OF THE SUBSTANCES USED IN THE FORMATION OF FIRE-WORKS.
Sect. I. Of Nitrate of Potassa, or Saltpetre.
Nitrate of potassa, nitre, or saltpetre, is composed, as its
name expresses, of nitric acid, and potassa. When pure, it
contains, according to Kirwan, potassa 51.8, nitric acid 44,
and water 4.2 in the hundred. This salt, when pure, or
even mixed with other saline substances, is recognised by
placing it on hot coals. Slight detonations, and a hissing noise,
with a vivid combustion take place. It is also decomposed
by sulphuric acid, and the nitrous vapour is apparent from
its smell and colour.
Nitrate of potassa crystallises in six-sided prisms, terminated
by six-sided pyramids. Its specific gravity is 1.933.
Its taste is sharp and cooling. One part is soluble in seven
parts of water, at the temperature of 60 degrees, and in
rather less than its own weight of boiling water.
It melts in a strong heat, and by cooling congeals into an
opaque mass, called crystal mineral, or sal prunelle.
Exposed to a red heat, it disengages oxygen gas, and
passes to the state of a nitrate; at a higher temperature, this
is decomposed, and oxygen, azote, and a portion of nitrous
acid, which has not been decomposed, are evolved. What
remains is potassa. When projected on ignited coals, it burns
brilliantly. Detonation also ensues by mixing nitre and
charcoal, and throwing the mixture into a red-hot crucible.
The residuum is carbonate of potassa. Fourcroy (Système
des Connoissances Chimiques, Tome iii, p. 124.) observes,
that metals, with nitrate of potassa, will decompose this salt,
and produce different coloured flame, extremely brilliant, on
which account such substances are used in fire-works.
The alchymists believed, they could obtain, from nitre, a
liquor, which would constitute, with other substances, the
philosopher's stone. The clyssus of nitre, they imagined,
possessed wonderful properties. The decomposition of nitre
by charcoal, they effected in two ways, viz. by submitting
the mixture to the action of heat in a crucible, or, otherwise
in an earthen or iron retort. In the latter case, they collected
a fluid, principally water, containing some carbonic acid,
and the aeriform product they suffered to escape. The residue
they named nitre fixed by charcoal, or, the extemporaneous
alkali of nitre. When, in the place of charcoal, a mixture
of sulphur and nitre was projected into a red-hot crucible,
they obtained a saline substance, to which they gave
the name of sal polychrest. This is the same as vitriolated
tartar, or sulphate of potassa, and is that salt which is formed
in the distillation of nitric acid from nitre, and sulphuric
acid. The crystal mineral, of some of the old pharmacopœias,
was nothing more than nitrate of potassa fused with
a portion of sulphur, and, therefore, a mixed salt, consisting
of nitrate and sulphate of potassa.
Nitrate of potassa, distilled with half its weight of sulphuric
acid, furnishes nitric acid, or concentrated spirit of
nitre. This, diluted with about an equal weight of water,
forms the aqua fortis of the shops.
A mixture of nitre and phosphorus, if struck with a hammer,
produces a violent detonation. Nitre oxidizes all the
metals at a red heat, even gold and platinum.
Nitre and sulphur, thrown into a red-hot crucible, produces
an instantaneous combustion, accompanied with a great
disengagement of light and heat. Sulphurous acid gas, with
sulphuric acid, is produced.
Equal parts of cream of tartar, (supertartrate of potassa,)
and nitre, deflagrated in a crucible, form white flux. Two
parts of tartar, and one of nitre, treated in the same manner,
produce black flux.
Three parts of nitre, one part of sulphur, and one part of
sawdust, mixed together, form the powder of fusion.
When three parts of nitre, two parts of potash, and one
of sulphur, all previously well dried, are mixed together, the
compound is called pulvis fulminans, or, fulminating powder.
A small portion of this powder, or as much as will lay on a
shilling-piece, put on a shovel, and exposed to heat, will first
melt, become liver-coloured, and then explode with great
noise. The theory of this explosion is, that a part of the sulphur,
and the potassa unite, and form a sulphuret; the sulphuret
then decomposes water, and produces sulphuretted hydrogen
gas, which appears to be decomposed by the nitric acid; and
there results sulphurous acid gas, water, and, as Thenard
observes, protoxide of azote, azotic gas, and sulphate of potassa.
The loudness of the report depends on the combustion
of the whole powder at the same instant, which is secured
by the previous fusion it undergoes. Gunpowder, on
the contrary, burns in succession, although apparently instantaneous.
In using common potash, there is also, as the alkali
contains it, carbonic acid, given out in the state of gas. In
fact carbonic acid appears to assist the explosive effect of this
powder, for when it is prepared with potash, containing
little carbonic acid, its detonating power is considerably less.
Nitre likewise enters into the composition of another fulminating
powder, invented by Dr. Higgins. Higgins's fulminating
powder is composed of three and a half parts of
nitre, two parts of crude antimony, and one part of sulphur.
This is used in the same manner as the former.
Nitre enters into the composition of gunpowder, which
we shall notice under a separate head. The proportions of
nitre, sulphur, and charcoal, for the formation of gunpowder,
which are considered the best, are, 75 parts of nitre, 121/2 of
charcoal, and 121/2 of sulphur.
The new powder of MM. Gengembrie and Bottée, which
inflames by percussion, but without explosion, is composed
of 21 parts of nitre, 54 parts of chlorate of potassa, 18 parts
of sulphur, and 7 parts of lycopodium.
A mixture of nitre and crude antimony projected into a
red-hot crucible, produces a deflagration more or less rapid,
forming a composition which is used in pharmacy, and medicine.
The quality of saltpetre may be determined by a variety
of experiments. Fire-workers judge of its quality by the
colour of its flame.
The flame should be white. If it be green or yellow, it is
said to be impure.
Nitric acid, obtained by distilling saltpetre and sulphuric
acid, has a powerful effect on inflammable substances. If
nitric acid, or in preference, the fuming nitrous acid, be
poured on spirit of turpentine, especially if it be old, it will
inflame. To succeed, however, in this experiment, a small
portion of sulphuric acid is usually added to the nitric acid.
As this effect is owing to the facility, with which the acid
parts with its oxygen to inflammable bodies, other essential
oils, besides turpentine, will have the same effect. If the same
acid is poured on finely pulverized charcoal, or on lampblack,
combustion will also take place. When oils are used,
water as well as carbonic acid is produced, and when charcoal
or lampblack, carbonic acid alone. There is also a large
quantity of carbon, in the former instance, which remains on
the plate, or dish. M. Delametherie (Journal de Physique,
1815) has shown, that olive oil may be converted into a
substance, resembling, and having many of the properties of,
wax, by mixing it with a given proportion of nitric acid. The
acid is decomposed, deutoxide of azote is formed, and the
oil acquires a hard consistence. A candle made with this
artificial wax, he observes, burns with a clear light and without
smoke. The experiment with the glace inflammable is
on the same principle.
Morey (Silliman's Journal, vol. ii, p. 121.) states a singular
experiment, in which nitre is used; viz: If to tallow or linseed
oil, a small quantity of saltpetre be added, and the temperature
raised to nearly that of the boiling point, the saltpetre
appears to be dissolved by the oil; they will evaporate
together, and the mixture, or the vapour, will burn, wholly
excluded from the atmosphere.
Saltpetre was one of the substances employed by the alchemists.
It appears from the memoir of Geoffroy, (Coll. Academ.
1722,) that the object of the alchemists was twofold; the
transmutation of metals, and particularly what were denominated
the baser metals into the precious, which they pretended
to effect by a universal spirit, the grand elixir, the
philosopher's stone, &c. and the reduction of metals to their
earths. Alchemy was introduced into Europe by the crusaders,
and it is remarkable, that, in the reign of Henry IV,
an act was passed to make it felony to transmute metals.
Mr. Boyle, aware of its absurdity, suggested the propriety
of repealing that act, which was done. One of their powders
was composed of nitre, cream of tartar, and sulphur.
Preparation. Although nitrate of potassa is generated in
abundance, particularly in the East, yet in all countries,
where the circumstances are favourable to its production, it
is found. It never occurs, native, in very large masses. It
is generally found in an efflorescence, on the surface of the
soil, or in caverns. It never exists in the soil more than a
few yards beneath the surface. We may remark, that native
nitre has never been found in pure clay, or pure sand, except
in the rock-ore, as it is called, of the western United
States. It is often found in caverns, and fissures in calcareous
rocks.
In the East Indies, the districts which furnish saltpetre,
are swept at certain seasons of the year. This is repeated
two or three times a week; for the saltpetre again appears in
the same places, in the form of efflorescence.
It is supposed that some countries furnish saltpetre, in
consequence of the drought, which continues for some time.
At Lima, M. Dombay informs us, there is seldom rain; and
the fields, which serve as pasturage for beasts, are so much
covered with saltpetre, as to be removed with the spade.
There must then be a rapid formation of nitre. M. Talbot
observes, that in the meridional provinces of Spain, the earth
frequented by animals, contains it, ready formed. When
saltpetre became an article of importance, the rulers of Germany,
&c. justified themselves in exclusively carrying away
the incrustations of walls from private houses, which, when
it could be used, became accessorium fundi. Accordingly this
regale, as it was called, was extended every where, and was
generally unpopular. In 1419, Gunther, archbishop of
Magdeburgh, issued the first grant, which was the right of
searching saltpetre and boiling it, during a year, in the district
of Gibicherstein, for which the person, to whom it was
granted, was to pay a barrel of saltpetre, and deliver to the
archbishop the remainder at a certain price.
The succeeding archbishop, Frederick, let, in 1460, to a
burgher of Halle, all the earth and saltpetre that could be
collected in the bailiwick of Gibicherstein, for four years, at
the annual rent of a given quantity of refined saltpetre.
Bishop Ernest, in 1477, let, for his time, the privilege of
collecting saltpetre. In 1544, saltpetre was collected, in the
same manner, from the rubbish before the gates of Halle;
and in the year following, the magistrates of Halle erected a
powder mill, and had saltpetre works. John VI, archbishop
of Triers, granted similar privileges in 1560. The
saltpetre regale, was long known, and confirmed by a Brandenburgh
decree in 1583.
Old walls, and the vicinity of stables, frequently exhibit
saltpetre in the state of efflorescence. It was the ancient scrophula
contra lapides, represented as a kind of leprosy. For
the spontaneous production of nitre, animal and vegetable
substances, in a state of decomposition, and the presence of
dry atmospheric air are necessary. That lime, and the calcareous
carbonates also promote its formation, there can be no
doubt.
Notwithstanding the large quantity of saltpetre collected
in the East Indies, we are told, that two-thirds of the whole
are annually sent into China, and other parts of Asia, to
make artificial fire-works. The pyrotechny of the Chinese
is said to be very perfect; in variety and beauty, some writers
assert they exceed all other nations. There is a natural
nitre bed at Apulia, near Naples, which affords 40 per centum
of nitre. Pelletier, (Ann. de Chim. tome xxii.) has published an
analysis. The cavity of Molfetta is one hundred feet deep,
containing grottos or caverns. Nitrate of potassa is found in
the interior, in efflorescence or crusts, attached to compact
limestone. On removing these efflorescences, others appear.
The soil in this cavity is richly impregnated with nitre.
In Switzerland, the farmers extract an abundance of saltpetre
from the stalls under their cattle. During the American
revolution, when every expedient was resorted to, to obtain
a supply of this article, the floors of tobacco houses, &c.
were dug up and lixiviated. In the reign of Charles the
First, certain patentees were authorised to dig up the floors
of all dove-houses, stables, &c. the floors being again laid
with mellow earth.
The Ukraine, Podolia, Hungary, Spain, Italy, Peru, and
India, furnish more or less of this salt, which is extracted by
lixiviating the earths that compose the soil. The springs, in
particular districts of Hungary, contain it.
We are informed, (Ann. de Chim. xx. 298,) that, during
the second and third years of the French Republic, the government
required every district to send two intelligent
young persons to Paris. This convocation, consisting of
nearly eleven hundred persons, received regular instruction
from their first chemists, partly concerning the manufacture
of cannon, and partly respecting the manufacture of saltpetre
and gunpowder. This body of pupils was afterwards distributed
among the different establishments in proportion to
their abilities, and saltpetre was soon furnished in abundance.
In the United States, we have an abundant source of saltpetre
in the nitre caves of the western country. There is now
no occasion for lixiviating the soil of tobacco houses, or of stables,
or the refuse of old buildings, the preparation of artificial
nitre beds, as adopted in France, or for any other expedient, to
furnish a supply of saltpetre; these caverns, which are calcareous,
producing it in great abundance. The earth of these caves
does not, however, contain pure nitrate of potassa, but generally
a mixture of this salt and nitrate of lime, a calcareous nitrate
which constitutes the principal part. The latter is changed
into nitrate of potassa, as we shall observe more particularly
hereafter, by making a lixivium of the earth in the usual
manner, and passing it through wood ashes. The alkali,
which the latter contains, decomposes the nitrate of lime, by
uniting with the nitric acid; hence the fluid, which passes
through, is nitrate of potassa or saltpetre. This is evaporated,
and suffered to crystallize. It is then the crude, or rough nitre,
which is purified, principally by re-solution, and crystallization.
The saltpetre makers, at the caves, have found, that two
bushels of ashes, made by burning the dry wood in hollow
trees, afford as much alkali as eighteen bushels of ashes obtained
from the oak. Notwithstanding the nitre earth contains
a mixture of the nitrates of potassa and lime, nitrate of
potassa, nearly pure, has been discovered. It is sometimes
found in the fissures of sandstone, or among detached fragments.
Some of these masses are said to weigh several hundred
pounds.
Besides these caverns, which have been accurately described
by Dr. Brown, in the Transactions of the American
Philosophical Society, (vol. v, vi.) similar caverns have been
discovered in Tennessee, and in some parts of Virginia and
Maryland. At Hughes' cave near Hagerstown, in Maryland,
this salt has also been made.
We are of opinion, that most of the calcareous caverns in
the United States, if carefully examined, might be found to
contain nitre, or at least, the calcareous nitrate, which is readily
converted into nitre by lixiviation with wood ashes, or
the addition of a due quantity of potash.
Professor Cleaveland, in noticing the saltpetre caves of the
western country, observes, (Elementary Treatise on Mineralogy
and Geology,) that one of the most remarkable of these
caverns is in Madison county, on Crooked Creek, about sixty
miles S. E. from Lexington. This cavern extends entirely
through a hill, and affords a convenient passage for horses
and wagons. Its length is six hundred and forty-six yards;
its breadth is generally about forty feet; and its average
height, about ten feet. One bushel of the earth of this cavern,
commonly yields from one to two pounds of nitre; and the
same salt has been found to exist, at the depth of at least fifteen
feet; even the clay, a fact which seems rather remarkable,
is impregnated with nitrate of lime. Kentucky also furnishes
native nitre under a very different form, and constituting
what is there called the rock ore, which is in fact a
sand stone, richly impregnated with nitrate of potassa. These
sand stones are generally situated at the head of narrow vallies,
which traverse the sides of steep hills. They rest on calcareous
strata, and sometimes present a front from sixty to
one hundred feet high. When broken into small fragments,
and thrown into boiling water, the stone soon falls into sand;
one bushel of which, by lixiviation and crystallization, frequently
yields ten pounds, and sometimes more than twenty
pounds of nitrate of potassa. The nitre from these rocks contains
little or no nitrate of lime. This account is corroborated
by Dr. Brown,[13] to whom our author is indebted for his remarks.
In a memoir in the American Philosophical Transactions
by Dr. Brown, then of Lexington Kentucky, we have a description
of a nitre cave on Crooked Creek, with the process
for extracting the saltpetre. From this memoir, the following
extracts are made: The water which percolates through
the cave in summer, as the walls and floor are dry in winter,
condenses upon the rocks, and the substance thus formed, has
the same properties as the salt obtained by lixiviating the
earth of the floor. As far as the workmen have dug, the
earth is strongly impregnated, every bushel of which, upon
an average, furnishes one pound of nitre. The same earth
will be again impregnated, if thrown into the cave. What
length of time it requires to saturate it, is not known.
The workmen have different modes of forming an opinion
with regard to the quantity of nitre, with which the earth
may be impregnated. They generally trust to their taste;
but it is always considered as a proof of the presence of the
nitre, when the impression made one day on the dust by the
hand or foot disappears the day following. Where there is
a great deal of sand mixed with the dust, it is commonly
believed that a small quantity of potash will suffice for the
operation. The method of making saltpetre, usually practised
in Kentucky, is as follows:
The earth is dug, and carried to hoppers of a very simple
construction, which contain about fifty bushels. Cold water
is poured on it for some time, and in a day or two, a solution
of the salts runs into troughs placed beneath the hoppers.
The lixiviation is continued as long as any strength remains
in the earth. The liquor is then put into iron kettles, and
heated to ebullition; it is afterwards thrown upon a hopper
containing wood ashes, through which it is suffered to filtrate.
As the alkaline part of the ashes is discharged before
the nitrate passes through, the first runnings of this hopper are
thrown back, and after some time, the clear solution of nitrate
of potassa runs out, mixed with a white curd, which
settles at the bottom of the trough. This clear liquor is
boiled to the point of crystallization, then settled for a short
time, and put into troughs to crystallize, where it remains
twenty-four hours; the crystals are then taken out, and the
mother water thrown upon the ash hopper, with the next
running of the nitrate of lime. When the quantity of the
nitrate of lime is too great for the portion of ashes employed,
the workmen say their saltpetre is in the grease, and that
they do not obtain a due quantity of nitre. If too much
ashes are used, they say it is in the ley; and when it is left to
settle previous to crystallization, a large quantity of salt will
be deposited in the settling troughs, which they call cubic
salts. These salts are again thrown upon the ash-hoppers,
and are supposed to assist in precipitating the lime from the
nitrate of lime, and in the opinion of the workmen are
changed into pure saltpetre. To make a hundred pounds
of good saltpetre at the great cave, eighteen bushels of oak
ashes are necessary; ten of elm, or two of ashes made by
burning the dry wood in hollow trees. The earth in some
caves does not require half this quantity of wood ashes to
decompose the earthy salts.
When wood ashes cannot be obtained in sufficient quantity,
they make a lixivium of the earth, and boil it down, which
they call thick stuff. This is put in casks, and transported
to a place where ashes can be had. When dissolved and
passed through wood ashes, it is changed, as in the former
process, into saltpetre. Having thus given the Doctor's account,
let us inquire, in the next place, into the theory of the
process.
The theory is very evident. The mixed nitrate, consisting
of variable proportions of nitrate of lime and nitrate of potassa,
is extracted from the saltpetre earth by water, which
dissolves it. Now, as the affinity of nitric acid for potassa
is greater than for lime, and consequently potassa will decompose
nitrate of lime, when the lixivium is passed through
wood ashes, the potassa they contain will unite with the nitric
acid, and the lime be separated, which remains in
the hopper. The liquor holds in solution no other salt
than nitrate of potassa, provided the quantity of alkali in
the wood ashes be sufficient to effect the decomposition;—if
more, it will pass through in an uncombined state; and if
less, the liquor will contain nitrate of lime. As the alkali
contains more or less carbonic acid, the decomposition is
not a case of single but of double affinity, in which we form,
at the same time, a carbonate of lime.
When the solution is boiled, and set aside in the troughs
to crystallize, the nitre will form in a regular manner. The
mother water, or the fluid which remains after the crystallization,
may contain, from the circumstance before stated, either
potash, or undecomposed nitrate of lime—hence it is
thrown on the hopper in a subsequent operation.
The nitre, however, as made at the caves, is called rough
or crude nitre. Before it is used for the manufacture of
gunpowder, and other purposes, it is purified or refined.
This operation, which we shall notice more fully hereafter,
is nothing more than the separation of all earthy salts, and
the alkaline muriates and sulphates; in other words, the conversion
of the whole by the separation of foreign substances,
into pure nitrate of potassa.
The mode of treating the rock ore, or sand rocks, which
contain nitre, is the same as before given. It contains more
nitrate of potassa, and therefore requires less potash, and in
some instances, the nitre is perfectly pure. The sand rocks
often yield twenty or thirty pounds per bushel. A mass of
pure nitre, weighing sixteen hundred pounds, has been discovered.
Smaller masses have also been found.
The rocks which contain the greatest quantity of nitre are
extremely difficult to bore, and are tinged brown or yellow.
Saltpetre makers find it to their interest to work the rock ore
in preference to the calcareous nitrate, as it yields more nitre.
It is a fact well known, that foreign saltpetre contains a variety
of deliquescent salts, or those salts which attract and
absorb moisture and also common salt. The efforts of European
refiners are directed to their separation. The saltpetre
of the Western country, Dr. Brown assures us, does not
contain common salt.
Dr. Brown, in Silliman's Journal, i, p. 147, in a letter
to professor Silliman, observes, that there exists a black substance
in the clay under the rocks, of a bituminous appearance
and smell. This black substance, it appears, accompanies the
sand-rock nitre, and is the same as that found in Africa,
which also accompanies nitre in that country. Animal matter
seems to have existed in the nitre caves of Africa, forming,
as Mr. Barrow expresses it, either a roof or covering; no
such matter, however, has ever been found in or adjacent to
the nitre caves of the Western country.
The observations of Mr. Barrow on the subject of the
saltpetre of Africa may be interesting to the reader. He
observes, (Southern Africa, p. 291,) that, about twelve miles
to the eastward of the wells, (Hepatic Wells), in a kloof of
the mountain, we found a considerable quantity of native nitre.
