stirred in a porcelain capsule with a
drop of hydrochloric acid, and one of ferric chloride solution; on
gently heating, there is produced first a rose colour, then a
violet-red, and lastly a blue.

§ 152. =Effects of the Administration of Turpentine.=--L. W.
Liersch[143] exposed animals to the vapour of turpentine, and found
that a cat and a rabbit died within half an hour. There was observed
uneasiness, reeling, want of power in the limbs (more especially in
the hinder extremities), convulsions partial, or general, difficulty
of respiration; and the heart’s action was quickened. Death took
place, in part, from asphyxia, and in part was attributable to a
direct action on the nervous centres. The autopsy showed congestion
of the lungs, ecchymoses of the kidney, and much blood in the liver
and spleen. Small doses of turpentine-vapour cause (according to Sir
B. W. Richardson)[144] giddiness, deficient appetite, and anæmia.
From half an ounce to an ounce is frequently prescribed in the
country as a remedy for tape-worm; in smaller quantities it is found
to be a useful medicine in a great variety of ailments. The larger
doses produce a kind of intoxication with giddiness, followed often
by purging and strangury, not unfrequently blood and albumen (or
both) is found in the urine. When in medical practice I have given
the oil, and seen it given by others, in large doses for tape-worm
to adults, in perhaps 40 cases, but in no one instance were the
symptoms severe; the slight intoxication subsided quickly, and in a
few hours the patients recovered completely. Nevertheless it has
been known to destroy the lives of children, and cause most serious
symptoms in adults. Two fatal cases are mentioned by Taylor; one was
that of a child who died fifteen hours after taking half an ounce of
the oil; in another an infant, five months old, died rapidly from a
teaspoonful. The symptoms in these fatal cases were profound coma
and slight convulsions; the pupils were contracted, and there was
slow and irregular breathing. Turpentine is eliminated in a changed
form by the kidneys, and imparts an odour of violet to the urine;
but the nature of the odoriferous principle has not yet been
investigated.

[143] Clarus in Schmidt’s _Jahrbücher_, Bd. cxvii., i. 1863; and _Vierteljahrsschr. für ger. Med._, xxii., Oct. 1862.

[144] _Brit. and For. Med.-Chir. Review_, April 1863.

II.--Camphor.

§ 153. A great many essential oils deposit, after exposure to air,
camphors produced by oxidation of their terpenes. Ordinary camphor
is imported in the rough state from China and Japan, and is prepared
by distilling with water the wood of _Camphora officinarum_; it is
resublimed in England. The formula of camphor is C₁₀H₁₆O; it has a
density of ·986 to ·996; melts at 175°, and boils at 205°. It is
readily sublimed, especially in a vacuum, and is indeed so volatile
at all temperatures, that a lump of camphor exposed to the air
wastes away. It is somewhat insoluble in water (about 1 part in
1000), but this is enough to impart a distinct taste to the water;
it is insoluble in chloroform, ether, acetone, acetic acid, carbon
disulphide, and oils. It has a fragrant odour and a burning taste. A
10 per cent. solution in alcohol turns a ray of polarised light to
the right +42·8°. By distillation with zinc chloride, cymene and
other products are produced. By prolonged treatment with nitric
acid, camphor is oxidised to camphoric acid (C₁₀H₁₆O₄). Camphor
unites with bromine to form a crystalline, unstable dibromide, which
splits up on distillation into hydrobromic acid and monobrom-camphor
(C₁₀H₁₅BrO). The latter is used in medicine; it crystallises in
prisms fusible at 76°, and is readily soluble in alcohol.

§ 154. =Pharmaceutical Preparations.=--The preparations officinal in
the British Pharmacopœia are _camphor water_--water saturated with
camphor, containing about one part per thousand.

=Camphor Liniment.=--A solution of camphor in olive oil, strength 25
per cent.

=Compound Camphor Liniment.=--Composed of camphor, oil of lavender,
strong solution of ammonia and alcohol; strength in camphor about 11
per cent.

=Spirit of Camphor.=--A solution of camphor in spirit; strength, 10
per cent.

