Charles D. F. (Charles Douglas Fergusson) Phillips.

Materia medica and therapeutics, inorganic substances; (Volume 2) online

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1 to 5 gr. Pyrophosphate of iron : dose, 5 to 10 gr. Hypophosphite of
iron syrup: dose, 1 dr. (Pharmaceutical Journal, v., vii.). ParrisWs
syrup of phosphates (compound), containing in each drachm 1 gr. phos-
phate of iron with soda and potash; Dr. Frederick Churchill's syrup
(v. British Medical Journal, March, 1880); Beef and iron wine (Bur-
roughs); MonseVs solution (liq. ferri subsulphatis); and many others.


Mercury is most frequently found in combination with sulphur, as
native sulphide or cinnabar, in mines in Almaden, Ydria,* China, Peru,
Japan, and California. It is obtained from the ore by fusion with lime,
which combines with the sulphur, while the mercury distils over. It oc-
curs, also, as a natural amalgam with silver " argental mercury " com-
bined with chlorine in small gray crystals, known as "horn mercury;"
also more rarely as an iodide, and sometimes in a pure state " virgin

CHARACTERS AND TESTS. Mercury is a silvery-white metal, with
bluish lustre, and is fluid at ordinary temperatures. When pure, it has
neither taste nor smell; it readidly oxidizes on exposure to the air, but
does not tarnish. Should tarnishing occur, it implies the presence of


other metals, as lead, zinc, or bismuth; it is susceptible of such division,
that it may be squeezed in minute globules through chamois leather. On
agitation with alcohol, ether, or turpentine, or on trituration with sul-
phur or unctuous substances, it loses its Quid character. With other
metals, and even with hydrogen, it forms soft compounds termed amal-
gams, and a mere trace of it will leave a white stain on silver or gold.
It has a sp. gr. of 13.59, which is exceeded only by that of gold and plati-
num, is slightly volatile at ordinary temperatures, boils at 662 F., and
freezes at 39 F., becoming crystalline, tough, malleable, and sonorous.
Its specific heat is low, but it is a good conductor, and has a regular rate
of expansion and contraction, hence it is well suited for thermometric
and barometric purposes: from its power of combining readily with silver
and gold, and yet afterward quickly volatilizing on being heated, it is
valuable in the arts of gilding and silvering, and alloyed with tinfoil it
forms the reflecting surface of mirrors.

Hydrochloric acid has no action on mercury, and hence the chlorides
cannot be prepared in a direct manner. Sulphuric acid, when boiling,
and nitric acid, whether cold or hot, form respectively salts of different
degrees of saturation proto- or sub-salts which are known as mercurous,
and per-salts, known as mercuric, and which have much more active pow-
ers than the former.

The per-salts of mercury are many of them (as the perchloride and
red iodide) soluble in ether when the sub-salts are not, so that by this
agent they may be' separated from each other.

If any salt of mercury be heated in a test tube with sodic carbonate,
the pure metal will sublime, and it may be obtained from its various com-
binations by distillation. With sulphuretted hydrogen in excess, mercurial
compounds give a black precipitate of sulphide; but the best general test
is the deposition of metallic mercury upon bright copper. It may be
applied by heating any mercurial salt with a strip of copper and a few
drops of hydrochloric acid, and, if the copper be afterward heated, small
globules of quicksilver may be obtained as a sublimate.


OMEL, Hg 3 Cl a ,=471.

PREPARATION. (1) Ten parts of sulphate of mercury are triturated
with seven of metallic mercury and a little water, so that a subsulphate
is formed thus

(2) Chloride of sodium is then added with trituration, the mixture is


heated, and tho subchloride of mercury sublimes as vapor, while sulphate
of sodium is left thus

Hg a S0 4 +2NaCl=Na s SO 4 +Hg,Cl t .

A large condensing chamber is required in order to obtain a. fine powder,
and this is washed with hot water in order to remove any perchloride
that may be formed.

CHARACTERS AND TESTS. Calomel usually occurs as a heavy, dull,
white powder, which is rendered yellow by trituration or by gentle heat:
if sublimed in a small chamber, fibrous crystalline lumps are produced.
The sp. gr. is 7.2. It has no taste, and hence its name of mercurius dul-
cis. It is not acted upon by hot water, ether, alcohol, or dilute acids,
but potash or soda decomposes it with precipitation of the black oxide
of mercury. Prussia acid also turns calomel black by causing the separa-
tion of metallic mercury. Pure calomel is entirely volatilized by heat, and
warm ether shaken with it should leave no residue on evaporation (show-
ing the absence of corrosive sublimate).