It was in a cavern similar to those used by the Bosgesmans
for their winter habitations. The under surface of
the projecting stratum of calcareous stone, and the sides
that supported it, were incrusted with a coating of clear,
white saltpetre, that came off in flakes. The fracture resembled
that of refined sugar; it burnt completely without leaving
any residuum; and if dissolved in water, and thus evaporated,
crystals of pure prismatic nitre were obtained. This
salt, in the same state, is to be met with under the sand-stone
strata of many of the mountains of Africa. There was also
in the same cave, running down the sides of the rock, a
black substance, that was apparently bituminous. The peasants
called it the urine of the das. The dung of this gregarious
animal was lying upon the roof of the cavern to the
amount of many wagon loads.
The Rev. Mr. Cornelius, in describing a cave in the Cherokee
country at Nicojack, the north west angle in the map of
Georgia, (Silliman's Journal, vol. i, p. 321,) observes, that
it abounds with nitrate of potassa, a circumstance very common
to the caves of the Western country, and is found covering
the surfaces of fallen rocks, but in more abundance beneath
them. There are two kinds; one is called the "clay
dirt," the other the "black dirt." The earth, however, contains
calcareous nitre, and for that reason an alkaline lixivium
is employed. In short, the process employed there is
the same as at the other saltpetre caves which we have described.
One bushel of the clay dirt yields from three to
five pounds of nitre, and the black dirt from seven to ten
pounds. It seems also, that the same dirt, if carried back to
the cave, will become impregnated with nitre.
Mr. Cornelius remarks, that these caves have been used
by the natives as burial places; in one of which he counted a
hundred human skulls in the space of twenty feet square; and
infers, that, by the decomposition of animal matter, the acid
of nitric salts arises, and therefore that this may have occasioned
the formation of the nitrates of potassa and lime.
At Corydon, in Indiana, there is a cave, which, according
to Stilson's account, contains both nitrate of lime, and
nitrate of magnesia. It is not worked.
Kain, in his remarks on the Geology and Mineralogy of
East Tennessee, (Silliman's Journal, vol. i, p. 65,) observes,
that the numerous caves which have been found in the Cumberland
mountains, and other parts of Tennessee have been
very productive of nitrate of potassa; and in confirmation of
the remarks before made, he adds, in investigating the causes
that have given rise to these salts, that wild animals burrow
in these caves; that, when pursued by the hunter, they
make them the places of their retreat, and probably die
there; that the aborigines have made them a place of burial;
and that the streams of water, which flow through them, in
wet weather, carry with them not only great quantities of
leaves, but many other vegetable productions.
Without offering any theory, by which we may account
for the formation of nitre, in nitre caves, or in situations
which cannot be influenced by the putrefactive process, we
may merely remark, that as nitric acid is composed of oxygen
and azote, there must be some operation unknown to us,
by which the union of these elements takes place. Nascent
azote must unite with the base of oxygen gas; but whence,
in saltpetre caves, proceeds the azote and the oxygen? It
appears that calcareous bodies facilitate the formation of
nitre, as they do in artificial nitre beds. The greater part
of the nitrous earth is lime; and it also appears, that the
same earth, after the extraction of the saltpetre, will again furnish
it. We know that lime is a compound of a base called
calcium united with oxygen; but in what manner it promotes
the union of azote and oxygen, or furnishes either one
or the other of these bodies, or perhaps both, is altogether
uncertain. Nor can we account for the formation of potash
in the native nitre of the nitre caves. In other situations,
as for instance where nitrous efflorescence appears on the
earth, and in artificial nitre beds, in which animal and vegetable
substances are in the act of decomposition by the putrefactive
fermentation, we may account for the generation
of nitric acid.
It is extremely probable, that the azote of the atmosphere,
and oxygen may combine spontaneously, under particular
circumstances, in various operations of nature. Azote, it is
known, forms with oxygen two gases, a protoxide and deutoxide,
and the same elements in other proportions form
nitric acid. Some condition, unknown to us, must, as an
operating cause, produce this compound. As a condition
for its generation, the presence of calcareous and alkaline
matter, favours the formation of nitric acid. Of this fact,
we have sufficient proof, in the generation of nitre in artificial
nitre beds. But, with respect to natural causes, although
the facts themselves are conclusive, we know little or nothing.
Atmospheric air is a mixture, or compound, according to
some, of two gases, oxygen and azote, with carbonic acid;
but the proportion of the latter rarely exceeds two per cent,
while the quantity of oxygen is about twenty-two. It is a
solvent, as well as a vehicle, and hence may contain water,
gaseous fluids, &c. Miasmata, which is contained often in
the air, are vapours or effluvia, that affect the human system,
and bring on diseases, of which the principal are the intermittent,
remittent, and yellow fevers, dysentery and typhus.
That of the last is generated in the human body itself. The
same, or analogous causes, that produce the formation of
nitric acid, may, under other circumstances, cause the formation
of miasmata; for moist vegetable and other matter, in
some unknown state of decomposition, generates it, and is
known to have caused the yellow and other malignant fevers.
(See an admirable work on the causes, &c. of the yellow fever
in Philadelphia, by Samuel Jackson, M. D. president of
the board of health, etc. in reply to the observations of Dr.
Hosack.) The contagious virus of the plague, small pox, etc.
as it operates in a more limited distance than marsh, or
other miasmata, is communicated only in certain localities,
and through the intermedium of the atmosphere. As to
the chemical nature of miasmata, there can be no doubt that
azote, under some form of combination, is one of its component
parts, and one of the causes of disease. Is not cyanogen,
or carburet of azote, perhaps combined with hydrogen,
in the form of hydrocyanic or prussic acid, the
substance, or principal substance, which forms the miasmata,
that engenders the yellow fever? What compounds may be
formed of hydrogen, sulphur, phosphorus, carbon, and azote,
so as to produce miasmata, that will act specifically on the
system for the production of intermittent, remittent, yellow,
typhus, and other fevers?[14] This inquiry, permit me to add,
is one of no small moment, as it involves in it a question
of great importance relative to the origin of yellow fever.
While we thus digress, in noticing the compounds of azote,
let us briefly remark, as an indisputable conclusion, that the
same causes of malignant disease in the West India islands,
operating under similar circumstances in every respect, may
engender the same disease in our cities.
The atmosphere is subject to changes of various kinds,
and may be considered not only as a solvent, but a repository
for different foreign bodies. Electricity, an agent so
essential in the economy of nature, has its ends, its uses; and
while, no doubt, it unites hydrogen with oxygen, in the most
elevated regions of the air, and forms water, it may act
under particular circumstances to produce a union of azote
and oxygen so as to generate nitric acid. Dr. Priestley,
(Transactions of the American Philosophical Society,) detected
nitric acid in snow. But of all atmospheric phenomena,
the formation of meteorolites, or meteoric stones, is the most
wonderful. If they be really formed in the atmosphere,
there can be no doubt, that the elementary principles which
compose them must exist in it; and that the phenomenon
denominated meteoric, in such cases, is no other than the
operating cause, by which meteoric stones are generated.[15]
Animal substances furnish azote, as it is one of their constituent
parts; and in the act of its separation, by uniting
with oxygen, principally furnished by the air, it forms nitric
acid; which, attaching itself to the alkali of the vegetable
matter, or the lime usually added to nitre beds, or to other
salifiable bases, forms either nitrate of potassa, nitrate of
lime, or a nitrate of the particular base. The lixiviation of
the nitrous substances, and the use of wood ashes, or potash
itself, will produce saltpetre.[16]
Brongniart has given the following process for purifying
or refining saltpetre: Pulverize the impure nitre, and wash
it three times in cold water, in the proportion of 35 lbs. of
water, to 100 lbs. of the salt, taking care to pour off the water
before another portion is added. These washings separate the
greater part of the muriate of soda, and the deliquescent salts,
such as nitrate of lime. When thus washed, the nitre is
to be dissolved in half its weight boiling water. On cooling,
the salt begins to crystallize, and, by agitating the liquid
during the process, minute crystals are obtained.
These crystals when dried are to be washed in 5 lbs. of cold
water for every 100 lbs. of the salt, and then dried in a temperature
of forty-five degrees.
In India, where nitrate of lime also occurs, but in situations
different from those in the United States, the natives
extract the saltpetre by a process similar to that we have described.
They refine it by solution in water, evaporation,
and crystallization. In France, the potash of commerce is
used; and the nitrates which are decomposed, are those principally
of lime and magnesia.
According to the analysis of M. Pelletier, and the experiments
of professor Vaizo, in 1781, they found the calcareous
earth of the cave at Naples, to contain forty or forty-two to
the hundred, of nitrate of potassa. (See Annales de Chimie,
tome 23.)
In 1792, M. Pickel announced the discovery of native
saltpetre, in a quarry in the neighbourhood of Wurtzburgh.
M. de la Rochefoucald discovered nitre in the neighbourhood
of chalk in France, in the departments of Seine and
Oise. MM. Lavoisier and Clouet, made a number of researches
with the same view. Since that time, saltpetre, or
nitrous earth has been found in several of the departments
of France; and it appears reasonable to conclude, that in all
situations favourable to the generation of nitre, where the
same causes operate, nitre must occur in more or less abundance.
From the rubbish of old buildings, saltpetre is obtained
in some quantity. Old plaster is said to give five per cent.
The soluble salts it contains, are six in number, viz: nitrate
and muriate of lime, nitrate and muriate of magnesia, and
nitrate of potassa, and muriate of soda. Now it is obvious,
that besides the decomposition of the earthy nitrates, the
earthy muriates also are decomposed by the potash, leaving
in solution, besides muriate of soda, if it is not decomposed,
by the potash, (which has this effect,) muriate, as well as the
nitrate of potassa. To refine the saltpetre prepared in this
manner, consists in separating the muriates. The proportions,
in which these salts are to each other in a hundred
parts, are stated by Thenard, (Traité de Chimie, Tome ii, p.
485,) to be ten, nitrate of potassa, seventy, nitrates of lime
and magnesia, fifteen, marine salt, and five, muriates of lime
and magnesia.
The mode of extracting saltpetre, and the various processes
which have been adopted for refining it, in France,
and on the continent generally, have but one object,—that of
lixiviating the substances which afford it, and subsequently,
separating all foreign salts. The best memoir was written
by count Chaptal, occupying forty-seven pages in the Annales
de Chimie, tome xx. In this he explains the theory at large.
In the same work, tome xxiii, there is also a paper by Guyton,
and many other memoirs of the same character. In Chaptal's
Chimie Appliqué aux Arts, tome iv, p. 119, in Thenard's
Traité de Chimie, tome ii, p. 485, and in the Annales de Chimie
et de Physique, tome v, p. 173, the subject is ably treated.
We will now give the process of extracting saltpetre from
the rubbish of old buildings, principally plaster, as adopted
in France. The lixiviation, in the first place, is performed in
the following manner: a certain number of casks or tubs,
thirty-six for instance, is placed in three ranges. These tubs
are pierced laterally near their bottom, by a hole of about
half an inch in diameter, and closed with a cork; they are
placed above a trough connected with a reservoir. There is
put then into each tub a bucket full of the plaster, previously
pounded, which is supported in the casks by cross sticks, a
certain distance from the hole, so as not to obstruct the passage
of the fluid. After this, a bushel of wood ashes is added,
and the tubs are then filled with the plaster. Water is then
put into the tubs of the first row, and after some time, the
stop cocks are turned; water is then put into the tubs of another
row, and the lixiviation is continued until the fluid indicates
the zero of Beaumé's areometer. The saline waters,
which are thus obtained, are divided into three parts, in proportion
to their specific gravity, or quantity of salt they contain.
The lixivium, of five degrees of the areometer, is
known under the name of eaux de cuite. The waters, which
are marked between three and five degrees, take the name
of eaux de forte; and those below three degrees are called eaux
faibles. According as the waters are weak, they are made to
run through another range of tubs, in order to saturate them.
When strong and weak solutions are made to pass through
the tubs in the same manner, proceeding from the second
row to the third, and from the third to the first, the earths
plaster, &c. being renewed, the lixiviation is not interrupted.
The lixiviation, it appears, is thus continued; for we obtain,
at the same time, weak waters from the second row, the
strong waters from the third, and the boiling waters, or those
fit to be put into the boilers, from the first.
When a sufficient quantity of the strong solution is obtained,
it is put into the copper, or boiler, and evaporated. During
the evaporation, there is a scum formed, and sundry earthy
substances, in the form of a mud, are deposited. This is usually
caught in a vessel placed in the boiler, which is raised
from time to time, by means of a rope, moved through a pulley,
and fastened to a chain from the handles of the vessel.
The solution is concentrated until it indicates the strength of
twenty-five degrees of Beaumé's areometer. It is then mixed
with the mother water of the preceding boiling, and a
concentrated solution of the potash of commerce is added,
until the precipitation ceases. The sulphate of potassa may
be used for the same purpose, at least to decompose the nitrate
of lime; but it must be used in the first instance, and
the operation finished in the common way, by the addition of
potash. The precipitation being finished, that is to say, the
nitrates of lime and magnesia, being transformed into nitrate
of potassa, the hot liquor is then carried in a large tub, called
the reservoir, and placed on the edge of the boiler. As soon
as the insoluble salts, which the solution contains, are deposited
there, which takes place immediately, the liquor is
drawn off clear by cocks, which are adapted to the tubs, and
received into the boiler, previously cleaned. The deposite
obtained in the boiling, is washed with a certain quantity of
the solution, which becomes clear, and is then mixed with
the preceding liquor.
From what has been said, the liquor must contain a great
quantity of nitrate of potassa, a small quantity of the salts of
lime and magnesia, and all the marine salt contained in the
plaster. It is frequently the case, that the liquor contains
muriate of potassa, and a small quantity of sulphate of lime.
It is, therefore, submitted again to evaporation. When it is
at the forty-second degree of concentration, some part of the
marine salt separates, which rises to the surface, and is taken
off, and drained through an osier basket placed over the
boiler. The solution being concentrated to the forty-fifth
degree of the hydrometer, it is put into copper vessels, in
which, by cooling, it crystallizes. The salt is then separated
from the mother water, drained and coarsely bruised, and
afterwards washed in a certain quantity of the first boiling.
It is now in a state to be delivered to the central administration,
under the name of crude saltpetre, or saltpetre of the
first boiling.
The crude saltpetre contains about seventy-five per cent of
nitrate of potassa. The quality may be determined by treating
it with a saturated solution of pure nitrate of potassa,
which cannot dissolve any more of the nitrate, but will dissolve
any foreign salts. The twenty-five parts of the foreign
substances, contained in the crude saltpetre, are composed of
a large quantity of marine salt, and of a small portion of muriate
of potassa. It is necessary to separate them, and other
foreign substances. The operation for this purpose, is called
the refining of saltpetre.
The refining of saltpetre is founded principally upon the
property, which nitre has, of being more soluble in warm water,
than the muriate of soda, and muriate of potassa. Thirty
parts of saltpetre, and six parts of water are put into a boiler
and the liquor is heated. By this means, there is precipitated
a large quantity of marine salt mixed with muriate of
potassa. A small quantity of water is added from time to
time, to keep the nitre in solution.
When the foreign salt is not fully deposited, the liquor is
clarified, and more water is added, sufficient to form ten parts,
including that which has already been poured upon it. The
liquor is removed, when it is clear and less heated, and put
into copper vessels, where it is agitated to prevent crystallization,
and to effect the pulverization of the saltpetre.
The saltpetre obtained by this process is not sufficiently
pure. The purification is completed by washing it with water
saturated with nitre, which dissolves the foreign substances.
This washing is completed in a vessel, the bottom of
which has been pierced with holes. The nitre, however,
is left some hours in contact with the water, when the latter
is permitted to run out. When the solution is of the same
degree of concentration as that of the saturated water, the
operation is finished. The nitre is dried for use.
The old process of refining saltpetre is thus described:
Put into a copper, one hundred pounds of nitre, and fourteen
gallons of water; let it boil gently half an hour, removing the
scum as it forms; then stir it, and before it settles put it into
filtering bags, which must be suspended from a rack. Put
under the filters glazed earthen pans, to receive the liquor;
in which place sticks for the crystals to form on. In two or
three days, it will all crystallize.
In some saltpetre works, sulphate of potassa is used with
advantage. This salt is furnished in abundance, by the combustion
of a mixture of nitre and sulphur, in the manufacture
of oil of vitriol. It forms the residue after the combustion.
It is likewise produced in the preparation of nitric
acid, in the decomposition of nitrate of potassa, by sulphuric
acid. It may, therefore, be obtained in quantity, from the
oil of vitriol manufacturers, and the aquafortis distillers. It
is usually called vitriolated tartar.
It is known that sulphuric acid forms, with lime, an almost
insoluble compound, called sulphate of lime, or gypsum;
and hence, when sulphate of potassa is mixed with a solution
of nitrate of lime, nitrate of potassa is formed, which remains
in solution, and sulphate of lime is precipitated. The same
effect takes place with all earthy nitrates. For the application
of sulphate of potassa, in this way, we are indebted to
M. Berard. It might be advantageously employed in decomposing
the calcareous nitrate of the nitre-caves of the
western country.
M. Longchamp has recommended the use of sulphate of
soda, or Glauber's salt, for decomposing the muriate of lime,
which exists occasionally in impure nitre. These two salts
reciprocally decompose each other; sulphate of lime is precipitated,
and muriate of soda remains in solution. The latter
is separated by evaporating the nitrous solution.
M. de Saluces (Mémoire de l'Académie des Sciences de
Turin, Année, 1805 à 1808,) has proposed a new process for
purifying nitre. It consists in filtering it through argillaceous
earth, or clay. Although the process is highly spoken
of, yet we can see no particular advantage it possesses.
Chaptal observes, that the process mostly in use is that of
dissolving 2000 pounds of crude saltpetre in a copper boiler,
in 1600 lbs. of water. As the solution is made by the heat,
the scum, which forms, is taken off. Twelve ounces of glue,
dissolved in ten pints of boiling water, and mixed with four
pails full of cold water, are then added. This addition cools
the solution. As to the manipulations of the process, they
have been given. The principal thing to be attended to, is
to separate the marine salt, which is done during the boiling.
To pass this saltpetre through a second operation, in
order the more to purify it, it is again dissolved, in the proportion
of 2000 pounds, in one-fourth of its weight of water.
Heat is applied. The scum is separated; a solution of 8
ounces of glue in one or two pails full of water is then
added. After the solution becomes clear, it is suffered to
cool, and at the expiration of five days, it will crystallize, or
form in a mass, which is then exposed to the air six or eight
weeks to become completely dry.
In treating of the formation of nitre in France, Bottée and
Riffault (Traité de l'Art de Fabriquer la Poudre à Canon,)
consider it under the following heads:
1. The constituent principles of nitre; its generation, and
the theories respecting it. In this article, the composition of
nitric acid and its union with potassa, and the production of
artificial nitre, are taken into view.
2. Nitrous earths, and substances which yield saltpetre.
This subject comprehends a view of the substances, which
contain saltpetre, as well as those which afford it by nitrification.
3. The preparation of the substances to produce saltpetre.
This article relates to the manipulations required for the
production of nitre.
4. The manner of lixiviating saltpetre earths. The lixiviation
is an important part of the process, however simple it
may appear; as upon its accuracy depends the quantity of
the product.
5. The treatment of the different waters (lixiviums) with
potash, sulphate of potassa, and wood-ashes. This article
points out the use of potash in decomposing the earthy salts,
such as nitrate of lime; of sulphate of potassa, which converts
the nitrate of lime by double decomposition into nitrate
of potassa, the sulphate of lime being precipitated; and of
wood-ashes, which act in the same manner as potash, as
they contain this alkali.
6. The evaporation of saltpetre waters, and the crystallization
of nitre. In this article, they consider the separation
of foreign alkaline salts, as muriate of soda, and the crystallization
of the nitre, to obtain it in a state of purity.
7. The treatment of the mother water of crystallization.
This article refers to the manner of using the mother water,
in order to obtain more nitre from it, and its employment in
lieu of fresh water for other lixiviums.
8. The refining of saltpetre by the old process. They describe
here the old process, in which a variety of substances
were used to purify the saltpetre, but which is now generally
abandoned, or laid aside.
9. The process of refining saltpetre, as adopted in the establishments
of the administration. Under this head they
give, in detail, the process employed throughout France, as
uniform and the same, in every refinery.
10. The manner of proceeding in the examination of various
kinds of saltpetre in the magazines of the administration.
This article relates to the different modes of examining saltpetre.
11. On the manufacture of potash and pearlash. This
subject is important, as potash is an indispensable article in
the preparation of saltpetre, and the formation of the alkali
may be considered as of primary magnitude in establishments,
conducted upon so large a scale as those of France.
It is thus, that a regular system is adopted, by the French
government, for the production of saltpetre; and we may
add also, for the manufacture of gunpowder, which we notice
in that article.
It may be proper to mention some facts, respecting the
formation of nitre-beds, and the means adopted, in this way,
to obtain saltpetre, and to offer, at the same time, some observations
on this mode of obtaining nitre.
The Mémoires de l'Académie des Sciences, 1720, contain the
observations of M. Bouldoc, relative to the process of lixiviating
saltpetre earths. Lacourt published a pamphlet some
years after, entitled, Instruction concernant la Fabrication du
Saltpetre. Various dissertations appeared on the same subject.
In 1775, the French Academy of Sciences proposed
a prize-question, which produced a more thorough investigation.
The Memoirs of Thouvenal, of the Chevalier de
Lorgna, and of MM. de Chevrand, and Ganivel, were
highly approved, some of which took the prize. Chaptal,
who has done more, perhaps, than any other person in
France, to promote this all-important object, published, in
1794, an excellent dissertation, founded on experiment and
observation. This Memoir was published in the Journal des
Arts et Manufactures, t. iii, p. 12.