Camphor is also a constituent of the _compound tincture of camphor_;
but in this case it may be considered only a flavouring agent. There
is a homœopathic solution of camphor in spirit (Rubini’s Essence of
Camphor). The solution is made by saturating alcohol with camphor;
it is, therefore, very strong--about half the bulk consisting of
camphor. Camphor is used in veterinary medicine, both externally and
internally.

§ 155. =Symptoms.=--Camphor acts energetically on the brain and
nervous system, especially if it is given in strong alcoholic
solution, and thus placed under conditions favouring absorption.
Some years ago, Dr. G. Johnson[145] published a series of cases
arising from the injudicious use of “homœopathic solution of
camphor,” from 7 to 40 drops of Rubini’s homœopathic camphor taken
for colds, sore throat, &c., having produced coma, foaming at the
mouth, convulsions, and partial paralysis. All the patients
recovered, but their condition was for a little time alarming.

[145] _Brit. Med. Journ._, Feb. 27, 1878, p. 272; see also _ibid._, Feb. 1875.

The cases of fatal poisoning by camphor are very rare. A woman, aged
46, pregnant four months, took 12 grms. (about 184 grains) in a
glass of brandy for the purpose of procuring abortion. In a very
short time the symptoms commenced; she had intolerable headache, the
face was flushed, and there was a sensation of burning in the
stomach. In eight hours after taking the dose, she had strangury and
vomiting, and the pain in the epigastrium was intense. These
symptoms continued with more or less severity until the third day,
when she became much worse. Her face was pale and livid, the eyes
hollow, the skin cold and insensible, pulse weak and thready,
breathing laboured. There were violent cramps in the stomach and
retention of urine for twenty-four hours, and then coma. The patient
lingered on yet another three days, aborted, and died.[146]

[146] _Journ. de Chim. Méd._, May 1860.

Dr. Schaaf[147] has recorded three cases of poisoning--one of which
was fatal. A woman gave about half a teaspoonful of a camphor
solution to each of her three children, the ages being respectively
five and three years and fifteen months. The symptoms noted were
pallor of the face, a burning pain in the throat, thirst, vomiting,
purging, convulsions, and afterwards coma. The youngest child died
in seven hours; the others recovered. The smallest dose known to
have produced violent symptoms in an adult is 1·3 grm. (20 grains);
the largest dose known to have been recovered from is 10·4 grms.
(160 grains).[148]

[147] _Journ. de Chim. Méd._, 1850, p. 507.

[148] Taylor on _Poisons_, 3rd ed., 661.

§ 156. =Post-mortem Appearances.=--The bodies of animals or persons
dying from poisoning by camphor, smell strongly of the substance.
The mucous membrane of the stomach has been found inflamed, but
there seem to be no characteristic lesions.

§ 157. =Separation of Camphor from the Contents of the
Stomach.=--The identification of camphor would probably in no case
present any difficulty. It may be readily dissolved out from organic
fluids by chloroform. If dissolved in fixed oils, enough for the
purposes of identification may be obtained by simple distillation.
It is precipitated from its alcoholic solution by the addition of
water.

III.--Alcohols.

1. ETHYLIC ALCOHOL.

§ 158. The chemical properties of ordinary alcohol are fully described, with the appropriate tests, in “Foods,” pp. 369-384, and the reader is also referred to the same volume for the composition and strength of the various alcoholic drinks.

=Statistics.=--If we were to include in one list the deaths indirectly due to chronic, as well as acute poisoning by alcohol, it would stand first of all poisons in order of frequency, but the taking of doses so large as to cause death in a few hours is rare. The deaths from alcohol are included by the English registrar-general under two heads, viz., those returned as dying from _delirium tremens_, and those certified as due directly to intemperance.

During the twenty-five years, from 1868 to 1892, 30,219 deaths have been registered as due to intemperance, which gives an average of 1209 per year. The rate per million has varied during the period from 29 to 71; and the figures taken as a whole show that deaths from intemperance appear to be increasing; the increase may be only apparent, not real, for it is a significant circumstance that deaths registered under liver diseases show a corresponding decrease; it is, therefore, not unlikely that deaths which formerly would be ascribed to liver disease, are more often now stated to be the effects of intemperance.

Deaths directly due to large doses of alcohol are not uncommon; during the ten years ending 1892, 105 deaths (81 males and 24 females) were ascribed under the head of “accident or negligence” directly to alcohol.