PREPARATION. By subliming dry mercuric sulphate with four-fifths
of its weight of dried sodium chloride, 2 or 3 per cent, of oxide of man-
ganese being previously added to the mixture. The reaction is as

HgSO 4 + 2NaCl= HgCl 2 + Na 2 SO 4 .

Sulphate of soda being left, and corrosive sublimate condensing in the
cooler part of the subliming apparatus. It will be noticed that the man-
ganese has no share in the decomposition; it is introduced in order that
it may set free from the excess of sodic chloride some free chlorine to
combine with any calomel that may be formed, and convert it into cor-
rosive sublimate: calomel would be formed if the mercuric sulphate con-
tained any mercurous salt, as it i apt to do. " The fumes are extremely
acrid and poisonous " (Miller).

CHARACTERS AND TESTS. Corrosive sublimate occurs in white crys-
talline heavy masses sp. gr. 5.2 it is entirely volatilized by heat, is solu-
ble in 16 parts of cold and 3 of boiling water, soluble also in alcohol, and
still more so in ether. The strong mineral acids dissolve it without de-
composition. Alkaline chlorides render it more soluble in water, and
hence ammonium chloride is introduced into the officinal solution of the
sublimate, and it forms with it a double salt (sal-alembroth). A simple
solution in water readily decomposes, calomel being precipitated, and if
exposed to light and to contact with organic substances, metallic mer-
cury separates. Ammonia gives a white precipitate of ammonio-chloride,
potassic iodide produces the red iodide, potash a precipitate of the yellow


oxide, and nitrate of silver a curdy white silver chloride. Albumen also
combines directly with corrosive sublimate, and precipitates its solutions.
Liquor Hydraryyri Perchloridi Solution of Perchloride of Mercury
(v. p. 224).

PRECIPITA TE, NH 2 HgCl, =251 .5.

PREPARATION. By adding solution of corrosive sublimate to ammo-
nia, chloride of ammonium is formed, and an ammonio-chloride of mer-
cury precipitated

HgCl, + 2NH 3 = NHJIgCl + NH 4 C1.

The ammonium salt is removed by washing, after filtration.

CHARACTERS AND TESTS. This compound occurs as a heavy white
powder, or in small cones marked by the linen filters: it has a metallic
taste; no odor; is insoluble in cold water, alcohol, and ether; soluble in
warm acids; decomposed by caustic potash, evolving ammonia, while yel-
low oxide of mercury is precipitated. Boiled with chloride of tin it gives
a precipitate first gray and then black, from the presence first of subchlor-
ide and metallic mercury, and next of the metal wholly; this has been
called the magpie test. " Chlorine and bromine both act violently on
white precipitate, forming mercuric chloride or bromide, the action in
many cases being attended with explosion. With iodine, an explosion
almost invariably takes placa after a few minutes: it would appear that
iodide of nitrogen is formed " (" Miller's Elements of Chemistry," 1878).



PREPARATION. By triturating together mercury and iodine in proper
atomic proportions: some rectified spirit is added in order to dissolve the
iodine, and to lessen, by evaporation, the heat evolved in the process.

CHARACTERS AND TESTS. The pure mercurous iodide is a yellow
powder, but according to the mode of preparation, or degree of exposure
to light, becomes greenish, and olive-colored or even black; it is insoluble
in water or ether; entirely volatilized when rapidly heated, but if warmed
slowly in a test tube, it yields a yellow sublimate (pure mercurous iodide),
metallic mercury being left: the yellow sublimate turns red on friction.


HgI 2 ,=454.

PREPARATION. By mixing together boiling solutions of iodide of po-
tassium and corrosive sublimate: doubie decomposition ensues, and the
red iodide is precipitated.

HgCl J +2KI=2KCl + HgT J .


CHARACTERS AND TESTS. A crystalline red powder, which becomes
yellow when gently heated, and again red upon friction or after cooling:
this change in color is due to a change in crystalline form, the yellow
crystals being rhomboidal, the red, octahedral prisms. The salt is insol-
uble in water, soluble in ether and solutions of iodide of potassium. The
presence of iodine may be verified by starch producing a blue color in a
solution which has been digested with soda and acidified with nitric acid.


HgO, =216.