Kirwan (Geological Essays, p. 143,) remarks, that the
saline crust, which is found on the walls of the houses of
Malta, is owing to the walls being built of fine grained limestone.
When wetted with sea-water, it never dries. The
crust is nitrate of potassa, nitrate of lime, and muriate of
soda, and is some tenths of an inch thick. Under this crust,
the stone moulders into dust. When the first falls off, it is
succeeded by a second, and so on, until the whole stone is
destroyed. This particular effect, however, is attributed to
the presence of marine salt.
Mr. Kirwan observes, that, "M. Dolomieu shows, at the
end of his Tract on the Lipari Islands, that the atmosphere
of Malta, in some seasons, when a south wind blows, is remarkably
fouled with mephitic air; and, at other times, when
a north wind blows, remarkably pure; and hence, of all others,
most fit for the generation of nitrous acid." Mr. Kirwan
remarks, "How the alkaline part of the nitre, which is one
of the products resulting from the decomposition of this
stone, is formed, is as yet mysterious: Is it not from the tartarin
lately discovered in clays and many stones?" He adds,
after speaking of animal and vegetable decomposition, "I
should rather suppose, that the alkali is conveyed into these
earths by the putrid air, than newly formed; and the reason
is, that tartarin, (potash,) notwithstanding its fixity, is also
found in soot; and, in the same manner, may be elevated
in putrid exhalations."
Artificial nitre-beds consist of the refuse of animal and
vegetable substances, undergoing putrefaction, mixed with
calcareous earth; the refuse of old buildings, particularly
plaster; earths from the vicinity of inhabited buildings; blood,
urine, &c. They are covered, from the rain, by a shed, open
at the sides. Cramer, an author of credit, informs us, that
he made a little hut, with windows to admit the wind. In
this, he put a mixture of garden mould, the rubbish of lime,
and putrid animal and vegetable substances. He frequently
moistened them with urine, and in a month or two found his
composition very rich in saltpetre, yielding at least one-eighth
part of its weight. The practice of obtaining nitre
from nitre beds, was followed in France and Germany. It
is extracted and refined by the process already given.
When oxygen gas is presented to azote at the moment of
its liberation, nitric acid is formed. As ammonia is the result
of animal putrefaction, or is formed in the process, hydrogen
must unite also with azote. The azote is furnished
by the animal substances. These facts being known, we are
enabled to account for the generation of nitric acid, and, consequently,
of the earthy and other nitrates, in artificial nitre
beds.
In noticing this subject, it is unnecessary to quote the
opinion of Stahl, who believed that there was but one acid
in nature, the sulphuric; and that nitric acid was the sulphuric
acid, combined with phlogiston, which he affirmed was
produced by putrefaction; nor is it necessary to mention the
opinion of Lemery, who believed that nitre exists ready
formed in animals and vegetables by the processes of vegetation
and animalization. The experiments of the French
philosophers have put these opinions at rest.
Thouvenal discovered, that nothing more was necessary
for the production of nitre than a basis of lime, heat, and
open air; so that nitre beds, formed of putrefying animal
and vegetable substances, with the conditions thus stated,
must produce saltpetre; a fact which experience abundantly
justifies.
The process for the formation of nitre, is called nitrification.
Although animal substances, by putrefaction, furnish azote,
and nascent azote unites with facility with the oxygen
of the atmosphere, by which nitric acid is generated—(hence
the spontaneous decomposition of nitre composts)—yet Vauquelin
is of opinion, that the presence of calcareous or alkaline
substances is indispensable, and that the production
of carbonate of ammonia from the animal matter, is another
compound, which results from the same decomposition. Ammonia
is produced by the union of azote and hydrogen, and
carbonic acid by that of carbon and oxygen. He considers
then, that the presence of lime, magnesia, potash, &c. determines
the union of the azote with oxygen, and of course,
the formation of nitric acid; and as this acid unites with
one or other of these substances, according to circumstances,
we have either nitrate of lime, or of magnesia, or nitrate of
potassa. The idea that water is decomposed in the change
which animal and vegetable substances undergo, in the process
of nitrification, is contrary to observation; for the presence
of air in dry situations, is indispensable to the process.
If a compost, made up of animal, vegetable, and calcareous
substances, and put in small beds or heaps, and covered with
a shed open at both sides, be frequently turned to admit new
surfaces to the air, and occasionally moistened with urine, &c.—nitric
acid will be generated as the putrefaction goes on.
When this process is suffered to proceed until the decomposition
is complete, and the beds then lixiviated, the quantity
of nitre will be considerable. In all cases, we are to observe,
that, as various earthy nitrates are produced, and mostly nitrate
of lime, potash, or wood-ashes which contain this alkali,
are to be used.
It was long since shown by Glauber, that a vault plastered
over with a mixture of lime, wood-ashes, and cows' dung,
soon becomes covered with efflorescent nitre; and that, after
some months, the materials yield, on lixiviation, a considerable
proportion of this salt. M. de Roder, speaking of nitrous
walls, observes, that the efflorescence of nitre on them
is in consequence of the stone, lime, and sand employed in
the building.
What is denominated the saltpetre rot, is an efflorescence
observed on the walls of old buildings, and on the ground.
Dr. C. F. Gren, professor at Halle, in Saxony, (Principles
of Modern Chemistry, vol. ii, p. 128), very justly remarks,
that, among the matters capable of corruption, those are the
most convenient in making nitre, which contain the greatest
portion of azote, of which animal substances are the first;
among which he enumerates flesh, blood, skins, excrements
of animals, old woolen stuffs, and urine. He also mentions
marsh plants, green herbs, mud from streets trodden by cattle,
and the ground from marshes or bogs. As a compost he
adds, that the ground from church-yards, where corpses
have successively, and during a long series of years, undergone
corruption, would be the best for artificial nitre beds.
On the subject of nitre beds, the reader may consult the
Recueil de Mémoires et de Pièces sur la formation et la fabrication
du saltpetre, à Paris, 1786, 4to. These remarks on
the generation of nitre, although of more ancient date, are
confirmed by James and Herman Boerhaave, (Chemistry,
&c.) Hoffman, (de Salium Medicorum, et de Præstantissima
Nitri Virtute), Stahl, (de Usu Nitri Medico), Neuman, (chemical
works), and Lewis, (Materia Medica)—all of whom
have written more or less on the formation of saltpetre; to
which we may add the observations of Parr, (London Medical
Dictionary, vol. ii, p. 24.)
The process for extracting saltpetre from damaged gunpowder
is nothing more than putting it into a boiler, and adding
water sufficient to cover it. On applying heat, the nitre
will be dissolved. If any scum forms, it must be removed.
When the solution is effected, pour it on a sufficient number
of filters, and collect the fluid which passes through. The
residue may be treated with more water, and the whole again
filtered. After boiling the solution, set it aside to crystallize.
The sulphur may be recovered, by subliming the residue
in a temperature not sufficient to inflame it. The charcoal
may be used again for the same purpose.
Saltpetre, when properly refined, does not contain any foreign
salts, and its purity may be known by a variety of experiments,
as follows: make a solution of the salt in distilled
water, and filter it through paper. Put a portion of it
in a wine glass, and add a solution of carbonate of potassa.
To another portion, add a small quantity of muriate, or in
preference, nitrate of barytes. To a third portion, add nitrate
of silver. If the fluid in the first glass remains clear, without
any turbidness, we are to infer the non-existence of earthy
salts; if turbid, that it contains lime, or some other
earth, either in the form of a nitrate or muriate. The addition
of oxalate of potassa to another portion of the solution
will show the presence of lime by forming a precipitate, and
the addition of carbonate of ammonia, and then of phosphate
of soda, will indicate magnesia. If the second glass remains
transparent, it shows that neither sulphuric acid, nor any of
the sulphates are present. If the fluid in the third glass continues
also clear, we infer that none of the muriates exist.
These experiments are sufficient to show the purity of
saltpetre. It would afford perhaps more satisfaction to
institute also the same experiments on other samples of nitre,
by which a comparison may be formed of the relative
purity of each. To make an analysis of the salt, with the
view to determine the proportion of the foreign substances
would be altogether unnecessary for common purposes. A
regularly defined crystal would, in a great measure, point
out its purity. The double refined saltpetre is chemically
pure. Artificers determine the purity of nitre by its flame;
if white, they call it pure, if yellow, impure.
The same reagents may be used in the examination of gunpowder,
as we shall notice hereafter. If a portion of powder be
mixed with distilled water, the water will dissolve only the
saline substances, leaving the charcoal and sulphur. When
the whole is thrown on a filter, the fluid, which passes
through, will contain the saltpetre, and foreign salts, if any
are present. The same experiments may then be performed
with the solution, and the quality of the nitre, of which the
gunpowder was made, be determined. Some gunpowder absorbs
a large portion of water, which is owing to the presence
of deliquescent salts. These salts may be detected by proceeding
in the way we have pointed out. The art of refining
saltpetre is so well known of late in the United States, especially
by the Messrs. Dupont of Brandywine, Delaware, that
our gunpowder is of a very superior quality. I have examined
various specimens of this saltpetre, and gunpowder made with
it, and could not detect any of the sulphates or muriates, either
alkaline or earthy. For the manufacture of gunpowder,
and fire-works generally, the nitre, it may be observed, cannot
be too pure.
In pyrotechny, it is necessary to have the nitre in powder.
Pulverizing it in a mortar is a tedious method, if a large
quantity is required for use. There is an advantage, likewise,
in the mode we will describe; because the saltpetre, besides
being extremely fine, is made perfectly dry. Put into a
copper kettle, whose bottom must be spherical, fourteen pounds
of refined saltpetre, with two quarts or five pints of water.
Put the kettle on a slow fire, and if any impurities rise and
form a scum, remove them; keep constantly stirring with two
large spatulas, till the water evaporates, and the nitre is reduced
to a powder. This will be perfectly white, and almost
impalpable. If it should boil too fast, remove the kettle, and
set it on wet sand, which will also prevent the nitre from adhering
to the pot. It should be kept in a dry place. This
process of powdering saltpetre is performed on a large scale
for the manufacture of gunpowder.
Sec. II. Of Nitrate of Soda.
This salt has been recommended in lieu of nitre, for preparing
certain fire-works; but we confess, we can see no particular
advantage in using it. It has the property of attracting
humidity from the air, and on that account is rendered
unfit for the manufacture of gunpowder. This salt is composed
of nitric acid and soda. It was formerly called cubic
nitre. It may be formed, very readily, by saturating nitric
acid with soda, and evaporating the solution. It crystallizes
in rhomboidal prisms. It may be formed more economically,
by mixing together the solutions of nitrate of lime and sulphate
of soda, filtering the mixture, and evaporating the filtered
liquor. It will be sufficient to observe, that it deliquesces,
or absorbs moisture, and in the fire, that its phenomena
are the same as those of nitre. It does not melt so readily.
Used in the same proportion as nitre, it will form a gunpowder,
which soon, however, spoils by exposure. It will,
like nitre, communicate a yellow colour to the flame of alcohol.
Experiments were made with this salt, with the view to
the fabrication of gunpowder, by MM. Bottée and Riffault.
Their conclusions, as we have stated, may be seen in their
work on gunpowder. Professor Proust says, that five parts of
nitrate of soda, with one of charcoal, and one of sulphur, will
burn three times as long as common powder, so as to form
an economical composition for fire-works.
The cubic nitre, and the nitrum flammans were known,
and so called, by the older chemists. The former we have
seen, is the nitrate of soda, and the latter, is a combination of
nitric acid and ammonia. Nitrate of soda, consists of 6.75
acid + 3.95 soda.
Nitrate of ammonia possesses the property of exploding;
and, when exposed to a temperature of about six hundred degrees,
is decomposed, furnishing the nitrous oxide, called also
the protoxide of azote, and exhilarating gas, besides water.
Nitrate of ammonia is composed of 6.75 acid + 2.13
ammonia + 1.125 water.
Sec. III. Of Chlorate of Potassa.
This salt, formerly called hyperoxymuriate of potassa, is
used for sundry preparations, and especially for experimental
fire-works. It is prepared by dissolving one part of carbonate
of potassa in six parts of water, and saturating it with
chlorine, formerly called oxymuriatic acid gas. This operation
is usually performed in a Woulfe's apparatus. The gas,
as it proceeds from the retort or gas bottle, is brought in contact
with, and passes through, the fluid. It is formed by
pouring liquid muriatic acid on the black oxide of manganese,
or by pouring sulphuric acid on a mixture of muriate
of soda, and the black oxide. When the saturation is nearly
complete, crystals fall down. These being dissolved in boiling
water, and the solution allowed to stand, pure chlorate of
potassa will be formed.
This salt is composed of 9.5, chloric acid, and 6 potassa;
and chloric acid is formed of 28.87, chlorine, and 32.28,
oxygen. It is to the oxygen in the salt, that its particular
properties in fire-works are to be ascribed.
This salt is decomposed by all combustible bodies, and detonations
generally accompany the decomposition. Hence it
is used in a variety of experiments, some of which we will
give.
Three parts of the salt and one of sulphur detonate when
rubbed in a mortar. The same mixture, struck with a hammer
on an anvil, produces a loud explosion. Phosphorus detonates
with this salt either by trituration or percussion. The
quantity of each should not exceed a grain. Treated in the
same manner with almost all the metals, the same effect takes
place. Cinnabar, antimony, pyrites, &c. produce the same effect.
Nitric acid, poured on a mixture of this salt with
phosphorus, produces flashes of fire. A mixture of the chlorate
and white sugar, when touched with sulphuric acid, immediately
inflames. Hence it is used in the preparation of
pocket lights; the mixture being put on a common sulphur
match, and immersed in sulphuric acid. The same preparation
of sugar and chlorate of potassa, put over a tube used
for firing artillery, will set fire to the priming fuse, by dropping
on it sulphuric acid. Owing to this effect, M. Gassicourt
(Archives des Découvertes), recommended a similar mixture
for discharging cannon by means of this acid. As it contains a
large quantity of oxygen, that gas may be obtained from it
by distillation. Light decomposes it. It should, therefore, be
excluded from the light.
As this salt, when mixed with inflammable substances, detonates
when struck with a hammer, it has been used for the
purpose of inflaming gunpowder without the use of the flint
and steel. There are several formulæ given for the purpose.
We remarked, when treating of the general theory of fire-works,
that the Rev. Alexander Forsyth discovered a new
kind of gunpowder, which inflames merely by percussion;
that the gun-lock, which he contrived, was calculated for firing
cannon, as well as musquetry; that it was so contrived as
to hold forty primings of such powder; and that the act of
raising the cock primes the piece. In his composition, each
charge of priming contains no more than one-eighth of a
grain of chlorate of potassa. Since that period, it appears,
that the lock, as well as the powder, has been improved, although
neither of them is in general use. Thenard, (Traité
de Chimie, tome ii, p. 559, troisième édition), has given a
formula for preparing a priming powder of this salt, adapted
to the new lock, which is made by mixing it with 0.55
of nitrate of potassa, 0.33 of sulphur, 0.17 of the raspings
of peach-wood passed through a fine sieve, and 0.17 of
lycopodium, or puffball. (See Inflammable Powder.)
This salt also produces powerful effects with charcoal and
sulphur. Three parts of it, with half a part of sulphur, and
half a part of charcoal powder, produce most violent explosions.
Two persons, in 1788, lost their lives by it. If this
mixture be thrown into concentrated sulphuric acid, a brilliant
flame is produced. Such mixtures, we are informed, will
explode spontaneously. It should not, for that reason, be kept
prepared. Chlorate of potassa has been used in the place of
nitre, for the manufacture of gunpowder, in consequence of
its decomposition by charcoal. From its explosive effects,
M. Berthollet was induced to propose it as a substitute for
nitre. The proportions used by Chaptal, (Chimie Appliqué
aux Arts, tome iv, p. 198), are six parts of chlorate of potassa,
one of sulphur, and one of charcoal. They are to be mixed
in a marble mortar with a wooden pestle. The first experiment
was made at Essone, in France, in 1788. No
sooner, however, had the workmen begun to triturate the
mixture, than it exploded with violence, and killed two persons.
The force of this gunpowder is greater than that of the
common sort; but the danger of preparing it, and even of
using it, is so great, that these circumstances will always prevent
its introduction. A salt, containing so much oxygen,
and so loosely combined, that even the slightest friction, in
contact with inflammable bodies, will separate it, must, of
necessity, prevent its use in that way.
The experiments, which were made at the arsenal at Paris,
on the 27th of April, 1793, comparing the effects of muriated
powder, and the superfine common powder, have given us
the following results:
1st. By the eprouvette of Darcy, consisting of a cannon,
which, being suspended to the extremity of a bar of iron,
described by its recoil an arc, of which the degrees can be
measured.
| | Recoil. |
| 2 drachms | muriatic powder, | 15 deg. | 2/20 |
| 2 —— | do do moistened, | 14 — | 1/20 |
| 2 —— | common powder, | 10 — | 7/20 |
| 2 —— | common powder, | 10 — | 1/20 |
| 3 —— | muriatic powder, | 20 — | 9/20 |
| 3 —— | common powder, | 16 — | 6/20 |
From these results, it appears, that, by the eprouvette of
Darcy, the muriated powder, or that prepared with chlorate
of potassa, gave a superiority of force of about one-fourth.
2nd. By the eprouvette of Regnier, which is repelled by
the explosion, to a distance greater or less, measured by the
degrees of the arc which it describes:
| Muriated powder, | 42 |
| Idem, | 51¾ |
| Idem, moistened, | 52 |
| Common powder, superfine, | 23 |
| Idem, | 22½ |
From which it results, that by the eprouvette of Regnier,
the force of the powder of the oxymuriate is double that of
the nitrate, or common powder.
M. Ruggieri is of opinion, that chlorate, or hyperoxymuriate
of potassa may be employed with advantage in the
composition of rockets, but we have not heard that it has
been used. It is more powerful in its effects, and probably
for this reason he recommended it. This salt, mixed with
other substances, will produce the green fire of the palm-tree,
in imitation of the Russian fire.
Chloric acid may be obtained in a separate state, by boiling
the compound solution formed by passing chlorine gas
through a solution of barytic earth, with phosphate of silver,
which separates the muriatic acid. By evaporation, the
chlorate of barytes will crystallize in fine rhomboidal prisms.
When these crystals are dissolved in water, and diluted sulphuric
acid added by degrees, an acid liquid will be obtained,
which, if the sulphuric acid be added cautiously, will be found
entirely free from the latter acid and barytes, and not affected
by nitrate of silver. This is the chloric acid dissolved in
water. Chloric acid unites with sundry bases. Combined
with ammonia, it forms a fulminating salt, formerly described
by M. Chenevix. This salt is formed, by mixing together
carbonate of ammonia, and chlorate of lime. The carbonate
of lime is then separated by the filter, and the clear liquid,
holding the chlorate of ammonia in solution, is evaporated.
Chlorate of ammonia is very soluble in water and alcohol,
and decomposed by a moderate heat.
Chlorates, as the chlorate of potassa, are formed more
readily in the manner already stated: viz. by saturating the
base with chlorine, but in this case two salts are produced,
the chlorate and hydrochlorate. Chloric acid has also been
obtained in a separate state, from chlorate of potassa, by a
process recommended by Mr. Wheeler.
Perchloric acid, composed of seven primes of oxygen
and one of chlorine, is obtained from chlorate of potassa,
treated in a particular manner. Three parts of sulphuric acid
and one of chlorate of potassa, when heated, will give a saline
mass, consisting of bisulphate of potassa, and perchlorate
of potassa. Deutoxide of chlorine will be evolved.
The perchlorate detonates feebly when triturated with sulphur.
Sec. IV. Sulphur.
Sulphur, or brimstone, is a principal ingredient in almost
all the compositions of fire-works. It should, therefore, be
pure. The flowers may be considered the purest kind of sulphur.
Sulphur is found native, either alone, or accompanying
certain minerals, such as gypsum, rock-salt, marl, and clay, as
in Switzerland, Poland, and Sicily. In the neighbourhood of
salt-springs, it is also found; and frequently in water, in
combination with hydrogen, forming the natural hepatic waters.
It is also found on the surface of the earth, as in Siberia.
Volcanic sulphur, or that which occurs in the fissures
and cavities of lava, near the craters of volcanoes, is
very common.
Solfatere, Sicily, the Roman states, Guadaloupe, and Quito,
in the Cordilleras, are most celebrated for native sulphur.
It has been found in the United States, but in no quantity.
We have a number of mineral springs, which deposite sulphur.
The Clifton Springs of Ontario are of this kind. It occurs
abundantly, in combination with hydrogen, as sulphuretted
hydrogen gas, in various parts of the United States.
Native sulphur is abundant in the island of Java. It is
obtained from the now almost extinct volcano, about sixty
miles from the town of Batavia. At the bottom of the crater,
there is said to lie many hundred tons of native sulphur.
Silliman (Journal, vol. i, p. 58) observes, that it is in the
crater of this volcano, that the celebrated lake of sulphuric
acid exists, "and from which it flows down the mountain,
and through the country below, a river of the same acid."
Sulphur, however, is usually obtained from pyrites or metallic
sulphurets, by fusion and sublimation. It is usually
denominated by the name of the place whence it comes.
Hence we have the Italian and Sicilian sulphur; the crude,
roche, or stone brimstone of Marseilles, &c.
The quantity of sulphur, which may be obtained from the
galena, or sulphuret of lead, by sublimation, is considerable.