THE MEDICAL “OFFICERS OF HEALTH” CHART.

ENT. AT STA. HALL.

Notes.
_Intemperance_ --------------
_Liver disease_ ..............
_The Scale for Intemperance is as printed._
_That for Liver diseases is 10 times larger._]

§ 159. =Criminal or Accidental Alcoholic Poisoning.=--Suicide by alcohol, in the common acceptation of the term, is rare, and murder still rarer, though not unknown. In the ten years ending 1892, only three deaths from alcohol (1 male and 2 females) are recorded as suicidal. Perhaps the most common cause of fatal acute poisoning by alcohol is either a foolish wager, by which a man bets that he can drink so many glasses of spirits without bad effect; or else the drugging of a person already drunk by his companions in a sportive spirit.

§ 160. =Fatal Dose.=--It is difficult to say what would be likely to prove a lethal dose of alcohol, for a great deal depends, without doubt, on the dilution of the spirit, since the mere local action of strong alcohol on the mucous membranes of the stomach, &c., is severe (one may almost say corrosive), and would aid the more remote effects. In Maschka’s case,[149] a boy of nine years and a girl of five, died from about two and a half ounces of spirit of 67 per cent. strength, or 48·2 c.c. (1·7 oz.) of absolute alcohol.

[149] Recorded by Maschka (_Gutachten der Prager Facultät_, iv. 239; see also Maschka’s _Handbuch der gericht. Medicin_, Band. ii. p. 384). The following is a brief summary:--Franz. Z., nine years old, and Caroline Z., eight years old, were poisoned by their stepfather with spirit of 67 per cent. strength taken in small quantities by each--at first by persuasion, and the remainder administered by force. About one-eighth of a pint is said to have been given to each child. Both vomited somewhat, then lying down, stertorous breathing at once came on, and they quickly died. The autopsy, three days after death, showed dilatation of the pupils; _rigor mortis_ present in the boy, not in the girl; and the membranes of the brain filled with dark fluid blood. The smell of alcohol was perceptible on opening the chest; the mucous membrane of the bronchial tubes and gullet was normal, both lungs œdematous, the fine tubes gorged with a bloody frothy fluid, and the mucous membrane of the whole intestinal canal was reddened. The stomach was not, unfortunately, examined, being reserved for chemical analysis. The heart was healthy; the pericardium contained some straw-coloured fluid. Chemical analysis gave an entirely negative result, which must have been from insufficient material having been submitted to the analyst, for I cannot see how the vapours of alcohol could have been detected by the smell, and yet have evaded chemical processes.

In a case related by Taylor, a child, seven years old, died from some quantity of brandy, probably about 113·4 c.c. (4 ozs.), which would be equal to at least 56·7 c.c. (2 ozs.) of absolute alcohol. From other cases in which the quantity of absolute alcohol can be, with some approximation to the truth, valued, it is evident that, for any child below ten or twelve, quantities of from 28·3 to 56·6 c.c. (1-2 ozs.) of absolute alcohol contained in brandy, gin, &c., would be a highly dangerous and probably fatal dose; while the toxic dose for adults is somewhere between 71·8-141·7 c.c. (2·5-5 ozs.).

§ 161. =Symptoms.=--In the cases of rapid poisoning by a large dose of alcohol, which alone concern us, the preliminary, and too familiar excitement of the drunkard, may be hardly observable; but the second stage, that of depression, rapidly sets in; the unhappy victim sinks down to the ground helpless, the face pale, the eyes injected and staring, the pupils dilated, acting sluggishly to light, and the skin remarkably cold. Fräntzel[150] found, in a case in which the patient survived, a temperature of only 24·6° in the rectum, and in that of another person who died, a temperature of 23·8°. The mucous membranes are of a peculiar dusky blue; the pulse, which at first is quick, soon becomes slow and small; the respiration is also slowed, intermittent, and stertorous; there is complete loss of consciousness and motion; the breath smells strongly of the alcoholic drink, and if the coma continues there may be vomiting and involuntary passing of excreta. Death ultimately occurs through paralysis of the respiratory centres. Convulsions in adults are rare, in children frequent. Death has more than once been immediately caused, not by the poison, but by accidents dependent upon loss of consciousness. Thus food has been sucked into the air-tubes, or the person has fallen, so that the face was buried in water, ordure, or mud; here suffocation has been induced by mechanical causes.