PREPARATION. By adding solution of perchloride of mercury to ex-
cess of solution of soda: chloride of sodium and water are formed, and
the yellow mercuric oxide precipitates.

CHARACTERS AND TESTS. A smooth yellow heavy powder, becoming
gray on exposure to light; it is insoluble in water, readily soluble in acid,
entirely volatilized by heat, being resolved into oxygen and mercurial va-
por. This oxide is an allotropic form of the red oxide; it is smoother,
and combines more readily with certain acids; it is better adapted for
ointment used on delicate surfaces, as the eyelids, and is preferred for
the preparation of oleates.


PREPARATION. By triturating and heating nitrate of mercury with
an equivalent of metallic mercury: nitrous oxide gas is given off.
Hg2NO 3 + Hg=2HgO+2NCv

CHARACTERS AND TESTS. An orange-red crystalline powder, almost
insoluble in water, soluble in acids, the solution giving a yellow precipi-
tate with caustic potash in excess, and a white one with ammonia; it is
wholly volatilized by a heat below redness, and was the salt from which
Priestley first disengaged oxygen (by .means of a lens and sun-light).


PREPARATION. By dissolving mercury in cold, slightly diluted nitric
acid, when mercurous nitrate is formed.

3Hg+4HNO 3 =3HgNO 3 + 2H,O+NO.
By subsequent boiling, this is changed into the mercuric nitrate.

3HgN0 3 +4HN0 3 =3(Hg2NO 3 ) + 2
Free nitric acid is also contained in the solution.


CHARACTERS AND TESTS. A colorless, strongly acid solution, from which
excess of caustic potash precipitates the yellow oxide; water also de-
composes the solution, precipitating oxynitrates. The presence of nitric
acid is shown by the darkening of crystals of ferrous sulphate when in-

NABAR, HgS,=232 (not officinal).

PREPARATION (L. P). By melting together, with proper precautions,
equivalents of mercury and sulphur, triturating the mixture, and then

CHARACTERS AND TESTS. In dark-scarlet crystalline masses, which,
when powdered, become vermilion; volatilizes on heating; on reduction
with potash, the metallic mercury separates.


PREPARATION. By heating mercury with sulphuric acid, sulphurous
acid gas escapes, and mercuric sulphate and water are formed, as repre-
sented in this formula:

Hg+2H a S0 4 =HgS0 4 +SO a +2H s O.
The mixture is then evaporated to dryness.

CHARACTERS. A heavy white crystalline powder, which is decomposed
by water into a soluble acid sulphate and a yellow oxysulphate, known
as turpeth mineral.



PREPARATION. By dissolving 1 part of ferro-cyanide of potassium in
15 of boiling water, adding 2 parts of mercuric sulphate, heating for ten
minutes, filtering, and cooling to crystallization: besides the cyanide,
mercury, ferric sulphate, and sulphate of potassium are formed in this

CHARACTERS AND TESTS. Rectangular prisms, sometimes transparent,
generally opaque and white, taste metallic. Is stable in air, soluble in
water, sparingly so in alcohol.

ABSORPTION AND ELIMINATION. Metallic Mercury. The question
whether mercury can be absorbed in its metallic state, either by the skin
or the digestive tract, has scarcely yet passed from the region of debate,
and contradictory facts have been alleged concerning it. Von Hasselt
found the metal in the blood of mercurialized persons (Stille), and Colson
obtained a deposit of it from a brass plate placed for a time in contact


with blood drawn from a patient who had taken the drug (Archives Gen.,
xii., p. 86). Claude Bernard filled the medullary cavity of a dog's femur
with quicksilver, closed the perforation with wax, and allowed the soft
parts to heal; three months afterward most of the metal had disappeared
from the bone, and was found in small globules encysted on the surface
of the lungs. In another dog the metal was injected into the jugular
vein, and twenty-five days afterward found " divise a, 1'infini," in the
cardiac tissue under the pericardium, so that it would not remain in the
blood, though taken up by it. Oesterlen used mercurial frictions on cats,
giving them also internally pills of blue ointment, and he Imported the
finding of mercurial globules, not only in the skin, but in most of the or-
gans. Overbeck confirmed these results on rabbits (quoted by Stille),
and Blomberg detected mercurial corpuscles in cats to which he had given
pills of citrine ointment (" Treatise on Absorption of Mercury," Hel-
singfors, 1868). The latter observer used mercurial friction on the arm
of a dead body, and found globules in the corium and mucous layers, but
not deeper.