Twenty-five per cent is the loss sustained in the reduction of
the lead ore, which occurs so abundantly in the neighbourhood
of St. Louis. When general, the then lieut. Pike,
(Expeditions, &c. Appendix) interrogated Mr. Dubuque in
1805, respecting the quantity of lead obtained from those
mines, a detailed account of which is given by Schoolcraft,
he replied that the mineral would yield seventy-five per cent.
of lead, and hence the twenty-five per cent. loss must be the
sulphur, together with any foreign matter it may contain.
The experiments of M. Vauquelin, (Annales de Chimie,
1811) to determine the quantity of sulphur contained in some
metallic sulphurets, show, at once, the proportion which may
be obtained from those combinations. Thus he found, that
sulphuret of copper contains 21.31 per cent of sulphur; sulphuret
of tin, 14.1; sulphuret of lead, 13.77; sulphuret of
silver, 12.73; sulphuret of iron, 22; sulphuret of antimony,
25; sulphuret of bismuth, 31.75; sulphuret of manganese,
74.5; and sulphuret of arsenic, 43.
Of native or prismatic sulphur, there are two species,
the common and volcanic. The former is of two kinds, the
compact and earthy.
Sulphur, says Hanway, (Travels, &c.) is dug at Baku on
the western side of the Caspian sea. It is found in the
neighbourhood of the celebrated naphtha springs, some of
which form a mouth of 8 or 10 feet diameter.
Von Humboldt (Annales de Museum National) communicated
to the French national institute, that he discovered,
in the province of Quito, a bed composed of sulphur and
quartz, in a mountain of mica slate, and also sulphur in primitive
porphyry. Kirwan (Geological Essays, p. 143) observes,
that sulphur promotes decomposition, by absorbing oxygen,
while it is thus converted into vitriolic acid; but moisture is
also requisite. He attributes, in the same manner, the decomposition
of stones that contain pyrites.
As the sulphur, which occurs in commerce, is chiefly obtained
from its native combinations, it may be proper to
make some brief remarks on this head. Sulphur in the state
of combination is abundantly met with, and in all countries.
It is found in the state of sulphuric acid, in various salts, as
gypsum, epsom salt, native alum, &c.; and united with metals,
forming natural sulphurets, as in sulphuret of iron, or
iron pyrites, sulphuret of copper, or copper pyrites, sulphuret
of lead, or potter's lead ore, called also galena, sulphuret
of antimony, or crude antimony, sulphuret of zinc, or blende,
sulphuret of mercury, or cinnabar, sulphuret of arsenic, or
orpiment, &c. In fact, it appears to be a general mineralizer.
It is found also in some plants, and in animal substances.
Without detailing minutely the processes employed for
extracting sulphur from its combinations, which may be seen
in Thenard, (Traité de Chimie, tome i, p. 184) it will be sufficient
to observe, that, in general, pyrites, both of iron and
copper, are arranged in alternate layers in the form of a pyramid,
and the roasting is continued for several months. Part
of the sulphur is consumed, and part is sublimed, and is
condensed and collected in hollows, in the upper part of the
pyramid, whence it is removed several times a day. It is
also obtained from pyrites, by a kind of distillation. They
are reduced to coarse powder, and put into hollow iron
cylinders, or retorts, where the sulphur is disengaged and
melted, and thence runs into vessels of water. This process
is employed in Saxony, where nine hundred pounds of pyrites
will yield one hundred to one hundred and fifty pounds
of sulphur, which is afterwards purified.
When melted and cast into wooden moulds, it forms the roll
brimstone; and, by sublimation, conducted in large chambers,
as we shall afterwards mention, it is converted into the flowers
of sulphur. The residue of the sublimation is sulphur
vivum, which is also used in fire-works. The roll brimstone
is frequently adulterated.
In the island of Anglesea, it is obtained by the sublimation
of the yellow copper ore. The operation is conducted in kilns,
and the sulphur is conveyed by means of long horizontal
flues, and collected in large chambers. As the United States
furnish an abundance of martial pyrites, and also galena,
sulphur might be manufactured in this country, and advantageously,
especially from galena, which is very abundant in
the neighbourhood of St. Louis. In the roasting of the ore,
all the sulphur is now lost, tons of which might be collected.
For the purpose of gunpowder, the purer the sulphur, the
better will be the powder; hence attention is always paid to
this circumstance. M. Michel, one of the principal refiners
of sulphur at Marseilles, has improved the process for purifying
sulphur for the purpose of gunpowder. M. Libaw,
connected likewise with the French national powder establishment,
has furnished a very useful and important memoir on
the same subject.
Two methods are proposed for the refining of sulphur,
which we will briefly state, namely, fusion, and sublimation.
The first is conducted in iron pots fixed in a furnace; and
the sulphur, before it is thrown in, is beaten into small pieces
with a mallet. This facilitates the fusion, and renders it
more uniform. Small portions at a time are thrown into the
boiler, and stirred frequently with a wooden spatula. This
manipulation ought to be continued till the boiler is filled.
The heat must be regulated so as not to inflame, or sublime
the sulphur.
The sulphur of commerce is commonly of three different
colours, viz: citron-yellow, deep yellow, and brownish-yellow.
These colours depend on the different degrees of heat
to which the sulphur was exposed, in its extraction. The
operation of refining consists in conducting the fire in such
a manner, as that the colour of the sulphur will assume a
brilliant yellow, bordering on a green. We must, therefore,
to produce this effect, operate on the sulphur according to
its colour. For the green sulphur, as little heat has been
used for its extraction, the fire may be left under the boiler
until there is no more left to melt than the top. The sulphur
of the yellow colour may be kept longer on the fire,
which may be removed when the mass is melted three-fourths.
The sulphur of a brown colour, being already much burnt,
may be removed when the mass is melted one-half. If it is
required to operate on all the varieties at the same time, in
order to produce sulphur of a uniform colour, in that case
we must fill the boiler one-half with the green sulphur, one-fourth
with the yellow, and the remainder with the brown,
and removing the fire when the yellow is almost wholly
melted. The boiler is then covered with a lid. The fusion
is completed by the heat of the mass. The light bodies then
raise themselves to the surface, forming a black scum, which
is removed, and the heavy bodies fall to the bottom. The
boiler remains for four or five hours, uncovering it from time
to time to take off the scum. The fluid part is removed,
and is suffered to congeal, taking care not to disturb the deposite.
The second process of refining is by sublimation. This
operation consists in subliming it in a close apparatus, which
in sulphur refineries are boilers placed in brick work, and
furnished with heads. These heads communicate by a pipe
with a vaulted chamber, placed at some distance from the
furnace. The chamber serves to collect the sulphur. There
is usually a stone slab fixed between the chamber and the
head. The chamber is furnished with one or two iron-plate
valves. There is an opening in the head of each boiler, in
order to renew the sulphur: it is closed very tight by a plate
of iron. There is an opening also in the chamber, to admit
a person, which is closed likewise by an iron plate. The
heads are luted before the process is commenced.
By this process the sulphur is refined; for the pure part
is sublimed, and the foreign substances remain in the pots.
The product thus obtained is the ordinary flowers of sulphur.
If the heat be moderate, the sublimation is more perfect. It
is necessary at the same time that the temperature of the
chamber should be low, otherwise the sulphur will melt,
which frequently takes place. Coarse particles are separated
from the flour, should they occur, by a sieve.
During the first part of the process, there is formed some
sulphurous acid gas, which is not produced after the vapour
of sulphur forms the atmosphere in the head. This is known
to exist, by the acid taste of the sulphur, and its black
colour.
Detonation very frequently takes place, and sulphurous
acid gas is produced. In the sublimation of brimstone,
about ten to eleven per cent. is the usual total loss, of which
six or seven per cent. is residue. The acid may be separated
from the sulphur by washing it in water, and afterwards
drying it. It is then called the washed flowers of sulphur.
(See Traité de l'Art de Fabriquer la Poudre à Canon, p.
153.) by MM. Bottée and Riffault, for a minute description
of this process.
Sulphur undergoes no change by exposure to the air. It
is insoluble in water. It breaks in the hand with a crackling
noise. At 170 degrees it begins to evaporate, and when
collected it is called sublimed, or flowers of sulphur. It
melts at 218 degrees. When melted and poured into water,
it forms the sulphurs for taking the impression of coin, &c.
If melted, and cooled slowly, it will crystallize in the form
of needles. It is soluble in different degrees in alcohol,
ether, and oils. When sulphur is burnt very slowly in the
open air, it unites with oxygen and forms sulphurous acid.
This acid is used in bleaching. When mixed with nitre,
and burnt in leaden chambers, it forms sulphuric acid, or
oil of vitriol, by which process it combines with a larger
quantity of oxygen. There is another compound called hyposulphurous
acid, all the salts of which are inflammable
and burn with a blue flame. Sulphur unites with the alkalies,
earths, and metals. If the alkaline sulphurets be dissolved
in water, and an acid added, the sulphur will precipitate of
a white colour, known by the name of milk of sulphur. It is
considered by some a hydrate of sulphur. The same preparation
is made by subliming sulphur in a vessel containing
the vapour of water. Sulphur unites with chlorine and
iodine, forming chlorides, and iodides. With hydrogen, it
forms the sulphuretted hydrogen, or hepatic gas, called also
the hydrothionic and hydrosulphuric acid; with carbon, the
sulphuret of carbon; and with nitre and charcoal, in the state
of mixture, it constitutes gunpowder.
The motionless ignes fatui of Italy, which are seen nightly
on the same spot, are attributed to the slow combustion of
sulphur, emitted through clefts and apertures in the soil of
that volcanic country; but the Will-with-the-Wisp, which
moves in undulations, near the surface of the ground, in
swampy situations, and where the putrefactive process is
going on, originates in all probability from decaying vegetable
and other matters, and the extrication of phosphorus. It
is known that the acid of phosphorus is found in plants, and
especially those that grow in marshy places, in turf, and
several species of the white woods.
Mealing of Brimstone. What is termed the mealing of
sulphur by fire-workers, is no other than reducing it, if it be
the roll, to powder. Large mortars and pestles made of
ebony, and other hard wood, and horizontal mills with brass
wheels are used. The mealing table is used by artificers.
It is generally made of elm, with a rim around its edge four
or five inches high. One end is narrow, and furnished with
a slider that runs in a groove, and forms part of the rim.
After using as much of the powdered brimstone as is required,
copper shovels being employed, the rest may be
swept out at the slider. This table is also used for the mealing
of gunpowder and saltpetre. The muller is generally
made of ebony. After reducing it to powder, it is then passed
through a lawn sieve, furnished with a cover.
As brimstone is frequently adulterated with different substances,
it may be of importance to discover the fraud. We
may remark, that, if it is pure, it will be taken up entirely
by chlorine gas, or by using a solution of caustic potassa.
The latter, however, cannot be depended on in all cases. But
the best mode, is that of melting some of it in a ladle; if any
residue remains, after the fumes have ceased, the presence
of foreign substances may be inferred, for pure sulphur will
sublime without leaving any residue. It is not unfrequently
adulterated with common flour. There is another mode of
determining the quality of sulphur, It should, if pure, be
completely soluble in boiling oil of turpentine. If any residue
remain, we may infer the presence of foreign substances,
either vegetable, earthy, or metallic.
It is obvious, that if the brimstone is impure, the effect of
it in fire-works will be imperfect. Flowers of sulphur,
however, may be almost always depended on. In all artificial
fire, in which sulphur forms a part, the flame is more
clear, as the sulphur is pure.
Several modes are recommended for the separation of
sulphur from charcoal, in gunpowder, which may be seen by
referring to the analysis, or chemical examination of gunpowder.
Sulphur constitutes one of the ingredients, generally speaking,
of incendiary compositions, used for military purposes,
and, in such cases, is usually mixed with pitch, tar, saltpetre,
and sometimes gunpowder. It is said to be one of the substances,
which entered into the composition of the ancient and
celebrated Greek fire; but the principal character of which,
that of burning in water, was owing to the presence of camphor.
This substance, associated with sulphur, pitch, and nitre,
forms one of the most effective incendiaries of all military
fire-works. For such purposes, it is hardly necessary to
add, that the common roll brimstone is sufficiently pure.
As to the mode of preparing these works, the custom is
to melt the resinous substances first, then to add the sulphur,
and finally the saltpetre; and after the whole are melted and
thoroughly mixed, to remove the pot from the fire, and add
gradually the gunpowder. If a carcass is to be made, tow
or hemp, or untwisted rope, is immersed in the composition
while hot, and taken out and formed into a ball of the size
required. Rope, treated in the same manner, with the same
composition, will make a more active tourteaux than the
common kind. (See Carcass and Tourteaux.)
All oils, whether expressed or essential, can dissolve sulphur.
To make this solution, the oil must be poured on the
sulphur, and sufficient heat applied to melt the substance.
While the oil dissolves the sulphur, it acquires a reddish or
brown colour, an acrid, disagreeable taste, and a strong fetid
smell, somewhat hepatic, resembling that of oil with sulphuric
acid.
Sec. V. Of Phosphorus.
We mention this substance, because it is used in some experiments,
although not in extensive fire-works. It is a very
inflammable substance, inflaming either by friction, or an increase
of temperature. It produces a most brilliant fire, and
when mixed with some substances, exhibits very pleasing phenomena.
It usually comes to us in sticks, which must be constantly
kept in water to prevent its inflammation. Phosphoric
matches, phosphoric fire-bottles, &c. are made of it. These
are made in various ways. Phosphorus and sulphur melted
together in a small phial, forms the fire-bottle, or some add
a portion of lime. A sulphur-match dipped in this mixture
and gently rubbed, immediately inflames. They do not last
any time, in consequence of the acidification of the phosphorus.
Phosphoric tapers are usually made with a glass tube,
on the breaking of which, it inflames. When rubbed upon a
wall in a dark room, it appears very luminous. Dissolved in
ether, and poured upon boiling water in the dark, the vapour
as it ascends appears remarkably luminous, and has a pleasing
effect. Dissolved in oil, as olive-oil, it forms the phosphorized
oil, which may be rubbed on the face and hands
without injury. This oil has the same appearance in the
dark. The time of night may be known by the light it produces.
When mixed with nitrate of silver, sulphuret of antimony,
sulphur, chlorate of potassa, &c. and struck with a
hammer, it produces an explosion more or less loud. A variety
of explosive compounds may be made with it, but they
must be used with great care.
When combined with hydrogen, it inflames spontaneously
when brought in contact with atmospheric air. It inflames
also in chlorine gas. It is supposed to be the cause of the
ignes fatui, or Will-with-the-Wisp. The formation of phosphoretted
hydrogen gas may be shown in a variety of ways,
as the following: throw some pieces of phosphuret of lime into
water, and bubbles of gas will rise, which will take fire on
coming to the air; or, put into a flask some phosphorus, iron
or zinc filings, water, and sulphuric acid, and the gas will
be generated; or, introduce into a small retort, a solution of
potassa, and a piece or two of phosphorus, and apply heat,
immersing the beak of the retort in a basin of water, the gas
will pass over, and inflame as it comes to the surface of the
water. In all these experiments, the water is decomposed;
its oxygen goes to a part of the phosphorus in the first experiment,
and the hydrogen of the water then unites with
another portion of phosphorus, which is then evolved; in the
second experiment, the oxygen oxidizes the metal, and the
hydrogen dissolves a part of the phosphorus; and in the third
experiment, the phosphorus unites with the potassa, forming
a phosphuret, which decomposes the water, the hydrogen of
which passes off in combination with some of the phosphorus,
forming the phosphuretted hydrogen gas.
The cause of the spontaneous combustion is, that the oxygen
of the atmosphere unites with the hydrogen and the
phosphorus, and forms water and phosphoric acid; the latter
producing a beautiful corona as it rises in the air. The
heat and light given out proceeds as well from the oxygen
gas, as from the phosphuretted hydrogen gas. When saturated
with oxygen, it is no longer inflammable.
There are some other experiments which can be made with
this singular substance.
It was formerly obtained from urine, as that fluid contains
some phosphoric salts. It is now prepared from bones. These
are burnt to an ash, and diluted sulphuric acid is poured on
it; the phosphoric acid it contains is then disengaged, and remains
in the fluid. The sulphate of lime is then separated,
the fluid boiled to dryness, and the dry mass is mixed with
charcoal, and distilled in the open fire.
The phosphoric pencil, for writing on a wall, paper, &c.
to be luminous in the dark, is nothing more than a bit of
phosphorus put into a quill. It must be kept in water, and
when used, frequently dipped in water, to prevent its taking
fire.
The phosphoric stone of M. Bucholz, described in the Archives
des Découvertes, ii, p. 109, is a phosphuret of magnesia,
prepared by melting thirty grains of phosphorus in a
small flask, and adding twenty or thirty grains of calcined
magnesia. Although this process is given by Bucholz, yet,
as it is difficult to prevent the inflammation of the phosphorus,
the best mode would be to bring the vapour of phosphorus
in contact with magnesia, in the same manner as in preparing
phosphuret of lime.
The pyrophorus of Wurzer is nothing than a phosphuret
of lime. It is prepared by taking two parts of pulverized
quicklime, and one part of phosphorus; introducing them into
a bottle, and covering it with three parts of quicklime,
leaving one-third of the bottle empty; then putting the bottle
into a crucible surrounded with sand, previously stopping
the mouth with clay, and applying heat. Remove the phial
when the phosphorus appears to sublime of a red colour.
When the bottle is opened it becomes luminous, and brought
out it inflames.
Phosphorus in the state of acidification, and united with
lime, is found in abundance. Whole mountains in the province
of Estremadura in Spain, are said to be composed of
this combination. According to Mr. Bowles, this stone is
whitish and tasteless, and affords a blue flame without smell
when thrown upon burning coals. Mr. Proust observes, that
it is a dense stone, not hard enough to strike fire with steel,
and is found in strata, which always lie horizontally upon
quartz, and which are intersected with veins of quartz. He
adds, that it does not decrepitate on burning coals, but burns
with a beautiful green light. This stone is the common phosphorite.
It contains, according to Klaproth, 32.25 per cent.
of phosphoric acid.
Several substances are known under the name of phosphorus,
although they do not contain it, such as Baldwin's phosphorus,
or ignited muriate of lime, Canton's phosphorus, or
oyster-shells calcined with lime, and Bologna phosphorus, or
calcined sulphate of barytes.
Sec. VI. Of Charcoal.
Charcoal performs an important part in all the various
kinds of fire-works. The facility with which it decomposes
nitric acid, when it is combined with salifiable bases, as with
potassa in saltpetre, and its action in all cases wherein nitre
is concerned, are sufficient examples of its effect.
Pure carbon is the diamond. It affords by combustion in
oxygen gas, the same gas as common charcoal, when charcoal
is burnt in oxygen, or in atmospheric air. This gas is
carbonic acid, or fixed air. Charcoal has been considered a
long time an oxide of carbon, and according to some, as Berthollet,
a compound of carbon, hydrogen, and oxygen.
Charcoal is insoluble in water. It is not affected by the
most violent heat, if confined in close vessels. It is an excellent
conductor of electricity, but a bad conductor of heat. It
is very indestructible; and, therefore, when wood is charred,
it will remain a long time under ground without rotting. As
an antiseptic, it is powerful. It will therefore prevent the putrefaction
of bodies, and even recover tainted meat. As a
preservative of water, for sea-voyages, it has been long
known. The charring of water casks is designed for the same
purpose. The quality of wine is said to be improved by having
the casks previously charred. It possesses the property
of absorbing gases, and to this property is ascribed its use
as an antiseptic, and its disinfecting quality. To the distiller
it is useful, as it destroys effectually the burnt or empyreumatic
smell of liquor. When heated to eight hundred degrees
in the open air, it burns. In oxygen gas the combustion
is brilliant, forming in both instances carbonic acid gas, called
also aerial acid, fixed air, mephitic air, and calcareous
acid. This acid is formed in a variety of processes, and is
carbon saturated with oxygen.
Carbon exists in various states of combination, and many
of the compounds into which it enters are inflammable; hence
carbonic acid is generated in the combustion of coal, oils,
fat, &c. In the form of an acid, it is abundant in various
stones, such as the calcareous carbonates, as chalk, marble,
limestone, and calcareous spar, barolite, &c. all which effervesce
with acids, the carbonic acid being liberated. When
limestone is burnt, to obtain quicklime, the carbonic acid is
disengaged, for the presence of this acid distinguishes limestone
from pure lime. Carbonic acid is generated in various
processes of nature as well as art. Hence it is produced in
the respiration of animals, and is found in a gaseous state in
wells, cellars, caverns, &c. It neither supports animal life,
nor combustion. In mines it is called choke damp; and the
Grotto del Cani, in the kingdom of Naples, has been long
celebrated, on account of it. This cave is in the side of a
mountain, near the lake Agnano, measuring not more than
eighteen feet from its entrance to the inner extremity; where
if a dog or other animal that holds down its head be thrust,
it is killed by the gas. Some experiments were made in this
cave with gunpowder, which see. Carbonic acid, during the
formation of alcohol, in the vinous fermentation, is generated,
and its production appears to be designed by nature to
carry off the excess of carbon, which gives rise to that phenomenon
called fermentation. When combined with water, it
forms aerated water, and with alkalies and water, the aerated
alkaline waters. Its union with bases forms salts called carbonates.
Plants have the property of decomposing it, and in
this respect nature has employed a mean of regenerating the
atmosphere, on the purity of which depends, in an eminent
degree, the very existence of animal life. The prime equivalent
of carbonic acid is 2.75, and carbonic acid is composed
of carbon 0.75 + 2.0 oxygen.