[150] _Temperaturerniedrigung durch Alcoholintoxication, Charité Annalen_, i. 371.

A remarkable course not known with any other narcotic is that in which the symptoms remit, the person wakes up, as it were, moves about and does one or more rational acts, and then suddenly dies. In this case also, the death is not directly due to alcohol, but indirectly--the alcohol having developed œdema, pneumonia, or other affection of the lungs, which causes the sudden termination when the first effect of the poison has gone off. The time that may elapse from the commencement of coma till death varies from a few minutes to days; death has occurred after a quarter of an hour, half an hour, and an hour. It has also been prolonged to three, four, and six days, during the whole of which the coma has continued. The average period may, however, be put at from six to ten hours.

§ 162. =Post-mortem Appearances.=--Cadaveric rigidity lasts tolerably long. Casper has seen it still existing nine days after death, and Seidel[151] seven days (in February). Putrefaction is retarded in those cases in which a very large dose has been taken, but this is not a very noticeable or constant characteristic. The pupils are mostly dilated. The smell of alcohol should be watched for; sometimes it is only present in cases where but a short time has elapsed between the taking of the poison and death; putrefaction may also conceal it, but under favourable circumstances, especially if the weather is cold, the alcoholic smell may remain a long time. Alcohol may cause the most intense redness and congestion of the stomach. The most inflamed stomach I ever saw, short of inflammation by the corrosive poisons, was that of a sailor, who died suddenly after a twenty-four hours’ drinking bout: all the organs of the body were fairly healthy, the man had suffered from no disease; analysis could detect no poison but alcohol; and the history of the case, moreover, proved clearly that it was a pure case of alcoholic poisoning.

[151] Seidel, Maschka’s _Handbuch_, Bd. ii. p. 380.

In a case related by Taylor, in which a child drank 4 ozs. of brandy and died, the mucous membrane of the stomach presented patches of intense redness, and in several places was thickened and softened, some portions being actually detached and hanging loose, and there were evident signs of extravasations of blood. The effect may not be confined to the stomach, but extend to the duodenum and even to the whole intestinal canal. The blood is generally dark and fluid, and usually the contents of the skull are markedly hyperæmic, the pia very full of blood, the sinuses and plexus gorged; occasionally, the brain-substance shows signs of unusual congestion; serum is often found in the ventricles. The great veins of the neck, the lungs, and the right side of the heart, are very often found full of blood, and the left side empty. Œdema of the lungs also occurs with tolerable frequency. The great veins of the abdomen are also filled with blood, and if the coma has been prolonged, the bladder will be distended with urine. A rare phenomenon has also been noticed--namely, the occurrence of blebs on the extremities, &c., just as if the part affected had been burnt or scalded. Lastly, with the changes directly due to the fatal dose may be included all those degenerations met with in the chronic drinker, provided the case had a history of previous intemperance.

§ 163. =Excretion of Alcohol.=--Alcohol, in the diluted form, is quickly absorbed by the blood-vessels of the stomach, &c., and circulates in the blood; but what becomes of it afterwards is by no means settled. I think there can be little doubt that the lungs are the main channels through which it is eliminated; with persons given up to habits of intemperance, the breath has constantly a very peculiar ethereal odour, probably dependent upon some highly volatile oxidised product of alcohol.

Alcohol is eliminated in small proportion only by the kidneys. Thudichum, in an experiment[152] by which 4000 grms. of absolute alcohol were consumed by thirty-three men, could only find in the collected urine 10 grms. of alcohol. The numerous experiments by Dupré also establish the same truth, that but a fraction of the total alcohol absorbed is excreted by the kidneys. According to Lallemand, Perrin, and Duroy the content of the brain in alcohol is more than that of the other organs. I have found also that the brain after death has a wonderful attraction for alcohol, and yields it up at a water-heat very slowly and with difficulty. In one experiment, in which a finely-divided portion of brain, which had been soaking in alcohol for many weeks, was submitted to a steam heat of 100°, twenty-four hours’ consecutive heating failed to expel every trace of spirit.