Such observations would seem conclusive, but that Barensprung,
Rindfleisch, and others find it impossible to verify them: they have made
the frictions and given the pills, but they cannot find the metal in the
blood, nor yet in the corium. Autenrieth could find no amalgam on
plates of gold introduced into the subcutaneous tissue under the place of
friction, and Gubler and Neumann, while they recognized the metal in
the sweat-glands and hair-follicles, could trace it no further. Rindfleisch,
it is true, found mercury once in mesenteric glands after giving mercurial
pills, but there were ulcerations in the intestinal mucous coat which might
have permitted the passage of the metallic globules (Archiv fur Derma-
tol., iii., 1870). The most recent observations are those of Fleischer, who
concludes from numerous experiments, that " frictions with mercurial
ointment cause the penetration of metallic particles into the superficial
layers of epidermis, but not deeper: " and a consideration of the whole
evidence warrants this negative conclusion, that although metallic mer-
cury, when administered by the mouth in substance, or actually placed
within the tissues, may circulate and be deposited, it does not seem to be
altered or absorbed in the ordinary sense, and when applied by friction it
usually does not pass either into the deeper tissues or into the blood.

The physiological effects of mercurial frictions must be connected,
therefore, with its absorption in some other form: either mercurial vapor
is inhaled during the process, or a sebacic oxide of mercury enters through
the skin. As to the former point, we know that sometimes salivation has
occurred in a wife, six hours after a friction made by the husband upon
himself only, both living in rather a small room (Samelsohn, quoted by
Hallopeau); and additional evidence in favor of such an effect is furnished
by the delicate observations of Merget. He demonstrated that mercury


volatilized at all temperatures, and, by means of iridium-paper (which
showed a dark stain on contact with the vapor), he proved its presence
on the hands or other parts of the body of persons who had spent only a
few hours in a workshop where it had been used ( Comptes JRendus, De-
cember, 1871). That the mercurial vapor is not absorbed only by the
lungs is evident from a carefully devised experiment by Fleischer (Er-
langen): he caused frictions to be made upon an arm while the patient
with face covered by a mask breathed only external air; the limb was
then carefully wrapped in wool and oiled silk for sixty hours, and during
that time tH% presence of mercury (in very small quantity) was verified in
the urine.

We may state then that mercurial vapor is absorbed, not only by tho
lungs but also by the skin, and indeed the results of ordinary fumiga-
tions when the head is external to the apparatus would be sufficient
to prove this. Gubler holds that the sweat-glands are the active agents
in this absorption, and Rohrig admits that mercury in vapor can pass
through the epidermis (Strieker's Jahrb., ii. 1873). It is probable also
that some may be absorbed as oxide in combination with fatty acids
(sebacic), or acids contained in the perspiration (Christison). Biiren-
sprung and others have proved the presence of such oxide in " blue oint-
ment;" Nevins calculated it at 1 part in 100, and Voit, analyzing por-
tions of skin which had been rubbed with it, found the oxide constantly
present. A soluble double salt may be formed with the chlorides of the
perspiration (Miiller), and, if mercurial oxides be given internally, Voit
argues that the chlorides of the blood can change suboxide into calomel
and peroxide into perchloride, which salts then combine with sodium
chloride and albumen.

Metallic mercury, given by the mouth, usually passes off unchanged
by the bowel; in the rare cases where it has given rise to constitutional
effects, a portion has probably been oxidized or changed into sublimate.
In the very finely divided form, when the metal is " extinguished " by
continued friction with chalk (gray powder), or with confection of roses
(blue pill), Rabuteau thinks it may be directly absorbed from the intes-
tine, but no doubt some oxidation occurs during trituration, and the
oxide would be soluble more readily in the acid of the gastric juice; mer-
cury in a volatile form would also be disengaged from such compounds as
readily within the body as without, at the same temperature. Mercurial
ointment or pill, introduced as a suppository into the rectum, produces
physiological effects perhaps more quickly than by the stomach. In the
various trades which require the handling of quicksilver such as barome-
ter- and mirror-making, gilding, and skin-dressing, and again, in miners at
Almaden and elsewhere the physiological effects produced are mainly
traceable to inhalation of the vapor.

Calomel. Calomel being not only insoluble, like metallic mercury, in


ordinary liquids, but being also non-volatile, there lias been still more
speculation as to how it could reach the current of the circulation.