Carbonic acid may be decomposed when combined with a
base, as lime, by phosphorus and heat, for charcoal and a phosphate
of lime will be produced. But carbonic acid in the state
of gas may be decomposed by potassium. Five grains of potassium
will decompose three cubic inches of gas, and be
converted into potassa, producing at the same time three-eighths
of a grain of charcoal. If passed over a coil of fine
iron wire heated to redness, in a porcelain tube, and the operation
repeated, the iron will be oxidized, and the carbonic
acid changed into carbonic oxide gas.
Charcoal will not burn in dry chlorine. It unites with a
less proportion of oxygen, and forms carbonic oxide gas,
which burns with a deep blue flame. This combination is
formed by distilling in a red heat, a mixture of equal parts
of iron filings and chalk. This gas mixed with chlorine gas,
and exposed to the sun's rays, will unite with it, and form
chlorocarbonic acid gas. Carbon unites with azote, and
forms cyanogen, the base of Prussic acid. It unites likewise
with hydrogen in two proportions, forming the hydroguret
and the bihydroguret of carbon, both of which are carburetted
hydrogen gases. The former is obtained by distilling a mixture
of four parts of sulphuric acid, and one of alcohol. The
gas is very inflammable, and burns with great splendour; and
on that account may be used for exhibition, in an apparatus
similar to that of Cartwright. (See Fire-works with Inflammable
air.) It was called by the German chemists olefiant gas.
The other species, called also the light carburetted hydrogen
gas, may be obtained by agitating the mud at the bottom of
stagnant pools; and by the distillation of moist charcoal, wood,
pitcoal, pitch, or almost any animal or vegetable substance.
The gas, used for gas-lights, is the same. It is usually obtained
from pit coal. We may merely observe, that the gas
used for that purpose, i. e. for illuminating streets, theatres,
manufactures, &c. as obtained in the common method, is not
altogether the bihydroguret of carbon; but, according to the
experiments of Dr. Henry, a mixture of that gas with the
hydroguret, and occasionally carbonic oxide.
Carbon enters into other combinations. It exists as a component
part of gums, resins, sugar-starch, and other vegetable
products, as the vegetable acids, its union with iron forms
steel, a substance greatly used in the preparation of some fire-works,
especially in some of the rains and stars, and in the
composition of brilliant fire. (See Iron.)
As charcoal enters into the composition of gunpowder,
and the effective force of powder depends considerably on
the quality, as well as the proportion of charcoal, it is obvious
for this purpose, it should be as pure as possible.
Carbon is always obtained from some of its combinations,
as from pitch, tar, rosin, wood, and oil. Various processes
are employed for this purpose. Thus, by the combustion of
rosin and oil, as well as pitch, tar, turpentine, &c. a soot is
formed that collects, called lampblack, which is nothing more
than the carbon or charcoal. When pit-coal is charred in an
oven, called a coke oven, all the bitumen and sulphur contained
in it are disengaged, and a charcoal remains, called,
however, coke. Wood, when charred is decomposed; all the
volatile parts are disengaged with carburetted hydrogen gas,
and the woody fibre is converted into coal. This coal is more
or less dense according to the compactness of the wood.
Hard woods furnish the most solid coal, and light woods on
the contrary.
When the solid parts of animals, as bone, are charred, the
volatile products, principally ammonia or volatile alkali, are
dissipated, and there remains a substance called bone-black,
improperly called, ivory black.
The carbonization of wood in the common way is well
known: after it is cut to the lengths required, it is piled on
the ground in a pyramidal form, and covered with sod and
clay, leaving a place for the current of air, and the smoke.
The wood is then set on fire, and when the whole is burnt to
a coal the vents, &c. are closed with sod and clay.
Nicholson (Chemical Dictionary) observes, that in the forest
of Benon, near Rochelle, great attention is paid to the
manufacture, so that the charcoal made there fetches twenty-five
or thirty per cent. more than any other. The wood is
that of the black oak. It is taken from ten to fifteen years old,
the trunk as well as the branches, cut into billets about four
feet long, and not split. The largest pieces, however, seldom
exceed six or seven inches in diameter. The end that rests
on the ground is cut a little sloping, so as to touch it merely
with an edge, and they are piled nearly upright, but never in
more than one story. The wood is covered all over about four
inches thick with dry grass or fern, before it is enclosed in
the usual manner with clay; and when the wood is charred,
half a barrel of water is thrown over the pile, and earth to
the thickness of five or six inches is thrown on, after which
it is left four-and-twenty hours to cool. The wood is always
used in the year in which it is cut.
Turf or peat has been charred lately in France, it is said,
by a peculiar process, and, according to the account given in
Sonnini's Journal, is superior to wood for this purpose.
Charcoal of turf kindles slower than that of wood, but emits
more flame, and burns longer. It boiled a given quantity of
water four times, while an equal weight of wood charcoal
boiled the same quantity but once. In a goldsmith's furnace,
it fused eleven ounces of gold in eight minutes, while wood
charcoal required sixteen. The malleability of the gold, too,
was preserved in the former instance, but not in the latter.
Iron heated red-hot by it, in a forge, was rendered more
malleable.
In charring wood it has been conjectured, that a portion of
it is sometimes converted into a pyrophorus, and that the explosions
that happen in powder-mills are sometimes owing to
this.
Bartholdi supposes, that such explosions are owing to the
formation of phosphoretted hydrogen gas, while others attribute
them to the absorption of oxygen, by the hydrogen
contained in the coal, and the consequent evolution of free
caloric. Percussion, which necessarily takes place in mixing
the materials of gunpowder by stampers, no doubt accelerates
the combustion. The addition of water, and having the charcoal
previously pulverized, will prevent such accidents. (See
Gunpowder.)
Coal prepared in the manner above stated, is liable to many
foreign admixtures, nor can the process be so well regulated
as to produce coal of a uniform quality throughout. The
present improved process has many advantages, as experience
has proved. It consists in charring the wood in confined
vessels, made of iron. These are usually cylindrical, furnished
with an iron cover, and placed in furnaces. The pyroacetic,
formerly called the pyroligneous, acid, which is
formed in the destructive distillation of wood, is caught for
use. This acid is useful to the calico printer, dyer, &c. in
making their iron liquor, and when purified, is employed in
Europe in the place of vinegar, as it is more pungent, and
highly concentrated.
When pine and various kinds of wood, which yield turpentine,
are carbonized, we obtain tar during the process.
Chaptal informs us, that tar is obtained from the wood of
the trunk, branches, and roots of the pine, which are heaped
together, covered with turf, and set on fire to produce a close
combustion, in the same manner as for making charcoal. The
oily parts which are disengaged, trickle down, and are received
in a gutter, which serves to convey them to a tub.
The most fluid part is sold under the name of huile de cade;
and the thicker part is the tar used for paying or painting
the parts of shipping and other vessels.
According to the wood submitted to the process of charring,
the products are, more or less, various; but in all cases
it is only the solid part, or ligneous fibre, that furnishes the
coal. By the ordinary process we obtain sundry volatile
products, among which are pyroacetic acid and carburetted
hydrogen gas.
When wood is carbonized in the usual manner, it yields
from 16 to 17 parts of charcoal in the hundred; but when
the operation is conducted in close vessels, the product is
28 per cent. a saving of eleven or twelve per cent. By this
difference in the quantity, it appears that eleven or twelve
per cent. is burnt in the common process.
M. Mollerat was the first who tried the experiment with
iron cylinders.
M. Vauquelin (Annales de Chimie, tome lxvi, p. 174) has
given some observations on the carbonization of wood in
close vessels, predicated on a Memoir of M. Mollerat; both
of which are interesting. The apparatus used by M. Mollerat
is described by Thenard, (Traité de Chimie, iii, p. 373,)
to be composed of two parts, viz: a furnace with a moveable
dome, and a cylindrical kettle, or vessel of iron sufficiently
large to contain a cord of wood. It is furnished with a cover
and pipe. The pyroacetic acid is collected. Smaller cylinders
are preferred, because the wood is ignited more readily
and the charcoal is more of a uniform quality.
From 100 parts of the following named woods, Messrs.
Allen and Pepys (Phil. Trans. 1807) obtained the following
proportional parts of charcoal:
| Beech | 15.00 | |
Oak | 17.40 |
| Mahogany | 15.75 | |
Fir | 18.17 |
| Lignum Vitæ | 17.25 | |
Box | 20.25 |
See also the experiments of Mr. Mushet, in the third
volume of Tilloch's Magazine.
It appears by the Annales de Chimie, vol. 66, and the
Retrospect of Discoveries, vol. vi, p. 100, that three brothers
have established at Pellerey, near Nuits, Cote d'Or, a manufactory
on a large scale, for making charcoal in close vessels.
The quantity of charcoal they obtained is double that by
the usual mode, while it requires only one-eighth part of
wood to be consumed in the distillation; it is also better than
the common, as a given quantity evaporates one-tenth more
water than the other; hence iron masters may obtain twice
as much iron from the use of a given quantity of wood; and
in addition to this, there is also prepared a number of other
articles, of each of which in order.
350 kilogrammes (700 lbs.) of wood, yield 25 or 30 of
tar, which retains so much acid that it is soluble in water;
but when it is washed, and rendered thick by boiling, for some
time, it offers more resistance to water. If mixed with one-fifth
of rosin it is rendered equally fit for the use of ships, &c.
as the common tar.
Four sorts of vinegar are prepared, all of which are perfectly
limpid, which do not, like the common, contain any
tartar, malic acid, resinous or extractive matter, nor indeed
any mineral acid, lime, copper, or other substances. The
simple vinegar marks—2° hydrometer for salts, at 12° centigrade
thermo. it is stronger tasted than common vinegar,
and produces a disagreeable irritation. The aromatic vinegar
is prepared with tarragon, the smell is agreeable, but
it has the same fault as the former. The vinous vinegar is
formed by adding some alcohol to simple vinegar; it has a
very sensible odour of acetic ether; the alcohol softens the
flavour in some degree, but the vinegar is still very sharp.
The acid, called strong vinegar, is in fact a very good acetic
acid at 101/2° hydr., it is very white, clear, and sharp, without
the usual burnt flavour, and seems to form the basis of
the preceding kinds. It can be sold for 8 or 9 francs (7s.)
per lb. which is only half the price of that distilled from
verdigris. Although not so agreeable to the taste as common
vinegar, these new kinds are more elegant to the eye,
and do not mother.
The editor of the Retrospect makes the following observations:
The proprietors of this manufactory seem to be perfectly
aware of all the several productions which could be prepared
from the refuse of their principal object; and we have no
doubt but that the substances they procure in this manner
will amply compensate them for the use of the capital that
must be invested in building the furnaces.
The nature of the vessels in which they distil the wood is
not mentioned, but they are probably cast iron retorts, or
vessels of a similar nature, in which a distillation per latus
takes place. The application, therefore, of lord Dundonald's
furnaces for procuring coke to this purpose would be still
more advantageous.
A cubic yard of wood yields 100 quarts of acid liquor,
besides 50 or 60 lbs. of thick oil.
The method of making charcoal of a uniform quality, for
which a Mr. Kurtz has taken out a patent, is the following:
A sheet-iron chest, which has a cover that fits it tight, and
a pipe, or tube, that descends nearly to the bottom, and coming
out from its side above, is fixed in brick work. In this
the billets of wood are put. Fire is then made underneath.
It is obvious, that the wood is kept at one temperature from
its being immersed in vapour, as the vapour cannot escape
at the top, but must descend to the bottom, and then proceed
up the pipe, by which it is conveyed away. The effect is,
that the charring process goes on regularly, and the wood is
charred equally. The carbonization is finished when the
vapour ceases to appear, and nothing but carburetted hydrogen
gas escapes. The charring of bones is performed in iron
cylinders, furnished with tubes to receive, and convey away,
the impure ammonia.
In the manufacture of powder, particular kinds of wood
are selected for carbonization. These are generally, willow,
hazle, maple, poplar, linden, buckthorn, or alder, or those
which are tender and light, because, as they are less dense,
and consequently more friable, they enflame and consume
more rapidly: they are known in the arts by the name of
white wood. When a less sudden effect is to be produced
with the gunpowder, and the combustion prolonged, as in
some sky-rockets, the charcoal of hard wood is to be preferred,
such as the oak, beech, &c. When the wood is gathered,
the bark is removed, and the wood exposed to the
sun to dry: it is then cut into billets, and charred. The
ashes, if any be formed, are to be carefully separated.
In considering the use of charcoal, therefore, for the preparation
of gunpowder, we are to direct our inquiries to the
choice of wood for carbonization, and the best process for
carbonizing it. All light woods, we remarked, as the linden,
willow, poplar, &c. furnish the lightest coal, and on that account
are preferred. It is remarked, that tender wood, besides
making a light, friable, and porous coal, is more combustible
than ordinary hard, and more compact wood, and
the coal that it furnishes leaves less residue after combustion.
Many experiments have been made with coal prepared
from different kinds of wood, with a view of ascertaining the
kind best adapted for the manufacture of gunpowder. M.
Letort, at the powder mills of Essonne, in France, instituted
a number of experiments of this kind. He made gunpowder
with the coal of several kinds of wood, and compared its
effects by a mortar eprouvette. The result was, that the
powder made with the coal of poplar, was the strongest; and
the other powder, made with the coal of the linden, willow,
&c. was of the same quality throughout. As to the second
inquiry, it is hardly necessary to repeat, that for the complete
and thorough carbonization of the wood, to produce at
the same time coal of a uniform quality, the process of charring
in iron cylinders or close vessels, is to be preferred.
The point to be attended to is, to bring the wood to a complete
state of ignition, and consequently to disengage all the
volatile or fluid parts. When the gas (carburetted hydrogen)
ceases to appear, it is a criterion that the operation is finished.
This gas, it is to be recollected, will come over even after
the whole of the wood is completely ignited. The first volatile
product is the pyroacetic acid. Some saturate the acid
liquor with chalk, and decompose the acetate of lime with
sulphate of soda, and separate the acetic acid from the acetate
of soda by distillation with sulphuric acid. The acetic
acid is then tolerably pure, and may be diluted for use.
It is observed, however, that when charcoal, prepared in
iron cylinders, is designed for gunpowder, the last portion
of vinegar and tar must be allowed to escape, and the reabsorption
of the crude vapours prevented, by cutting off the
communication between the interior of the cylinders and the
apparatus for condensing the pyroacetic acid, whenever the
fire is withdrawn from the furnace. If this precaution be
not taken, the gunpowder made with the charcoal would be
of inferior quality.
On a large scale, when the object is also to prepare the
vinegar of wood, a series of cast-iron cylinders, about four
feet diameter, and six feet long, are built horizontally, in
brick-work, so that the flame of one furnace may play round
about two cylinders. Both ends project a little from the
brick-work. One of them has a disc of cast iron well fitted
and firmly bolted to it, from the centre of which disc an iron
tube about six inches diameter proceeds, and enters at a right
angle, the main tube of the refrigeration. The diameter of
this tube may be from 9 to 14 inches, according to the number
of cylinders. The other end of the cylinder is called
the mouth of the retort. This is closed by a disc of iron,
smeared round the edge, with clay lute, and secured in its
place by wedges. The charge of wood for such a cylinder
is about 8 cwt. The hard woods, oak, ash, birch, and beech,
are alone used. Fir does not answer. The heat is kept up
during the day-time, and the furnace is allowed to cool during
the night. Next morning the door is opened, the coal removed,
and a new charge of wood is introduced. The average
product of crude vinegar is 35 gallons. Its total weight
is about 300 lbs. But the residuary charcoal, according to
Ure, (Chemical Dictionary), from whom we have taken this
account, is found to weigh no more than one-fifth of the wood
employed. The crude pyroacetic acid is rectified by a
second distillation, in a copper still, in the body of which
about 20 gallons of viscid tarry matter are left for every 100.
Its acid powers are now superior to the best household
vinegar in the proportion of 3 to 2. Ure observes, that by
distillation, saturation with quicklime, evaporation of the
liquid acetate to dryness, and gentle torrefaction, the empyreumatic
matter is so completely dissipated, that on decomposing
the calcareous salt by sulphuric acid, a pure, perfectly
colourless, and grateful vinegar rises in distillation. Pyroacetic
acid is said to be a powerful antiseptic. M. Monge, Dr. Jorg,
and more lately, Mr. Ramsay, of Glasgow, have made experiments
with it. Fish dipped in it have been preserved for
many days, and meat treated in the same manner, has also
been preserved from putrefaction.
With respect to the pulverization of charcoal, the operation
is so exceedingly simple, that we deem it unnecessary to notice
it. It is obvious, that mortars, mills, &c. may be used, with
fine or coarse sieves. For fire-works, charcoal is frequently pulverized
in a leather sack, in the same manner as grained powder
is reduced to meal-powder. It may be made either coarse
or fine, to answer different purposes, by employing sieves of
different kinds. Charcoal may be separated from nitre and
sulphur, in gunpowder, by a simple process, which may be
seen by referring to the section on gunpowder.
The quantity of carbon in coal, is directly proportionate
to the quantity required for the decomposition of nitrate of
potassa, a fact necessary to be considered in the theory of the
action of charcoal in gunpowder. Thus, Mr. Kirwan found
that, 12.709 of carbon are necessary to decompose 100 of
nitrate of potassa. It will be easy to deduce the quantity of
carbon, in a given weight of coal, from the quantity of nitrate
of potassa it is capable of decomposing. The experiment is
made very readily by fusing in a crucible, five hundred or
more grains of nitre, and when red-hot projecting by degrees
the powdered coal on the nitre. When the detonation produced
by one projection of coal has ceased, add a new portion
till it produces no farther effect.
Charcoal may be made intensely black, resembling ivory
black, according to M. Denys-de-Montfort, (Bibliothèque
Physico-Economique, for March 1815,) by pulverizing it very
fine, mixing it with wine lees, and drying the mixture, and
then subjecting it to a strong heat in a covered crucible, or
other vessel.
Sec. VII. Of Gunpowder.
Having remarked, that the quality of gunpowder depends
upon the purity of the materials, of which it is formed, and
that they should be prepared in a state of purity; the subject
that will now particularly claim our attention, is the proportions
of the ingredients, their mixture, and the final preparation
of gunpowder for use. To this, we purpose to add, the
theory of its explosive effects, the different modes of proving
it, and the experiments necessary to determine the quality
of its respective ingredients, on all which we will be as brief
as the importance of the subjects will admit. Previously,
however, it may be interesting to notice the history of gunpowder,
the invention of which has so completely changed
the art of war.
The history of gunpowder has been fully treated by
many writers of eminence; but by none more largely, and, at
the same time, more satisfactorily than by the French. Beckman,
in his History of Inventions, is full on this subject.
Our purpose is not to go into details, as it would enlarge
our volume, to the exclusion, perhaps, of other and more
important matter. We shall, therefore, confine ourselves to
a few facts and observations.
Notwithstanding much has been written on the subject,
the original invention of gunpowder seems to be in obscurity.
By whom, and at what time it was invented, is a question
not fully settled. It is said to have been known in the east
from time immemorial, and whatever claim Roger Bacon,
who died in 1292, may have had to the discovery, or that he
knew the properties of gunpowder, it is certain, that the use
of fire-arms was then unknown in Europe.
Professor Beckman, who examined all the authors extant
on the origin of gunpowder, is of opinion, that it was invented
in India, and brought by the Saracens from Africa to the
Europeans, who improved the preparation of it, and employed
it in war, as well as for small arms and cannon.
M. Langles, who read a memoir on this subject to the
National Institute, in 1798, observes, that the Arabians obtained
a knowledge of gunpowder from the Indians, who had
been acquainted with it from the earliest periods. The use
of it was forbidden in their sacred books, the veidam
or vede. It was employed in 690 at the battle near
Mecca. As nitre was employed in all probability in the
Greek fire, invented about the year 678, it is supposed, that
that composition gave rise to the invention of gunpowder.
Various prescriptions, or formulæ, have been given for
the preparation of this fire. The oldest is by princess Anna
Commena, in which, however, there is only resin, sulphur,
and oil. Beckman observes, that the first certain mention
of saltpetre will be found in the oldest account of the preparation
of gunpowder, which, in his opinion, became known
in the thirteenth century, about the same time that the use
of the Greek fire, of which there were many kinds, began to
be lost. The oldest information on this subject is to be
found in the works of Albertus Magnus, and the writings of
Roger Bacon. The true recipe for making the Greek fire,
and the oldest for gunpowder, were found in a manuscript,
preserved in the electoral library at Munich. Various copies
of this manuscript were made. Bacon employed this writing,
which was mentioned by Jebb, in the preface to his
edition, from a copy preserved in the library of Dr. Mead.
Whether the writer was Marcus Græcus, is of no moment;
for Cardan observes, that the fire that can be kindled by
water, or rather not extinguished by water, was prepared by
Marcus Gracchus.
The former Marcus, mentions two kinds of fire-works; and
the composition, which he prescribes for both, is two pounds
of charcoal, one pound of sulphur, and six pounds of saltpetre,
well powdered and mixed together in a stone mortar.
Friar Bacon, who lived three centuries after Græcus, was
in possession of the recipe. It was concealed, however,
from the people, veiled in mystery. In his treatise De Secretis
Operibus Artis et Naturæ, &c. the secret of the composition
is thus expressed: "sed tamen salispetræ, LURU
MOPE CAN URBE et sulphuris; et sic facies tonitrum et corruscationem,
si scias artificium." Luru mope can urbe, is the
anagram for carbonum pulvere. Bacon supposes, that it was
with a similar composition that Gideon defeated the Midianites,
with only three hundred men. Besides the use of gunpowder
in the 9th century, in the war between the Tunisians
and the Moors, in which the former are said to have
employed "certain tubes or barrels, wherewith they threw
thunderbolts of fire," the Venetians employed it against the
Genoese, and it was reprobated as a manifest contravention
of fair warfare.