[152] See Thudichum’s _Pathology of the Urine_, London, 1877, in which both his own and Dr. Dupré’s experiments are summarised.

It is probable that true alcoholates of the chemical constituents of the brain are formed. In the case of vegetable colloidal bodies, such, for example, as the pulp of cherries, a similar attraction has been observed, the fruit condensing, as it were, the alcohol in its own tissues, and the outer liquid being of less alcoholic strength than that which can be expressed from the steeped cherries. Alcohol is also excreted by the sweat, and minute fractions have been found in the fæces.

§ 164. =Toxicological Detection of Alcohol= (see “Foods,” pp. 406-419).--The living cells of the body produce minute quantities of alcohol, as also some of the bacteria normally inhabiting the small intestine produce small quantities of alcohol, and it is often found in traces in putrefying fluids. Hence, mere qualitative proofs of the presence of alcohol are insufficient on which to base an opinion as to whether alcohol had been taken during life or not, and it will be necessary to estimate the quantity accurately by some of the processes detailed in “Foods,” p. 409, _et seq._ In those cases in which alcohol is found in quantity in the stomach, there can, of course, be no difficulty; in others, the whole of the alcohol may have been absorbed, and chemical evidence, unless extremely definite, must be supplemented by other facts.

2. AMYLIC ALCOHOL.

§ 165. =Amylic Alcohol=--_Formula_, C₅H₁₁HO.--There is more than one
amylic alcohol according to theory; eight isomers are possible, and
seven are known. The amylic alcohols are identical in their chemical
composition, but differ in certain physical properties, primary
amylic alcohol boiling at 137°, and iso-amyl alcohol at 131·6°. The
latter has a specific gravity of ·8148, and is the variety produced
by fermentation and present in fusel oil.

§ 166. The experiments of Eulenberg[153] on rabbits, Cross[154] on
pigeons, Rabuteau[155] on frogs, and Furst on rabbits, with those of
Sir B. W. Richardson[156] on various animals, have shown it to be a
powerful poison, more especially if breathed in a state of vapour.

[153] _Gewerbe Hygiene_, 1876, p. 440.

[154] _De l’Alcohol Amylique et Méthyl sur l’Organisme (Thèse)_, Strasburg, 1863.

[155] “Ueber die Wirkung des Aethyl, Butyl u. Amyl Alcohols,” _L’Union_, Nos. 90, 91, 1870. Schmidt’s _Jahrb._, Bd. 149, p. 263.

[156] _Trans. Brit. Association_, 1864, 1865, and 1866. Also, _Brit. and Foreign Med. Chir. Rev._, Jan. 7, 1867, p. 247.

Richardson, as the result of his investigations, considers that amyl
alcohol when breathed sets up quite a peculiar class of symptoms
which last for many hours, and are of such a character, that it
might be thought impossible for the animal to recover, although they
have not been known to prove fatal. There is muscular paralysis with
paroxysms of tremulous convulsions; the spasms are excited by
touching the animal, breathing upon it, or otherwise subjecting it
to trifling excitation.

§ 167. Hitherto, neither the impure fusel oil, nor the purer
chemical preparation, has had any toxicological importance. Should
it be necessary at any time to recover small quantities from organic
liquids, the easiest way is to shake the liquid up with chloroform,
which readily dissolves amylic alcohol, and on evaporation leaves it
in a state pure enough to be identified. Amyl alcohol is identified
by the following tests:--(1) Its physical properties; (2) if warmed
with twice its volume of strong sulphuric acid, a rose or red colour
is produced; (3) heated with an acetate and strong sulphuric acid,
_amyl acetate_, which has the odour of the jargonelle pear, is
formed; (4) heated with sulphuric acid and potassic dichromate,
valeric aldehyde is first produced, and then valeric acid is formed;
the latter has a most peculiar and strong odour.

§ 168. =Amyl Nitrite, Iso-amyl Ester Nitrite= (C₅H₁₁NO₂).--Boiling
point 97° to 99°, specific gravity ·877. Amyl nitrite is a limpid,
and, generally, slightly yellow liquid; it has a peculiar and
characteristic odour. On heating with alcoholic potash, the products
are nitrite of potash and amylic alcohol; the amylic alcohol may be
distilled off and identified. The presence of a nitrite in the
alkaline solution is readily shown by the colour produced, by adding
a few drops of a solution of meta-phenylenediamine.