According to the classic theory of Mialhe, it becomes, like other mer-
curial compounds, changed more or less into the soluble perchloride by
the action of the gastric fluids, and is absorbed only to the extent of such
change. Mialhe argued from the results obtained by heating together
calomel and ammonium chloride in a test tube, but Buchheim and others
failed to verify any formation of perchloride in such a mixture at the
temperature of the body. Rutherford, experimenting more recently, di-
gested 5 gr. of pure calomel in distilled water, with .02 per cent, of free
hydrochloric acid (the same proportion as in gastric juice) at 100 F.
for seventeen hours, and obtained % gr. of perchloride, but it is unlikely
that even so much as this would be formed in the stomach; and the
action of calomel so far differs from that of corrosive sublimate as to
render it, clinically speaking, improbable that it only depends upon some
formation of the latter. Rabuteau, however, maintains that calomel does
become changed into perchloride and metallic mercury; also that this
perchloride combining with soda salts forms chloride of sodium, and sets
free more of the metal that under the influence of such changes the com-
pounds are absorbed acids and alkalies being afterward eliminated, and
the metallic mercury in part deposited. In this view, though complex,
there seems some analogy with what is known of the behavior of salts of
gold, silver, and some other metals, and calomel certainly resembles in
action preparations of metallic mercury otherwise we have no proofs
of such direct absorption of it, but rather the reverse.

Various observers have directed attention to the possibility of calomel
being rendered soluble in other combinations, e.g., with albumen (Buch-
heim), or as a double salt formed with chlorides of the blood (Graham).
Headland pointed out that bile exerts some solvent power on calomel
(Lancet, i., 1858), and Gubler asserts that an excess of various organic
materials albumen, mucous, epithelium acts similarly; some limit, how-
ever, must be placed to this observation, for the excess of mucin in the
stomach of a dog entirely prevented the absorption of calomel that had
been in jected into the stomach (Rutherford, Exper. 38). An experiment
of Tuson's is more to the point: he placed in one vessel calomel witli
dilute hydrochloric acid, and in another the same mixture with a propor-
tion of pepsine : after digestion for an equal number of hours sulphuretted
hydrogen was passed into the solutions and produced a black precipitate
in that with pepsine, but none in the other, proving clearly the effect of
the organic subtance in promoting the solution of the calomel (Medical
Times, i. , 1872, p. 518). Jeannel pointed out the importance of fatty
matters for the solution of calomel: in the presence of an alkaline carbon-
ate, it is readily decomposed with precipitation of gray oxide; of this lat-
ter a small proportion is retained in solution by the water, but if a fatty


oil be mixed with the alkaline solution, this proportion is very much in-
creased: the same might readily occur in the intestine (Abstract :
Schmidts Jahrb., 1869, Bd. cxliii., s. 9).

It is quite possible, as H. Wood remarks, that in consequence of the
varying composition of the intestinal fluids and the complex chemical
relations of calomel, its solution and ultimate absorption may be accom-
plished in several ways: when more chlorides are present some per-
chloride may be formed, and when sulphuretted hydrogen is in excess
it may produce some amount of soluble sulphide.

Dr. Law, of Dublin, was the first to notice how much the absorption
of calomel could be promoted, especially in severe illness, by minute sub-
division of the dose, giving, e.g., T ^ gr. every hour (Dublin Quarterly
Journal, xiv., p. 393). Trousseau amply corroborated this observation,
and it is, d priori, reasonable, for the smaller quantities more readily
come in contact with the intestinal fluids to form the double salts or
soluble compounds described.

Bellini indicated a difference in the mode of absorption of calomel ac-
cording to the condition of the stomach: thus, when taken fasting, only
a small amount was at first dissolved, with formation of double chloride
of mercury and sodium, and lactate of mercury; more was dissolved in the
intestine, under the influence of alkaline carbonate, an oxide of mercury
being at first formed, and then a double salt; in the large intestine a sul-
phide was formed (except in the case of infants). Introduced into the
stomach during digestion, it was wholly, or almost wholly, decomposed
under the action of proteinous substances, metallic mercury being formed
and a soluble albuminate.

From the cellular tissue some calomel may be absorbed, since consti-
tutional effects have been produced by its hypodermic injection when
simply suspended in liquid, but the major part remains unabsorbed, and

Online LibraryCharles D. F. (Charles Douglas Fergusson) PhillipsMateria medica and therapeutics, inorganic substances; (Volume 2) → online text (page 23 of 40)