Peter Mexia, in his "Various Readings," relates, that the
Moors, being besieged, in 1349, by Alphonso the eleventh,
king of Castille, discharged a kind of iron mortars upon them,
which made a noise like thunder. This, with the sea-combat
between the Tunisians and the Moors, stated on the authority
of don Pedro, bishop of Leon, places the invention
much earlier than by some writers.
Polydore Virgil ascribes the invention of gunpowder to
a chemist, who, having put some of his composition in a
mortar, and covered it with a stone, was blown up, in consequence
of its accidentally taking fire. The person here
alluded to, according to Thevet, was a monk of Friburg,
named Constantine Anelzen. Others, as Belleforet, with
more probability, hold it to be Bartholodus Schwartz, or the
black, who discovered it, as some say, about the year 1320.
Du Cange, however, remarks, that there is no mention made
of gunpowder in the registers of the chamber of accounts in
France, as early as the year 1338. Roger Bacon knew of
gunpowder, near one hundred years before Schwartz was
born. (See the invention of cannon, in military fire-works,
fourth part.)
It is certain, that Albert de Bollstædt indicated the constituent
parts of gunpowder, when he says, in his Mirabilis
Mundi, "Ignis volans, accipe libram unam, sulphuris, libras
duas, carbonas salicis, libras sex, salis petrosi, quæ tria subtilissime
terantur in lapide marmorea; postea aliquid posterius
ad libitum in tunica de papyro volante, vel tonitrum faciente
ponatur.
"Tunica ad volandum debet esse longa, gracilis, pulvere
illo optime plena, ad faciendum vero tonitrum brevis, grossa
et semiplena."
Gunpowder was of a much weaker composition than that
now in use, or that described by Marcus Græcus. Tartalgia,
(Ques. and Inv. lib. 3, ques. 5), observes, that, of twenty-three
different compositions, used at different times, the first,
which was the oldest, contained equal parts of the three
ingredients. When guns of modern construction came into
use, gunpowder of the present strength was introduced.
The strength of powder depends upon the proportions of
the ingredients, they being pure; and Mr. Napier observes,
(Trans. Royal Irish Academy, ii.) that the greatest strength
is produced, when the proportions are, nitre, three pounds,
charcoal, nine ounces, and sulphur, three ounces. The cannon
powder was in meal, and the musket powder in grain.
In the time of Tartalgia, the cannon powder was made of
four parts of nitre, one of sulphur, and one of charcoal; and
the musket powder of forty-eight parts of nitre, seven parts
of sulphur, and eight parts of charcoal; or of eighteen parts
of nitre, two parts of sulphur, and three parts of charcoal.
The intimate mixture, therefore, and the determinate proportions
of saltpetre, charcoal, and sulphur, form gunpowder;
the different qualities of which, depend, as well upon
the proportions which are used, as on the purity of the
materials, and the accuracy with which they are mixed.
Gunpowder is reckoned to explode at about 600° Fahr;
but, if heated to a degree just below that of faint redness,
the sulphur will mostly burn off, leaving the nitre and charcoal
unaltered.
The saltpetre should be perfectly refined, and entirely free
from deliquescent salts; the sulphur as pure as possible, and,
for that reason, a preference should be given, to that which
is sublimed, or distilled; and the charcoal should be prepared
in iron cylinders, as described under that head, from woods,
which are light and tender, as the linden, willow, hazle, dogwood,
etc.
There is a considerable difference in the proportions used
by different nations; but, from the many accurate and conclusive
experiments of the French chemists, their formula is
certainly the most perfect. In English powder, three-quarters
of the composition are nitre, and the other quarter is
made up of equal parts of charcoal and sulphur; but sometimes,
to seventy-five parts of nitre, fifteen of charcoal is used,
adding ten of sulphur. Their government powder is the
same for cannon, as for small-arms.
According to a number of experiments, made at Grenille,
it was found, that the proportion of saltpetre in gunpowder,
must be in a given ratio with the charcoal, so that the latter
might effectually decompose it in the act of combustion; and
hence the ratio is as 12 of the latter to 75 of the former,
and these, with 12 of sulphur, are the proportions generally
employed. Ruggeri (Pyrotechnie Militaire, p. 91,) gives,
as the proportions, 12 parts of saltpetre of the third boiling,
2 parts of charcoal, and 1 part of sulphur. The proportions,
used in Sweden, are 75 saltpetre, 9 sulphur, and 16 charcoal;
in Poland, 80 saltpetre, 8 sulphur, and 12 charcoal; in Italy,
76 saltpetre, 12 sulphur, and 12 charcoal; in Russia, 70 saltpetre,
11 sulphur, and 181/2 charcoal; in Denmark, 80
saltpetre, 10 sulphur, and 10 charcoal; in Holland, 76 saltpetre,
12 sulphur, and 12 charcoal; in Prussia and Austria, 78
saltpetre, 11 sulphur, and 11 charcoal; and in Spain, 77 saltpetre,
111/2 sulphur, and 111/2 charcoal.
According to Klaproth and Wolff, (Dictionnaire de Chimie,
translated into French by MM. Lagrange and Vogel),
Berlin powder is composed of three-quarters nitre; one-eighth
sulphur, and one-eighth charcoal; Chinese powder, of 16
parts nitre, 6 charcoal, and 4 sulphur; Swedish powder, of
75 parts nitre, 16 sulphur, and 9 charcoal; the powder of
Lissa, of 80 nitre, 12 sulphur, and 8 charcoal; and English
powder, on the authority of Beckman, as follows: Powder
for war, 100 parts of nitre, 25 charcoal, and 25 sulphur;
musket powder, 100 nitre, 18 sulphur, and 20 charcoal;
pistol powder, 100 nitre, 23 sulphur, and 15 charcoal; strong
cannon powder, 100 nitre, 20 sulphur, and 24 charcoal;
strong musket powder, 100 nitre, 15 sulphur, and 18 charcoal;
and strong pistol powder, 100 nitre, 10 sulphur, and
18 charcoal. German powder, for war, is composed, generally,
of 0.70 saltpetre, 0.16 charcoal, and 0.14 sulphur.
A small portion of gum is sometimes added, to make the
grain firmer; but such additions retard the combustion, and
the effect.
The addition of gum arabic, however small, must injure
the quality of gunpowder, although it has the effect of making
the grain firmer, and less liable to fall into meal powder.
The grain is also made heavier, and less liable to absorb
moisture. M. Proust, in his second memoir on gunpowder,
mentions the use of icthyocolla, a fish glue, for the same
purpose; and, nevertheless, speaks of some advantages that
the gunpowder, prepared with it, possesses.
It is observed by Mr. Coleman, of the Royal Powder
Mills of Waltham abbey, that it is not exactly ascertained,
whether there is any one proportion, which ought always
to be adhered to, and for every purpose. We have no hesitation
in believing, for our own part, that the French formula
is the most correct, from the numerous experiments made
at the royal manufactory at Essone, near Paris.
A very considerable variation is found in the proportions
of the ingredients of the powder of different nations and different
manufactories. The powder made in England, is the
same for cannon as for small arms, the difference being only
in the size of the grains; but in France, it appears, that there
were formerly six different sorts manufactured; namely, the
strong and the weak cannon powder, the strong and the weak
musquet powder, and the strong and the weak pistol powder.
The following are the proportions in each, though
the reason of this nicety of distinction is not very obvious.
For the strong cannon powder, the nitre, sulphur,
and charcoal were in the proportions of 100 of the first, 25
of the second, and 25 of the third: for the weak cannon powder,
100, 20, and 24: for the strong musket powder, 100,
18, and 20; for the weak, 100, 15, and 18: for the strong
pistol powder, 100, 12, and 15; for the weak, 100, 10, and
18.
The Chinese powder appears, by the analysis of Mr. Napier,
to be nearly in the proportions of 100 of nitre, 18 of
charcoal, and 11 of sulphur. This powder, which was procured
from Canton, was large-grained, not very strong, but
hard, well coloured, and in very good preservation.
The following proportions are now used in France, for
the manufacture of gunpowder for war, for hunting, and for
mining.
| | For war. | For the chase. | For mining. |
| Saltpetre, | 75.0 | 78 | 65. |
| Charcoal, | 12.5 | 12 | 15. |
| Sulphur, | 12.5 | 10 | 20. |
After having made choice of the materials, the nitre being
pulverized, is passed through a brass sieve; the sulphur is
pulverized by means of a muller, or other contrivance, and
also sifted in a bolter; the quantities are then weighed, as
well as the charcoal.
The mixing of these substances is performed in a series
of mortars, hollowed out of a strong piece of oak wood; and
by the aid of pestles or stampers, which are set in motion
by machinery and water power, the mixture is thoroughly
made. The end of the stampers is usually covered with,
and sometimes made of, brass, and the mortars are also, in
some powder mills, lined with brass. The mill has generally
two rows of mortars and stampers, of ten each. The
nitre, sulphur, and charcoal, in proper proportions, are put
into each mortar. The charcoal is first introduced into the
mortar, being sometimes previously pulverized; then wetted
with water, and the pounding is continued for thirty minutes.
The nitre and the sulphur are then added, and the
whole is stirred with the hand. More water is then added;
it is again stirred, and the operation of pounding is continued.
The object of adding the water is to prevent the so called
volatilization of the ingredients, and to give the mixture the
consistency of paste, and at the same time to prevent the
explosion of the powder; a circumstance, which must be
always guarded against.
After the operation is continued for half an hour, the
pounders are stopt, and the powder is then re-exchanged by
means of copper or brass ladles; that is to say, the powder
of the first mortar is removed, and put into a box, and the
contents of the second mortar are put into the first, that of
the third is put into the second, that of the fourth into the
third, &c. in succession, and in the last, the contents of the
first mortar.
We make, in this manner, twelve exchanges, allowing one
hour between two, and adding water from time to time, to
the mixture, and especially during the summer months. After
this, the pounders are again set in motion, for the space
of two hours, and the operation is finished. Fourteen hours
are generally required to complete the mixture, which is then
in the form of paste. It is then granulated. After being
partially dried, the graining is performed by passing it
through sieves, which are more generally formed of parchment.
These sieves are made to work horizontally, and the
powder is caught in vessels placed beneath. The size of the
grain depends on the sieve; hence, fine grain, or coarse grain
powder is thus obtained. In the sieve is usually placed a
contrivance to break the masses, and to cause the powder
to pass through in grains. After this, the powder is
again passed through a second sieve, commonly called a
grainer, the holes of which are of the same diameter as the
powder we wish to obtain. It is then put into another sieve,
which permits only the dust to pass, whilst the grain-powder
remains. As the powder, however, contains some grains
too large, as well as others too small, we may separate the
former by a fourth sieve, of a suitable size. The dust and
fine grain are carried to the mill, and worked over. The
powder for war, and for mining, is dried immediately after
the graining.
Formerly, the powder was dried in the open air, by
spreading it on tables lined with cloth, or in oblong boxes;
but serious inconveniences resulted from it, and, particularly,
the powdermakers were obliged to watch the temperature,
as well as the state of the atmosphere. When the latter
was moist, the drying was suspended.
M. Champy, however, has obviated these inconveniences
by a very advantageous process, which consists in raising
the temperature of the air to 50 or 60 degrees, and causing
it to pass from the chamber in which it is heated, through
cloths, on which is spread a bed of powder, of a certain
thickness. By this means, large quantities of powder may
be dried, in all seasons of the year, in a short time, and at
little expense. In whatever manner the drying is performed,
there is always more or less dust formed, which, to make
the grain of one uniform appearance, must be separated by
a hair sieve. This operation is called the dusting.
Whether we adopt the plan recommended by M. Champy,
or heat the rooms for the drying of powder to a certain temperature,
by means of steam pipes, a plan which presents
every advantage, or use the old mode, the effect is the same.
The musket, or hunting powder, undergoes an operation
more than the powder for war, namely, that of glazing,
which is performed before it is dried. With the exception
of this process, it is made in the same manner, using, however,
a finer sieve in granulating it. The glazing has for its
object the smoothing, or removing the asperities of the grain,
and to prevent its falling into dust, and soiling the hands.
The powder intended for glazing is first exposed an hour
to the sun on one cloth, in winter, and between two cloths in
summer, in order to dry it more perfectly, which is very necessary
before the operation of glazing. For this purpose,
it is put into a vessel like a barrel, which is turned horizontally
upon its axis, by machinery. This barrel is furnished with
bars that go across, intended to augment the friction, or
rubbing of the grain, and expedite the process. The barrels
are made to turn slowly, to avoid breaking the grain, and at
the expiration of eight or twelve hours, the glazing is
finished, the powder having acquired a sufficient hardness
and polish. After removing the powder, the dust is separated
in the usual manner.
Gunpowder-mills are mills, in which powder is prepared,
by pounding and beating together the ingredients of which
it is composed. They are always worked by water-power,
and as there are generally many of them belonging to the
same manufactory, one dam of water will furnish a sufficient
supply. In the construction of powder-mills, the
frame of the house is made very stout, and the roof put on
lightly, so that in case of explosion, it may be carried off
easily, and thus give vent to the powder, without much injury
to the works. The lights, to enable the work to be
carried on at night, are placed on the outside of the building,
beyond the reach of the powder, and by means of glass
windows, the light passes into the mill. It is lamentable,
indeed, that so many accidents occur in the operation of making
powder. This may take place, as it has to our knowledge,
by the friction of the pounders. Their weight, the rapid
succession of the blows, and the dryness of the powder,
are the principal causes of such accidents, and sometimes by
the inattention of the workmen, suffering nails, and the like,
to get among the materials. I once witnessed the effect of an
explosion of the kind, in the neighbourhood of Frankford, in
the vicinity of Philadelphia, at the old and well-known powder
mills, at that place. It was produced, in consequence of
the friction, by the neglect of the men not adding water at a
proper time, to keep the materials moist. The mill in which
the explosion took place was not much injured; but the roof,
together with the men, were sent a considerable distance.
Some of the latter fell into the mill-race, and were much injured.
The effect, however, did not stop here; for the fire
communicated, strange as it may appear, to some of the
other mills, although at some distance, and blew them up.
Several explosions have happened at the same mills.
An experiment, made at the same works, by the then proprietor,
the father of the late commodore Decatur, by putting
the nitre, charcoal, and sulphur, into a barrel, with iron
balls covered with lead, which was turned upon its axis, terminated
in the same way. It exploded, but no other injury
or accident was sustained. On examining the balls, we
found, that the lead was entirely worn off, and the explosion
must have been owing to the iron. This experiment was
performed, in order to find if the mixture could be made in
this manner, a plan which was afterwards adopted in France,
with success, but brass balls were used. In a series of essays,
which I wrote for, and published in, the Aurora, in
1808, on the "Application of Chemistry to the Arts and Manufactures,"
as manufactures are vitally important to the
practical independence of this country, I mentioned the subject
of gunpowder, and the different modes of preparing it,
and among which, the various experiments on this subject.
The machinery, required in gunpowder mills, is exceedingly
simple. The power of the water, which may be given
by an overshot, or undershot wheel, is communicated to the
parts of the mill, which perform the work. Thus it is, that
pounders, like the snuff, or plaster-paris mill, are put in motion,
by a horizontal shaft, furnished, at different distances,
with pieces of wood, which, by the revolution of the shaft,
and meeting with the projecting pieces from the pounders,
raises them in succession. They fall, then, in the same order
of succession, in the respective mortars.
The mortars of the powder-mill, are hollow pieces of wood,
capable of holding twenty pounds of paste, composed of the
substances before mentioned, which are incorporated by means
of the pestle. There are usually twenty-four mortars in
each mill, where are made, each day, four hundred and eighty
pounds of gunpowder; care being taken, to sprinkle the
ingredients with water, from time to time, lest they should
take fire. This precaution is absolutely necessary, and if
attended to, would prevent many of the explosions, which,
unhappily, take place, in the manufacture of powder. The
friction must be great, and, therefore, the increase of temperature,
occasioned in this manner, ought to be guarded
against. This can only be done, by diminishing the time, or
number of the blows, or by proportioning the weight of the
pestle, and the frequent addition of water. The last is the
most certain, and indeed, the water is in some respects, necessary
to promote a more intimate mixture of the materials.
The observations of M. David, on the use of water in the
manufacture of powder, are certainly correct. The pestle
is a piece of wood, ten feet high, and four and a half inches
broad, armed at the bottom with a round piece of metal. It
weighs about sixty pounds.
Having mentioned one cause of the explosion of powder-mills,
that of friction produced by the pestle, we find that it
has been accounted for on another principle. The Annales
de Chimie, tome xxxv, mentions some instances of spontaneous
combustion in powder mills. It is well known, that charcoal
has the property of absorbing several gases, and the observations
of Rouppe and Berthollet, on this subject, are
conclusive. It is also known, that charcoal, which contains
hydrogen, when exposed to atmospheric air, will absorb oxygen,
and form water; and during this combination, heat must
be generated, by the emission of caloric from the oxygen
gas. It is said, then, that in cases of spontaneous combustion,
when nitre, sulphur, and charcoal, are mixed together,
(unless water be added to prevent it), this effect will ensue,
and fire be produced. We know, however, that percussion is
one source of heat; and in truth, if that opinion be well
founded, percussion itself may facilitate the union of hydrogen,
with the oxygen of the air, and necessarily operate
as a secondary cause of such explosions.
Another opinion has been advanced by Bartholdi, to account
for the spontaneous combustion in powder mills: namely,
that charcoal sometimes contains phosphorus, combined
with hydrogen, which, by the action of the pestle, is disengaged
in the form of gas, and inflames, the moment it comes
in contact with the air. Others again suppose, that it sometimes
contains pyrophorus.
Pulverizing the charcoal, in the first instance, by itself,
and adding water, during its mixture, from time to time, a
measure proposed in 1808, by M. David, and now generally
adopted, will prevent such accidents; for it appears, they
have not occurred in France, since the adoption of this plan.
Some remarks on spontaneous combustion, may be seen in
the article on artificial volcanoes.
M. Sage, (Journal de Physique, vol. lxv, p. 423, or Nicholson's
Journal, vol. xxiii, p. 277), has written on the
spontaneous ignition of charcoal, and adduced some facts on
the subject; by which it appears, that M. de Caussigni was
the first, who observed, that charcoal was capable of being
set on fire, by the pressure of mill stones.
Mr. Robin, commissary of the powder mills of Essonne,
has given an account, in the Annales de Chimie, of the spontaneous
inflammation of charcoal, from the black berry bearing
alder, that took place the 23d of May, 1801, in the box
of the bolter, into which it had been sifted. This charcoal,
made two days before, had been ground in the mill, without
showing any signs of ignition. The coarse powder, that
remained in the bolter, experienced no alteration. The light
undulating flame, unextinguishable by water, that appeared
on the surface of the sifted charcoal, was of the nature of
inflammable gas, which is equally unextinguishable.[17]
The moisture of the atmosphere, of which fresh made
charcoal is very greedy, appears to have concurred in the
development of the inflammable gas, and the combustion of
the charcoal.
It has been observed, that charcoal powdered and laid in
large heaps, heats strongly.
Alder charcoal has been seen to take fire in the warehouses,
in which it has been stored.
About thirty years ago, M. Sage saw the roof of one of
the low wings of the mint set on fire by the spontaneous
combustion of a large quantity of charcoal, that had been
laid in the garrets.
Mr. Malet, commissary of gunpowder at Pontailler, near
Dijon, has seen charcoal take fire under the pestle. He also
found, that when pieces of saltpetre and brimstone were
put into the charcoal mortar, the explosion took place between
the fifth and sixth strokes of the pestle. The weight
of the pestles is eighty pounds each, half of this belonging
to the box of rounded bell metal, in which they terminate.
The pestles are raised only one foot, and make forty-five
strokes in a minute.
"In consequence of the precaution now taken," M. Sage
observes, "to pound the charcoal, brimstone, and saltpetre
separately, no explosions take place; and time is gained in
the fabrication, since the paste is made in eight hours,
that formerly required four and-twenty.
"Every wooden mortar contains twenty pounds of the
mixture, to which two pounds of water are added gradually.
The paste is first corned: it is then glazed, that is, the
corns are rounded, by subjecting them to the rotary motion
of a barrel, through which an axis passes: and lastly, it is
dried in the sun, or in a kind of stove.
"Experience has shown, that brimstone is not essential to
the preparation of gunpowder; but that which is made without
it falls to powder in the air, and will not bear carriage.
There is reason to believe, that the brimstone forms a coat
on the surface of the powder, and prevents the charcoal
from attracting the moisture of the air.
"The goodness of the powder depends on the excellence
of the charcoal; and there is but one mode of obtaining this
in perfection, which is distillation in close vessels, as practised
by the English.
"The charcoal of our powder manufactories is at present
prepared in pots, where the wood receives the immediate action
of the air, which occasions the charcoal to undergo a
particular alteration."
In 1724, (Coll. Academ. t. v, p. 413,) M. de Moraler proposed
a new mode of mixing the materials for gunpowder.
In 1759, M. Musy proposed another method to prevent explosions;
and in 1783, the baron de Gumprecht constructed
a very ingenious powder mill, a model of which he presented
to the king of Poland, whose approbation it received.
There is an account in detail, of the results of the experiments
made by MM. Regnier and Pajot Laforet, with
different fulminating powders, in the Archives des Découvertes,
iii, p. 337. These experiments, although interesting
in a philosophical view, cannot be of service in the present
case. They were made with gunpowder, fulminating silver,
fulminating silver and mercury combined, fulminating mercury
alone, &c. See also the Bulletin de la Société d'Encouragement,
cahir 65.