Sir B. W. Richardson and others have investigated the action of amyl
nitrite, as well as that of the acetate and iodide; they all act in
a similar manner, the nitrite being most potent. After absorption,
the effects of amyl nitrite are especially seen on the heart and
circulation: the heart acts violently, there is first dilatation of
the capillaries, then this is followed by diminished action of the
heart and contraction of the capillaries.

According to Richardson, it suspends the animation of frogs. No
other substance known will thus suspend a frog’s animation for so
long a time without killing it. Under favourable circumstances, the
animal will remain apparently dead for many days, and yet recover.
Warm-blooded animals may be thrown by amyl nitrite into a cataleptic
condition. It is not an anæsthetic, and by its use consciousness is
not destroyed, unless a condition approaching death be first
produced. When this occurs there is rarely recovery, the animal
passes into actual death.

=Post-Mortem Appearances.=--If administered quickly, the lungs and
all the other organs are found blanched and free from blood, the
right side of the heart gorged with blood, the left empty, the brain
being free from congestion. If administered slowly, the brain is
found congested, and there is blood both on the left and right sides
of the heart.

IV.--Ether.

§ 169. =Ether, Ethylic Ether, Ethyl Oxide,= (C₂H₅)₂O.--Ethylic ether is a highly mobile liquid of peculiar penetrating odour and sweetish pungent taste. It is perfectly colourless, and evaporates so rapidly, that when applied in the form of spray to the skin, the latter becomes frozen, and is thus deprived of sensibility.

Pure ether has a density of ·713, its boiling-point is 35°, but commercial samples, which often contain water (1 part of water is soluble in 35 of ether), may have a higher gravity, and also a higher boiling-point. The readiest way to know whether an ether is anhydrous or not, is to shake it up with a little carbon disulphide. If it is hydrous, the mixture is milky. Methylated ether is largely used in commerce; its disagreeable odour is due to contamination by methylated compounds; otherwise the ether made from methylated spirit is ethylic ether, for methylic ether is a gas which escapes during the process. Hence the term “methylated” ether is misleading, for it contains no methylic ether, but is essentially a somewhat impure ethylic ether.

§ 170. =Ether as a Poison.=--Ether has but little toxicological importance. There are a few cases of death from its use as an anæsthetic, and a few cases of suicide. Ether is used by some people as a stimulant, but ether drinkers are uncommon. It causes an intoxication very similar to that of alcohol, but of brief duration. In a case of chronic ether-taking recorded by Martin,[157] in which a woman took daily doses of ether for the purpose of allaying a gastric trouble, the patient suffered from shivering or trembling of the hands and feet, muscular weakness, cramp in the calves of the legs, pain in the breast and back, intermittent headaches, palpitation, singing in the ears, vomitings, and wakefulness; the ether being discontinued, the patient recovered. In one of Orfila’s experiments, half an ounce of ether was administered to a dog. The animal died insensible in three hours. The mucous membrane of the stomach was found highly inflamed, the inflammation extending somewhat into the duodenum; the rest of the canal was healthy. The lungs were gorged with fluid blood.

[157] Virchow’s _Jahresber._, 1870.

§ 171. =Fatal Dose.=--The fatal dose of ether, when taken as a liquid, is not known. 4 grms. (1·28 drms.) cause toxic symptoms, but the effect soon passes. Buchanan has seen a brandy-drinker consume 25 grms. (7 drms.) and yet survive. It is probable that most adults would be killed by a fluid ounce (28·4 c.c.).