The observations of M. Proust (Journal de Physique for
May, 1815) on the mixing of powder, and the consequences
that result by following the old process, may be consulted.
The process of manufacturing gunpowder, which we have
described, is followed in all, or the greater part of the factories
of France. It is, however, tedious, and not exempt from
danger. The same process, with some modifications or improvements,
is adopted in this country; but of all our gunpowder
manufactories, that of the messrs. Dupont of
Brandywine, Delaware, has heretofore produced the best
powder. Powder, however, equally powerful, has been made
in other factories.
The improved process of M. Champy, which, in many
respects, is superior to the foregoing, is the following:
1. The nitre, sulphur, and charcoal are first reduced, separately,
to very fine powder. This operation is performed
in barrels, which are made to turn upon their axis, similar to
the barrel-churn, and the substances are introduced gradually.
Balls, made of an alloy of copper and tin, are then
put in, which by their action reduce the substances to powder.
2. The second operation has for its object, the intimate
mixture of the ingredients. The quantities to be mixed are
weighed, and put into a drum with a quantity of shot, which
is made to revolve during an hour and a quarter. In this
manner, three hundred pounds of the mixture are at once
operated upon.
3. The mixture is then moistened with water. About
fourteen per cent. is added. It is then passed through a sieve
made with round holes, and then put into a drum, and submitted
for a half hour, to a rotary motion. A number of
small round grains are thereby formed, which are separated
from the mass by means of a sieve, the holes of which are
very small.
4. When a sufficient quantity of these grains are procured,
they are put into another drum, of a suitable size,
with one and a half times their weight of the original mixture.
The drum being put in motion, some water is added, which
serves to make them increase in size, by constant rubbing:
at the end of a certain time, the whole becomes granulated,
or perfectly round. The density of the grains depends on
the mixture, and the time they were kept in motion.
5. The powder being thus grained, is passed through
sieves, whose holes are of different diameters; and hence it
is divided into three kinds: viz. cannon powder, musket powder,
and fine grained powder.
6. Finally, the powder is dried, and preserved in the usual
manner. Its strength is equal to that made by the old process,
and is perfectly round.
It may be proper to observe, that this process presents
many important and decided advantages. Although, in our
description, we have not gone into details, yet the whole operation
will be seen at one view. It was practised in France,
by its inventor, M. Champy, and, besides being introduced
into the United States, it has also been adopted in Prussia.
M. Proust endeavoured to show, that charcoal made of
shoots or branches, makes the best powder, and will mix with
more facility with the nitre and sulphur; and in employing
the ordinary charcoal, two hours beating is necessary to obtain
a perfect mixture. The pestles, as Chaptal observes,
usually make fifty-five strokes in a minute. Their weight is
various; he gives them at eighty pounds.
M. Carney discovered a new process for the fabrication of
powder, and although Chaptal himself made some advantageous
changes in the process, yet the merit of the discovery
he gives entirely to Carney. The process of M. Champy,
is in some particulars the same. It will be sufficient, however,
to observe, that it is reduced to three heads: viz.
1. The pulverization, and sifting of the materials;
2. Mixing the materials intimately in vessels similar to
casks; and,
3. Giving the mixture the necessary consistence, and the
final granulation.
For some details of the process, the reader may consult
Chaptal's Chimie Appliqué aux Arts, tome iv, p. 145.
Chaptal is of opinion, that Carney's mode of fabricating
powder, presents many advantages, among which he considers
the facility of its formation, economy in the expense,
and the superiority of the powder. In a memoir on the subject,
and the formation of powder at Grenelle, Chaptal has
described the process very minutely.
Bottée and Riffault reduce the manufacture of gunpowder
in France to the following heads:
1. The mixture of the ingredients. This relates to the
manner of uniting the nitre, charcoal, and sulphur, the quantity
of the composition put into each mortar, and observations
respecting the manipulation.
The time required for reducing gunpowder to its proper
consistency, and for effecting the mixture is termed by the
French, Battage. They are usually twenty-four hours, (or
eight according to the new mode,) in pounding the materials
to make good gunpowder. Supposing the mortar to contain
sixteen pounds of composition, it would require the application
of the pestle 3500 times each hour.
The order in which they are beaten, and mixed, is as before
given, and also the rechanging, or transferring the materials
from one mortar to another.
2. Granulation, (Grenage Fr.) This operation consists, as
before observed, in passing the mixture through different
sized sieves, employing also parchment sieves, and afterwards
separating the dust by a fine sieve. The size of the
grain depends altogether on the sieve. Hence we have cannon-powder,
gunning or musket-powder, pistol-powder, and
mining-powder. Superfine powder is the very small grained.
3. Glazing. (Lissage Fr.) This operation takes off the asperities
of the grain, renders it hard and less liable to soil
the hands, and gives it a kind of lustre. It is only used for
fine powder, such as the pistol, and hunting-powder. Cannon
powder is never glazed. It is performed in a barrel-shaped
vessel, which is made to revolve on its axis, like the ordinary
barrel-churn. The quantity of powder glazed in one of
these barrels at a time, in France, is 150 kilogrammes.
By the rotary motion, the grains of powder rub against
each other, by which each grain becomes smooth, and receives
a polish. According to the motion of the barrel, so
is the glazing more perfect. This, however, is regular. After
the operation, which continues several hours, the dust is
separated from the grain by a sieve. The state of the atmosphere
influences the process. If dry, the grain receives a better
polish; if wet or damp, the operation is retarded, and the
gloss imperfect. It has been customary to introduce a very
small portion of finely pulverized plumbago, (carburet of iron),
in order to give the grain a better polish. But such additions,
however small, are obviously injurious to the powder. It is
said that it prevents the absorption of moisture. Powder,
which has been glazed with black lead, (plumbago), may be
known by its peculiar shining lustre, and also by experiment.
M. Cagniard Latour made some experiments with glazed
powder, which may be seen in the work of Bottée and Riffault,
p. 233.
4. Drying. (Séchage. Fr.) The drying of powder is performed
in two ways, viz. by exposure to the sun, and by exposure
to heat in close rooms. The English mode, that of
drying by steam pipes, MM. Bottée and Riffault are of opinion,
presents many advantages, and particularly that the powder
may be dried in all weathers, and with perfect safety.
The mode of drying gunpowder by the vapour of water,
(confining it, however, in iron pipes or vessels,) was suggested
in 1781, and 1787. See Mémoires de l'Académie des
Sciences de Suede, 1781, the Journal des Savants, 1787, and
the Transactions of the Society of Arts, vol. xxiv. Mr. Snodgrass,
in the last work, gave an account of a method of communicating
heat by steam, by using pipes of cast iron, for
which the society of arts voted him forty guineas.[18] Chaptal
(Elements de Chimie) has some judicious remarks on the exsiccation
of powder.
The experiment made at Essonne near Paris, by M.
Champy, in 1808, on a contrivance for the drying of powder,
was satisfactory. This experiment may be seen in page
242 of Bottée and Riffault.
5. Dusting, (Epoussetage.) This operation is confined
merely to the sifting. It is nothing more than the separation
of the dust from the grain, which we have before noticed.
The dust is put in the mortars, and worked over.
6. Barrelling &c. After the powder has gone through
the several operations described, it is then put into barrels,
and taken to the magazine.
After speaking of gunpowder under these heads, they
describe the manner of treating the green, (verd) and dry
meal powder; the police of powder establishments, for order
and economy; the workmen necessary in a powder manufactory;[19]
the process of making powder in the revolution;
and for the manufacture of imperial powder (which contains
0.78 saltpetre 0.10 sulphur, and 0.12 charcoal); the process
of Berne, where the powder is made of 0.76 saltpetre, 0.14
charcoal, and 0.10 sulphur; the process of Mr. Champy,
noticed in this article; observations respecting different processes;
on powder magazines; gunpowder made of other
saline substances besides nitre; different modes of proving
powder, examination of powder; description of workshops,
mechanics, and utensils, &c. &c. with a variety of engravings.
We have merely to remark, that this work of Bottée and
Riffault (a large quarto volume, of 340 pages, besides the
plates, which make a distinct volume) ought to be in the possession
of every gunpowder manufacturer, as it contains all
the information known on that subject. Of this fact there
can be no difference of opinion, that in consequence of the
great attention paid to the subject of gunpowder in France,
not only by the government, but by scientific associations and
individuals, their knowledge generally must be more minute
and accurate, and their works, as authentic records of facts,
more to be depended on.
Besides many interesting works, and memoirs in French,[20]
there have appeared some valuable dissertations in the English
language. Mr. Coleman, in his paper in the Phil.
Mag. ix, p. 355, may be considered the first, who, as superintendant
of one of the Royal powder mills, was enabled to
present a body of facts on this subject.
As the mode of manufacturing gunpowder at the Royal
Powder Mills of Waltham Abbey, in England, may be interesting
and useful, in connection with the different processes
already given; we will introduce in this place the account
of Mr. Coleman, having extracted it from the Artist's
Manual, &c. of the author, and having taken it from the
original memoir of that gentleman.
The ingredients of gunpowder are taken in the following
proportion, namely, 75 of saltpetre, 15 of charcoal, and 10
of sulphur. The saltpetre used is almost entirely that which
is imported from the Indies, which comes over in the rough
state mixed with earthy and other salts, and is refined by
solution, evaporation, and crystallization. After this it is
fused in a moderate heat, so as to expel all the pure water,
but none of the acid, and is then fit for use. The great use
of refining the nitre is to get rid of the deliquescent salts,
which by rendering the powder made of it liable to become
damp by keeping, would most materially impair its goodness.
The sulphur used is imported from Italy and Sicily,
where it is collected in its native state in abundance. It is
refined by melting and skimming, and when very impure,
by sublimation. It should seem that the English sulphur,
extracted in abundance from some of the copper and other
mines, is too impure to be economically used for gunpowder,
requiring expensive processes of refining.
The charcoal formerly used in this manufacture was prepared
in the usual way of charring wood, piles being formed
of it and covered with sods or fern, and suffered to burn
with a slow smothering flame. This method however cannot
with any certainty be depended on to produce charcoal
of a uniformly good quality, and therefore a most essential
improvement has been adopted in this country, to which the
present superior excellence of American powder may be in a
good measure attributed, which is, that of enclosing the
wood, cut into billets about nine inches long, in iron cylinders
placed horizontally, and burning them gradually to a
red heat, continuing the fire till every thing volatile is driven
off, and the wood is completely charred. But as the
pyroligneous acid, the volatile product of the wood heated
per se, is of use in manufacture, it is collected by pipes passing
out of the iron cylinder, and dipping into casks where
the acid liquor condenses. This acid is used in some parts
of calico-printing, chiefly as the basis of some of the iron
liquors and mordants for dark-coloured patterns. The wood
before charring is barked. It is generally either alder or
willow, or dog-wood, but there does not appear to be any
certain ground for preferring one wood to another provided
it be fully charred.
The above three ingredients being prepared, they are
first separately ground to fine powder, then mixed in the
proper proportions, after which the mixture is fit for the important
operation of thoroughly incorporating the component
parts in the mill. A powder mill is a slight wooden
building, with a boarded roof, so that in the event of any
moderate explosion, the roof will fly off without difficulty,
and the sudden expansion will thus be made in the least
mischievous direction. Stamping mills were formerly used
here, which consisted simply of a large wooden mortar, in
which a very ponderous wooden pestle was made to work,
by the power of men, or horses, or water, as convenience
directed. These performed the business with very great accuracy,
but the danger from over-heating was found to be
so great, and the accidents attributable to this cause were so
numerous, that stamping mills have been mostly disused in
large manufactures, and the business is now generally performed
by two stones placed vertically, and running on a
bed-stone or trough.
The mixed ingredients are put on this bed-stone in
quantities not exceeding 40 or 50 pounds at a time, and
moistened with just so much water, as will bring the mass
in the grinding to a consistence considerably stiffer than
paste, in which it is found by experience that the incorporation
of the ingredients goes on with the most ease and accuracy.
These mills are worked either by water or horses.
The composition is usually worked for about seven or
eight hours before the mixture is thought to be sufficiently
intimate, and even this time is often found, by the inferior
quality of the powder, to be too little. The fine powder
manufactured at Battle in Sussex, is still however made in
large mortars or stamping mills, in the old way, with heavy
lignum vitæ pestles. Only a very few pounds of the materials
are worked at a time.
The composition is then taken from the mills and sent to
the corning-house, to be corned or grained. This process
is not essential to the manufacture of perfect gunpowder,
but is adopted on account of the much greater convenience
of using it in grains than in fine dust. Here the stiff paste
is first pressed into hard lumps, which are put into circular
sieves with parchment bottoms, perforated with holes of
different sizes, and fixed in a frame connected with a horizontal
wheel. Each of these sieves is also furnished with
a runner or oblate spheroid of lignum vitæ, which being set
in motion by the action of the wheel, squeezes the paste
through the holes of the parchment bottom, forming grains
of different sizes. The grains are then sorted and separated
from the dust by sieves of progressive dimensions.
They are then glazed or hardened, and the rough edges
taken off, by being put into casks, filling them somewhat
more than half-full, which are fixed to the axis of a water-wheel,
and in thus rapidly revolving, the grains are shaken
against each other and rounded, at the same time receiving
a slight gloss or glazing. Much dust is also separated by
this process. The glazing is found to lessen the force of
the powder from a fifth to a fourth, but the powder keeps
much better when glazed, and is less liable to grow damp.
The powder being thus corned, dusted and glazed, is sent
to the stove-house and dried, a part of the process which
requires the greatest precautions to avoid explosion, which
in this state would be much more dangerous than before the
intimate mixture of the ingredients.
The stove-house is a square apartment, three sides of
which are furnished with shelves or cases, on proper supports,
arranged round the room, and the fourth contains a
large cast-iron vessel called a gloom, which projects into the
room, and is strongly heated from the outside, so that it is
impossible that any of the fuel should come in contact with
the powder. For greater security against sparks by accidental
friction, the glooms are covered with sheet copper, and
are always cool when the powder is put in or taken out of
the room. Here the grains are thoroughly dried, losing in
the process all that remains of the water added to the mixture
in the mill, to bring it to a working stiffness. This
Mr. Coleman finds to be from three to five parts in 100 of
the composition. The powder when dry is then complete.
The government powder for ordnance of all kinds as well
as for small arms, is generally made at one time, and always
of the same composition; the difference being only in the
size of the grains as separated by the respective sieves.
A method of drying powder by means of steam-pipes
running round and crossing the apartment has been tried
with success: by it all possibility of an accident from over-heating
is prevented. The temperature of the room when
heated in the common way by a gloom-stove is always
regulated by a thermometer hung in the door of the stoves.
The strength of the powder is sometimes injured by being
dried too hastily and at too great a heat, for in this case
some of the sulphur sublimes out (which it will do copiously
at a less heat than will inflame the powder) and the intimate
mixture of the ingredients is again destroyed. Besides if
dried too hastily, the surface of the grain hardens leaving
the inner part still damp.
Mr. Coleman deduces from experiment the following inferences,
namely: that the ingredients of gunpowder only
pulverized and mixed have but a very small explosive force:
that gunpowder granulated after having been only a short
time on the mill, has acquired only a very small portion of
its strength, so that its perfection absolutely depends on
very long-continued and accurate mixture and incorporation
of the ingredients: that the strength of gunpowder does not
depend on granulation, the dust that separates during this
process being as strong as the clean grains: that powder
undried, is weaker in every step of the manufacture than
when dried: and lastly, that charcoal made in iron cylinders
in the way already mentioned, makes much stronger powder
than common charcoal. This last circumstance is of so
much consequence, and is so fully confirmed by experience,
that the charges of powder now used for cannon of all kinds
have been reduced one-third in quantity, when this kind of
powder is employed.
In barrelling powder, particular care must be taken to
avoid moisture, and this business is also generally reserved
for dry weather.
When powder is only a little damp, it may be restored to
its former goodness merely by stoving; but if it has been
thoroughly wetted, the nitre (the only one of the ingredients
soluble in water) separates more or less from the sulphur
and charcoal, and by again crystallizing, cakes together the
powder in whitish masses, which are a loose aggregate of
grains covered on the surface with minute efflorescences of
nitre. In this case the spoiled powder is put into warm
water merely to extract the nitre, and the other two ingredients
are separated by straining and thrown away.
The specific gravity of gunpowder is estimated by Count
Rumford to be about 1.868.
The strength and goodness of powder is judged of in
several ways; namely, by the colour and feel, by the flame
when a small pinch is fired, and by measuring the actual
projectile force by the eprouvette, and by the distance to
which a given weight will project a ball of given dimensions
under circumstances in all cases exactly similar.
When powder rubbed between the fingers easily breaks
down into an impalpable dust, it is a mark of containing too
much charcoal, and the same if it readily soils white paper
when gently drawn over it. The colour should not be absolutely
black, but is preferred to be more of a dark blue with
a little cast of red. The trial by firing is thus managed; lay
two or three small heaps of about a dram each on clean
writing paper, about three or four inches asunder, and fire
one of them by a red-hot iron wire: if the flame ascends
quickly with a good report, sending up a ring of white
smoke, leaving the paper free from white specks and not
burnt into holes, and if no sparks fly off from it, setting fire
to the contiguous heaps, the powder is judged to be very
good, but if otherwise, either the ingredients are badly mixed,
or impure.
Gunpowder mixed with powdered glass, and struck with
a hammer is said to explode.
An advertisement appeared in the public papers some
time in 1813 or 14, signed T. Ewel, addressed to powder
manufacturers, by which it appears, in the words of the advertisement,
that "he obtained from the United States a
patent right for three very simple and important improvements
in the manufacture of gunpowder, which do most
truly diminish more than one half the risk, the waste, and
the expense of the manufacture. They consist in boiling
the ingredients by steam, in incorporating them without the
objection of barrels, the danger of pounders, or the tediousness
of stones running on the edge: and in the granulation
effected by a simple machine turning by hand or water, and
graining more in a day than twenty hands, losing not a particle
of dust, and making not half the quantity for re-manufacture.
The advantages of this mode have been so great
that he had to discharge half his workmen from his manufactory,
as will be readily accounted for by those accustomed
to the tediousness and loss from graining, particularly the
press powder by the sifter and rollers, &c."
We have not seen the plan in operation, and, therefore,
can say nothing respecting it; but it would appear, from the
description, that the process was conducted altogether by
steam. It is true, that the use of steam is no new application,
nor was it then, as it had been used in Europe for
heating of dye kettles, in soap boiling, distilling, for warming
apartments, and many other purposes. The application
to that particular use, that of the manufacture of gunpowder,
may be original as far as we know, notwithstanding steam
has been applied by means of pipes, &c. as is used at present
in some manufactories, for the drying of gunpowder. Professor,
now president Cooper, of Columbia College, S. C.
(Emporium of Arts and Sciences vol. ii, p. 317) in making
some observations respecting that publication, believes, that
the application of steam to the manufacture of gunpowder
to be practicable, and in reference to the advertisement, also
a real improvement; and speaking of steam for that purpose
adds, "whether it be adopted in England or not, or whether
among the numerous patents granted for the application
of steam to the arts and manufactures of that country, I
know not."
On a general principle of heating apartments by steam,
we may remark, that one cubic foot of boiler will heat about
two thousand feet of space, in a cotton mill, whose average
heat is from 70° to 80° Fahr. One square foot of surface
of steam pipe, is adequate to the warming of two hundred
cubic feet of space. Cast iron pipes are preferable to all
others for the diffusion of heat. For drying muslins and
calicoes, large cylinders are employed, and the temperature
of the apartment is from 100° to 130°. Dr. Black observes
that steam is the most effectual carrier of heat that
can be conceived, and will deposite it only on such bodies as
are colder than boiling water.
Dr. Ure (Researches on Heat) has given a new table of
the latent heat of vapours, by which it appears that the vapour
of water, at its boiling point, contains 1000 degrees,
while that of alcohol of the specific gravity, .825 contains
457°, and ether, whose boiling point is 112°, only 312.9. We
see then not only by the recent experiments of Ure, but also
those of Dr. Black, Lavoisier and Laplace, Count Rumford,
Mr. Watt and some others, that water is the best carrier of
heat, using the expression of Dr. Black, and hence is admirably
calculated for the warming of apartments and other
purposes.
Steam may be applied for the heating of water or other
fluids, either for baths or manufactures, and consequently for
the saltpetre and sulphur refineries, attached to a gunpowder
establishment, either by plunging the steam pipe with an open
end into the water cistern, if it be for the heating of water,
or by diffusing it around the liquid in the interval between
the wooden vessel and an interior metallic case. This last
mode is applicable to all purposes.
A gallon of water in the form of steam will heat 6 gallons
at 50° up to the boiling point, or 162 degrees; or one gallon
will be adequate to heat 18 gallons of the latter up to 100
degrees, making an allowance for waste in the conducting
pipe.
Mr. Woolf (Monthly Magazine vol. xxxii, p. 253) has
taken out a patent for a steam apparatus for various purposes,
among which that for the drying of gunpowder is
specified. This patent is considered under three heads; viz.
the construction of the boilers, which are cylindrical vessels
properly connected together, and so disposed as to constitute
a strong and fit receptacle for water, or any other fluid,
intended to be converted into steam, and also to present an
extensive portion of convex surface to the current of flame,
or heated air or vapour from a fire. Secondly, of other
cylindrical receptacles placed above these cylinders, and
properly connected with them, for the purpose of containing
water and steam, and for its reception, transmission, &c.
Thirdly, of a furnace so adapted to the cylindrical parts just
mentioned, as to communicate heat with facility and economy.