§ 172. =Ether as an Anæsthetic.=--Ether is now much used as an anæsthetic, and generally in conjunction with chloroform. Anæsthesia by ether is said to compare favourably with that produced by chloroform. In 92,000 cases of operations performed under ether, the proportion dying from the effects of the anæsthetic was only ·3 per 10,000 (Morgan), while chloroform gives a higher number (see p. 149). The mortality in America, again, from a mixture of chloroform and ether in 11,000 cases is reckoned at 1·7 per 10,000; but this proportion is rather above some of the calculations relative to the mortality from pure chloroform, so that the question can hardly be considered settled. The symptoms of ether narcosis are very similar to those produced by chloroform. The chief point of difference appears to be its action on the heart. Ether, when first breathed, stimulates the heart’s action, and the after-depression that follows never reaches so high a grade as with chloroform. Ether is said to kill by paralysing the respiration, and in cases which end fatally the breathing is seen to stop suddenly: convulsions have not been noticed. The _post-mortem_ appearances, as in the case of chloroform, are not characteristic.

§ 173. =Separation of Ether from Organic Fluids, &c.=--Despite the low boiling-point of ether, it is by no means easy to separate it from organic substances _so as to recover the whole of the ether present_. The best way is to place the matters in a flask connected with an ordinary Liebig’s condenser, the tube of the latter at its farther end fitting closely into the doubly perforated cork of a flask. Into the second perforation is adapted an upright tube about 2 feet long, which may be of small diameter, and must be surrounded by a freezing mixture of ice and salt. The upper end of this tube is closed by a thistle-head funnel with syphon, and in the bend of the syphon a little mercury serves as a valve. Heat is now applied to the flask by means of a water-bath, and continued for several hours; the liquid which has distilled over is then treated with dry calcic chloride and redistilled exactly in the same way. To this distillate again a similar process may be used, substituting dry potassic carbonate for the calcic chloride. It is only by operating on these principles that the expert can recover in an approximate state of anhydrous purity such a volatile liquid. Having thus obtained it pure, it may be identified (1) by its smell, (2) by its boiling-point, (3) by its inflammability, and (4) by its reducing chromic acid. The latter test may be applied to the vapour. An asbestos fibre is soaked in a mixture of strong sulphuric acid and potassic dichromate, and then placed in the tube connected with the flask--the ethereal (or alcoholic) vapour passing over the fibre, immediately reduces the chromic acid to chromic oxide, with the production of a green colour.

V.--Chloroform.

CHLOROFORM, TRICHLOROMETHANE OR METHENYL CHLORIDE (CHCl₃).

§ 174. Chloroform appears to have been discovered independently by Soubeiran and Liebig, about 1830. It was first employed in medicine by Simpson, of Edinburgh, as an anæsthetic. Pure chloroform has a density of 1·491 at 17°, and boils at 60·8°; but commercial samples have gravities of from 1·47 to 1·491. It is a colourless liquid, strongly refracting light; it cannot be ignited by itself, but, when mixed with alcohol, burns with a smoky flame edged with green. Its odour is heavy, but rather pleasant; the taste is sweet and burning.

Chloroform sinks in water, and is only slightly soluble in that fluid (·44 in 100 c.c.), it is perfectly neutral in reaction, and very volatile. When rubbed on the skin, it should completely evaporate, leaving no odour. Pure absolute chloroform gives an opaline mixture if mixed with from 1 to 5 volumes of alcohol, but with any quantity above 5 volumes the mixture is clear; it mixes in all proportions with ether. Chloroform coagulates albumen, and is an excellent solvent for most organic bases--camphor, caoutchouc, amber, opal, and all common resins. It dissolves phosphorus and sulphur slightly--more freely iodine and bromine. It floats on hydric sulphate, which only attacks it at a boiling heat.

Chloroform is frequently impure from faulty manufacture or decomposition. The impurities to be sought are alcohol, methylated chloroform,[158] dichloride of ethylene (C₂H₄Cl₂), chloride of ethyl (C₂H₅Cl), aldehyde, chlorine, hydrochloric, hypochlorous, and traces of sulphuric acid: there have also been found chlorinated oils. One of the best tests for contamination by alcohol, wood spirit, or ether, is that known as Roussin’s; dinitrosulphide of iron[159] is added to chloroform. If it contain any of these impurities, it acquires a dark colour, but if pure, remains bright and colourless.

[158] Methylated chloroform is that which is prepared from methylated spirit. It is liable to more impurities than that made from pure alcohol, but, of course, its composition is the same, and it has recently been manufactured from this source almost chemically pure.

[159] Made by slowly adding ferric sulphate to a boiling solution of ammonic sulphide and potassic nitrite, as long as the precipitate continues to redissolve, and then filtering the solution.

The presence of alcohol or ether, or both, may also be discovered by the bichromate test, which is best applied as follows:--A few milligrammes of potassic bichromate are placed at the bottom of a test-tube with four or five drops of sulphuric acid, which liberates the chromic acid; next, a very little water is added to dissolve the chromic acid; and lastly, the chloroform. The whole is now shaken, and allowed to separate. If the chloroform is pure, the mass is hardly tinged a greenish-yellow, and no layer separates. If, however, there is anything like 5 per cent. of alcohol or ether present, the deep green of chromium chloride appears, and there is a distinct layer at the bottom of the tube.

Another way to detect alcohol in chloroform, and also to make an approximate estimation of its quantity, is to place 20 c.c. of chloroform in a burette, and then add 80 c.c. of water. On shaking violently, pure chloroform will sink to the bottom in clear globules, and the measurement will be as nearly as possible the original quantity; but if anything like a percentage of alcohol be present, the chloroform is seen to be diminished in quantity, and its surface is opalescent, the diminution being caused by the water dissolving out the alcohol. The addition of a few drops of potash solution destroys the meniscus, and allows of a close reading of the volume. The supernatant water may be utilised for the detection of other impurities, and tested for sulphuric acid by baric chloride, for free chlorine and hypochlorous acid by starch and potassic iodide, and for hydrochloric acid by silver nitrate.[160] Fuchsine, proposed by Stœdeler, is also a delicate reagent for the presence of alcohol in chloroform, the sample becoming red in the presence of alcohol, and the tint being proportionate to the quantity present. The most delicate test for alcohol is, however, the iodoform test fully described in “Foods,” p. 375.[161] Dichloride of ethylene is detected by shaking up the chloroform with dry potassic carbonate, and then adding metallic potassium. This does not act on pure chloroform, but only in presence of ethylene dichloride, when the gaseous chlor-ethylene (C₂H₃Cl) is evolved. Ethyl-chloride is detected by distilling the chloroform and collecting the first portions of the distillate; it will have a distinct odour of ethyl-chloride should it be present. Methyl compounds and empyreumatic oils are roughly detected by allowing the chloroform to evaporate on a cloth. If present, the cloth, when the chloroform has evaporated, will have a peculiar disagreeable odour. Aldehyde is recognised by its reducing action on argentic nitrate; the mineral acids by the reddening of litmus paper, and the appropriate tests. Hypochlorous acid first reddens, and then bleaches, litmus-paper.

[160] Neither an alcoholic nor an aqueous solution of silver nitrate causes the slightest change in pure chloroform.

[161] An attempt has been made by Besnou to estimate the amount of alcohol by the specific gravity. He found that a chloroform of 1·4945 gravity, mixed with 5 per cent. of alcohol, gave a specific gravity of 1·4772; 10 per cent., 1·4602; 20 per cent., 1·4262; and 25 per cent., 1·4090. It would, therefore, seem that every percentage of alcohol lowers the gravity by ·0034.

Dr. Dott, _Pharm. Journ._, 1894, p. 629, gives the following tests:--Specific gravity, 1·490 to 1·495. On allowing ½ fluid drm. to evaporate from a clean surface, no foreign odour is perceptible at any stage of the evaporation. When 1 fluid drm. is agitated with an equal volume of solution of silver nitrate, no precipitate or turbidity is produced after standing for five minutes. On shaking up the chloroform with half its volume of distilled water, the water should not redden litmus-paper. When shaken with an equal volume of sulphuric acid, little or no colour should be imparted to the acid.

§ 175. The ordinary method of manufacturing chloroform is by distilling alcohol with chlorinated lime; but another mode is now much in use--viz., the decomposition of chloral hydrate. By distilling it with a weak alkali, this process yields such a pure chloroform, that, for medicinal purposes, it should supersede every other.

Poisonous Effects of Chloroform.

1. AS A LIQUID.

§ 176. =Statistics.=--Falck finds recorded in medical literature 27 cases of poisoning by chloroform having been swallowed--of these 15 were men, 9 were women, and 3 children. Eighteen of the cases were suicidal, and 10 of the 18 died; the remainder took the liquid by mistake.