By means of this invention, he states, that any desired
temperature, necessary for the drying of gunpowder, may be
produced where the powder is to be dried, without the
necessity of having fire in, or so near the place as to endanger
its safety; for by employing steam only, conveyed
through pipes, and properly applied and directed, without
allowing any of it to escape into the room or apartment where
the powder is, any competent workman can produce a heat
equal to that found necessary for drying gunpowder, or
much higher if required. The heat may be regulated, to
effect the purpose, without producing the sublimation of the
sulphur, which has sometimes taken place.
Among the numerous patents of the late D. Pettibone are
some for ovens, both fixed and portable, for the drying of
gunpowder. Speaking of the use of heated air (Description
of the Improvements of the Rarefying air-stove, p. 19)
he observes, that powder makers would derive a very great
advantage by using rarefied air for drying their gunpowder.
Mr. Ingenhouz (Nouvelles experiences et observations sur
divers objects de physique) attributed the effect of gunpowder
to the simultaneous disengagement of dephlogisticated air
from the nitre, and inflammable air from the charcoal at the
moment of ignition. He followed the calculation of Bernouilli
with respect to the quantity of gas generated, viz:
that one cubic inch of gunpowder at the moment of inflammation,
calculating at the same time its expansion, occupies
not less than 2276 cubic inches.
That the effective force of gunpowder depends on the
generation and expansion of sundry gaseous fluids, is evident,
from the chemical action which takes place in the combustion.
At a red heat gunpowder explodes. This ensues
even in a vacuum; a fact at once conclusive, that, while it
possesses the inflammable principle, it has also the supporter
of combustion. It is to be observed that the particle
of powder which is struck by the spark, is instantaneously
heated to the temperature of ignition, and is thereby decomposed;
and the affinity existing between its oxygen or the
oxygen of the nitric acid, and the charcoal and sulphur produces
the principal part of the gases. The caloric thus evolved,
inflames successively, though with rapidity, the remaining
mass. The expansive force of powder, is therefore attributed
to the sudden production of carbonic acid gas, sulphurous
acid and nitrogen gas, with the water which is instantaneously
converted into steam; all of which are greatly
augmented by the quantity of caloric liberated.
The combustion, therefore, is owing to the action of the
charcoal and sulphur on the nitre; and the decomposition is
the effect of the union of the charcoal with a part of the oxygen
of the nitric acid, with which it forms carbonic acid, and
also with the sulphur producing sulphurous acid gas. It is
asserted, that sulphuretted hydrogen gas is also produced; if
so, there must be a sulphuret formed, which decomposes a
part of the water. After combustion, what remains is carbonate
of potassa, sulphate of potassa, and a small proportion
of sulphuret of potassa and unconsumed charcoal. Good powder,
however, should leave no very sensible residue when
inflamed: this is one of the proofs recommended. Thenard
observes, (Traité de Chimie, ii, p. 498,) that the products of
the combustion of gunpowder are numerous; some gaseous,
and some solid. The gaseous products are carbonic acid, deutoxide
of azote (nitrous gas) and azotic gas, besides the vapour
of water; and the solid products are sub-carbonate of
potassa, sulphate of potassa, and sulphuret of potassa.
M. Proust considers, that nitrite of potassa, prussiate of potassa,
charcoal, sulphuretted hydrogen gas, carburetted hydrogen
gas, nitrous gas, and carbonic oxide gas may be generated
or result, as the products of the combustion, when
the materials have not been properly mixed. Our object
in all cases should be to render the materials pure, and the
proportions so accurate, as to produce the greatest possible
effect, which, of course, must depend on the formation
and the consequent expansion of the gases. The effect of
fired gunpowder is owing in a great degree to the generation
of carbonic acid gas; for while the charcoal acts primarily in
the combustion, by taking a greater part of the oxygen from
the nitric acid of the nitre, with which we have said it produces
carbonic acid; the sulphur has a secondary influence,
by forming sulphurous acid gas, although it renders the combustion
more rapid, and in this respect enables the charcoal
to act at once on the nitric acid of the saltpetre.
We learn then, that in gunpowder, the quantity of charcoal
should be such as to effect the decomposition; and, that
while the sulphur has a secondary effect, in the formation of
sulphurous acid gas, it promotes, if so we may term it, the
rapid combustion, and consequent action of the charcoal.
MM. Bottée and Riffault (Traité de l'art de Fabriqué la
poudre à canon, p. 197,) after making some observations on
the constitution of powder, and the action which takes
place when it is burnt, with the aeriform products that result,
give some remarks on the proportion of charcoal necessary
to decompose a given quantity of nitric acid; and conclude
generally, that in the production of carbonic acid gas, the
principal gas which is formed, while the nitric acid is decomposed,
and gives up its oxygen to the carbon, the azote
is liberated in the state of gas, and at the same time caloric
is evolved. They observe then, that the ancient formula for
the manufacture of gunpowder, as used in France, consists
of the following proportions, viz: 0.750 saltpetre, 0.125
charcoal, and 0.125 sulphur, which agrees with modern experiments,
although chemistry at that period was in its infancy.
M. Pelletier, a member of the National Institute, and
M. Riffault made several experiments at Essonne, on different
proportions of nitre, charcoal, and sulphur in the fabrication
of powder. It is unnecessary to state the different proportions,
made use of, or the experiments on the strength of the
powder made with the eprouvette. They observe, however,
that powder made in the following proportions, was more
satisfactory, viz. 0.76 saltpetre, 0.15 charcoal, 0.09 sulphur,
and 0.76 saltpetre, 0.14 charcoal, and 0.10 sulphur.
Before we give the gaseous products, according to these
gentlemen, it will be necessary to observe, that the quantity
of nitric acid in nitrate of potassa, is 48.62 in the hundred,
and according to Gay-Lussac, nitric acid is composed in volume
of 250 oxygen and 100 azote, or in weight of 69.488
oxygen, and 30.512 azote.
Using the French gramme in the present instance, it appears
that 75 grammes of nitrate of potassa, the proportion of
this salt which enters into 100 grammes of gunpowder for
war, contains 36.47 grammes of nitric acid; and that this
quantity of acid is formed of 25.34 grammes of oxygen,
and 11.13 grammes of azote. That quantity of oxygen (25.34)
is disengaged from its combination with azote in the nitric
acid, at the instant of the inflammation of the powder by
the charcoal, forming carbonic acid; the constituents of which,
according to the proportions established by Gay-Lussac
and others, must be in the ratio of 27.376 of carbon and
72.624 of oxygen. If 25.34 grammes of oxygen exist in
75 grammes of nitrate of potassa, the proportion usually
admitted, then it will require 9.55 grammes of carbon to
saturate it, so as to produce carbonic acid. It is necessary
to consider, that this is independent of any foreign earthy
or saline matter or moisture which may exist.
With respect to the presence of hydrogen in charcoal, the
observations of Dr. Priestley, Cruikshanks, Kirwan, Berthollet,
Gay-Lussac, Thenard, Vauquelin, Lowitz and some
others, are conclusive on that head. Lavoisier made the
quantity of hydrogen in charcoal upon an average, to be
0.125 of its weight. See Memoirs de la Société d'Arcueil,
tome ii, p. 343, and the Statique Chimique, tome ii, pages 44
and 45, and also charcoal in a preceding section.
It is said, that by employing more charcoal than is necessary
to decompose the nitric acid of the nitre, the excess
passes off, not as carbonic acid, but carbonic oxide, or gaseous
oxide of carbon, which is necessarily inflamed, and
finally forms carbonic acid, as one of the products with the
carbonic acid originally formed. But the carbonic oxide,
to be changed into carbonic acid, requires in fact the oxygen
of the atmosphere.
If 34.89 grammes of carbonic acid result from the combustion
of 9.55 grammes of carbon, it must unite with a quantity
of oxygen, as before expressed, and according to the temperature,
be more or less expanded. The 11.13 grammes of
azote thus disengaged from its combination with oxygen, in
the nitric acid, remains, of course, in the gaseous state,
and is also expanded by caloric. The quantity of the latter
is stated by Lavoisier, to be 430 degrees, using a scale of
80 parts; and according to more recent experiments, it is
fixed at 600 degrees of the centigrade thermometer. The
experiments of Gay-Lussac are more recent, in which he has
given the dilatation of the gases, and the quantity of free
caloric evolved, which corresponds with the last data. We
have not room to insert his remarks.
The use of sulphur with the charcoal, in the fabrication of
powder, Bottée and Riffault state to be, (page 204) that it
inflames more rapidly than charcoal, and at a lower temperature,
which accelerates the combustion of the charcoal, and
consequently the detonation of the powder. The presence
of the sulphur augments the volume of gas, by producing
sulphurous acid gas. The proportion of sulphur in the powder
for war, is, 0.125, for musket powder, 0.10, and for mining
powder, 0.20, according to the same gentlemen.
M. Fourcroy (Système des Connaissances Chimiques, tome
iii, p. 122.) among other products of the combustion of
powder, mentions ammonia. If ammoniacal gas be formed,
the hydrogen must proceed from decomposed water, and the
azote from the nitric acid. Prussine, cyanogen, or carburet
of nitrogen, the radical of prussic acid, may also be generated
by the union of carbon and nitrogen or azote, in the
same manner. We know that cyanogen may exist in the
form of gas; but as it is inflammable, burning with a bluish
flame mixed with purple, we may infer, nevertheless, that,
if generated, it must undergo decomposition by the process
of combustion. Although I know of no experiments on
this subject, either by Gay-Lussac, Vauquelin or Davy, all
of whom have investigated the properties of this compound
of carbon and azote, which Dr. Ure has called prussine; yet
it would appear, that during its combustion, the carbon is
changed into carbonic acid, and whether the azote be also
combined with oxygen, or merely set at liberty, is altogether
uncertain. Many difficulties present themselves to a complete
and satisfactory set of experiments on the gaseous products
of fired gunpowder.
With respect to the granulation of powder, we may observe,
that although some writers consider that granulated
powder is stronger than the fine powder, yet others are of
opinion, that its strength is not increased by granulation.
Grained powder is more fit for use; but the graining of it prevents
the whole of the powder from taking fire instantaneously.
Gunpowder, although prepared in the best manner, is not
wholly consumed by inflammation. However remarkable it
may appear, yet nevertheless it is true, that a considerable
portion of gunpowder fired in a confined space is thrown out
without being kindled. That gunpowder passes through a
volume of fire without being consumed, may seem incredible,
yet the fact may be proved by firing with a musket upon
snow, or upon a paper screen.
M. Morveau communicated to the Institute some experiments,
which may be seen in the Archives des Découvertes,
i, p. 269, relative to the time necessary for the inflammation
of a given mass of gunpowder, &c. He infers that large grain
powder inflames more readily than the fine grain.
Since during the combustion of powder, gaseous bodies
more or less considerable are generated, it follows that
the full force of fired gunpowder must depend on the
maximum of the quantity of those gases; and the powder is
more strong as it is susceptible of forming more gas in a
given time. Besides the purity and the proper proportion
of the materials, the gunpowder, to produce the greatest
possible effect, should not only be intimately mixed, but dried
perfectly and with care.
It is a fact which is well known, that a musket, fowling
piece, &c. are very apt to burst, if the wadding is not rammed
down close to the powder. Hence it is obvious, that in
loading a screw barrel pistol, care should be taken that the
cavity for the powder be entirely filled with it, so as to leave
no space between the powder and the ball.
Experience has shown, that if a shell is only half or two-thirds
filled with gunpowder, it breaks into a great number
of pieces, and on the contrary, if completely filled, it separates
only into two or three pieces, which are thrown to a very
great distance.
It is also found that the same principle, of leaving a space
for air, is applied with success in blasting rocks, and splitting
trunks of trees. If the trunk of a tree is charged with
gunpowder, and the wadding is rammed down very hard
upon the powder, in that case (unless the quantity of powder
is great,) the wadding is only driven out, and the tree remains
entire; but if, instead of ramming the wad close to
the powder, a certain space is left between them, the effects
of the powder are then such as to tear the tree asunder.
Addison (Travels through Italy and Swisserland) speaking
of the celebrated Grotto Del Cani, which contains carbonic
acid gas, and on that account extinguishes flame, and is
fatal to animal life, observes, that he laid a train of gunpowder
in the channel of a reed, and placed it at the bottom of
the grotto, and on inflaming it, that it burnt entirely away,
although the carbonic acid gas in the same spot would immediately
extinguish a lighted taper, snuff and all; for, he
remarks, fire is as soon extinguished in it as in water. If
gunpowder did not contain within itself that which was
necessary to produce combustion, how are we to account for
its combustion in an atmosphere of carbonic acid gas, or in
vacuo?
Whether gunpowder be fired in a vacuum or in air, a
permanently elastic fluid is generated, the elasticity or
pressure of which is, cæteris paribus, directly as its density.
Gregory, (Treatise on Mechanics, &c. ii, p. 56) has given
a summary of the results of the experiments of Mr. Robins,
which we insert verbatim. "To determine the elasticity
and quantity of this fluid (the elastic) produced from the explosion
of a given quantity of gunpowder, Mr. Robins
premises, that the elasticity increases by heat, and diminishes
by cold, in the same manner as that of the air; and that
the density of this fluid, and consequently its weight, is the
same with an equal bulk of air, having the same elasticity at
the same temperature. From these principles, and from
the experiments by which they are established (for a detail
of which we must refer to the book itself,) he concludes that
the fluid produced by the firing of gunpowder, is nearly
3/10ths of the weight of the generating powder itself; and
that the volume or bulk of this air or fluid, when expanded
to the rarity of common atmospheric air, is about 244 times
the bulk of the said generating powder. Count Salace in
his Miscel. Phil. Math. Soc. Priv. Taurin, p. 125, makes the
proportion as 222 to 1; which he says agrees with the computation
of Messrs. Hawkesbe Amontons, and Belidor.
Hence it would follow that any quantity of powder fired
in any confined space, which it adequately fills, exerts at
the instant of its explosion against the sides of the vessel
containing it, and the bodies it impels before it, a force
at least 244 times greater than the elasticity of common
air, or, which is the same thing, than the pressure of the atmosphere;
and this without considering the great addition
arising from the violent degree of heat, with which it is
endued at that time; the quantity of which augmentation
is the next head of Robins's inquiry.
He determines that the elasticity of air is augmented in a
proportion somewhat greater than that of 4 to 1, when heated
to the extremest heat of red-hot iron; and supposing that the
flame of fired gunpowder is not of a less degree of heat,
increasing the former number a little more than four times,
makes nearly 1000; which shows that the elasticity of flame,
at the moment of explosion, is about 1000 times stronger
than the elasticity of common air, or than the pressure of
the atmosphere. But, from the height of the barometer, it
is known that the pressure of the atmosphere upon every
square inch is on a medium of 143/4ths, and therefore 1000
times this, or 14750 lbs. is the force of pressure of inflamed
gunpowder, at the moment of explosion, upon a square
inch, which is very nearly equivalent to six tons and a
half. This great force, however, diminishes as the fluid
dilates itself, and in that proportion; viz. in proportion to
the space it occupies, it being only half the strength, when it
occupies a double space, one-third the strength, when a
triple space, and so on. Mr. Robins further supposed the
degree of heat above mentioned to be a kind of medium
heat; but that in the case of large quantities of powder the
heat will be higher, and in very small quantities lower; and
that therefore in the former case the force will be somewhat
more, and the latter somewhat less, than 1000 times the
force of the atmosphere.
He further found, that the strength of powder is the same
in all variations in the density of the atmosphere: but that
the moisture of the air has a great effect upon it; for the
same quantity which in a dry season would discharge a bullet
with the velocity of 1700 feet in one second, will not in
damp weather give it a velocity of more than 12 or 1300
feet in a second, or even less, if the powder be bad, or
negligently kept. Robins's Tracts vol. i, p. 101, &c. Further,
as there is a certain quantity of water, which, when mixed
with powder, will prevent its firing at all, it cannot be
doubted but every degree of moisture must abate the violence
of the explosion; and hence the effects of damp powder
are not difficult to account for.
The velocity of expansion of the flame of gunpowder,
when fired in a piece of artillery, without either bullet or
other body before it, is prodigiously great, viz. 7000 feet
per second. But Mr. Bernoulli and Mr. Euler think it is
still much greater.
Dr. Hutton, after applying some requisite corrections to
Mr. Robins's numbers, and after remarking that the powder
does not all inflame at once, as well as that about 7/10ths
of it consist of gross matter not convertible into an elastic
fluid, gives
| v = 125 |
√ | ( | n · q |
× log.of | b |
) |
| 16 + q | a |
for the initial velocity of any ball of given weight and magnitude, and
| n = | p + w |
v2 ÷ log. | b |
| 3180 ad2 | a |
for the value of the initial force
n of the powder in atmospheric pressures: when a = length of
the bore occupied by this charge, b = whole length of the
bore, d = diameter of the ball, w = its weight, 2 p = weight
of the powder, q = a/d. In his experiments and results, he
found n to vary between 1700 and 2300, and the velocity of
the flame to vary between 3000 and 4732; specifying, however,
the modification in his computations, which would give
more than 7000 feet per second for that velocity. Taking
2200 for an average value of n, and substituting 47 for its
square root in the above formula for v, it becomes
| v = 5875 |
√ | ( | q |
× log.of | b |
) |
| 16 + q | a |
for the velocity of the ball, a
theorem which agrees remarkably well with the Doctor's numerous
and valuable experiments. (Tracts, vol. iii, p. 290, 315.)
In a French work entitled, "Le Mouvement Igné considéré
principalement dans la charge d'une pièce d'artillerie," published
in 1809, there are advanced, among other notions
which we apprehend few philosophers will be inclined to
adopt, some which may demand and deserve a careful consideration.
The author of this work observes, that if a fluid
draws its force partly from a gaseous or aeriform matter, and
partly from the action of caloric, which rarefies that aeriform
matter; then its density in proportion to its dilatation, will
follow the inverse ratios of the squares of the spaces described.
He then investigates two classes of formulæ: the
first appertains to fluids which possess simply the fluid or
aeriform elasticity, which are free from all heat exceeding the
temperature of the atmosphere. Whether there be one or
many gaseous substances signifies not, provided their temperature
agrees with that of the atmosphere; for when these
dilate they conform to the inverse of the spaces described.
The second relate to those which derive their elasticity as
well from the aeriform fluids, as from the matter of heat which
pervades them, and which are denominated fluids of mixed
elasticity, to distinguish them from those of simple or purely
aeriform elasticity. These fluids, in dilating, conform to the
inverse ratio of the squares of the spaces described. Thus
the celerity of action of mixed elastic fluids, is to that of simple
elastic fluids as S2 to S; whence it follows that mixed
elastic fluids are more prompt and energetic in their action
than others; and hence also is inferred why the fluid produced
by the combustion of gunpowder, is more impetuous
and more terrible in its operation than atmospheric air, however
compressed it may be. The force exerted by the caloric
to dissolve a quantity of powder, is regarded as equal
to that possessed by the fluid which results from that dissolution,
and is named the force of dissolution of powder by
fire: and the surface of least resistance is that (as of the ball,)
which yields to the action of the fluid. The gunpowder subjected
to experiment by this author, was of seven different
qualities, varying from 1000, the density of water, down to
946, the density of powder used by sportsmen. It was found
by theory, and confirmed by experiment, that the real velocity
with which the elastic fluid, considered under the volume
of the powder, and penetrated by a degree of heat capable
of quadrupling the volume, would expand, when it
had only the resistance of the atmosphere to surmount, is
2546.49 feet, that is, about 2734.4 feet English.
Comparing the several forces which were calculated for
the same quantity of powder, in three different circumstances:
1. When the fluid has only to surmount the atmospheric
pressure, it has a force of dissolution which is proper to it,
and which in a charge of 8 lbs. of powder (the specific gravity
944.72, for a 24 pounder,) acts upon the surface of the least
resistance with an energy equivalent to 9747.8074 lbs.
2. The fluid retarded in its expansion by a surface of least
resistance, whose tenacity (occasioned by the compactness
and pressure of the wadding, &c.) is t = 31, acquires by its
elasticity of force = 52839.1463 lbs. at the instant when
that surface yields to its action.
3. If the tenacity t = 298 lbs., the force of the fluid at the
moment when the resisting surface yields to it, will be equivalent
to 417371.4275 lbs. If each of these forces be divided
by the surface of least resistance, the quotient will indicate
the equation of each filament, namely, 1st. That of the force
of dissolution = 173.63 grains; 2d. when t = 31 lbs. that of
elasticity = 923.26 grains; 3d. when t = 298 lbs. force
elastic equal to 7433.99 grains.
Dividing again these latter values by the length of the
charges, we shall have for the mean force of each elementary
fluid particle,
1. Force of dissolution, 0.14205 grains.
2. When t = 31 lbs. the force elastic = 0.75540 grains.
3. When t = 298 lbs. the force elastic = 6.08174 grains.
It appears, however, that equal charges of powder of the
same quality employed in the same piece, produce very different
velocities; the more considerable being the resistance
to the expansion of the fluid, the less the velocity becomes.
Thus, it is found, when t = 31 lbs. the velocity of the
ball when expelled at the mouth of the piece, is 1563.6 feet:
when t = 298 lbs. v = 1350.9 feet.
The following table will exhibit in one view the velocities
with which a 24 lb. ball issues from the mouth of a gun,
when propelled with the several charges expressed in the first
column.
1st. According to the theory developed in the volume,
from which we have made these extracts.
2d. According to the experiments of M. Lombard, at
Auxerre, on guns for land service.
3d. According to the experiments of M. Teixiere de Norbec,
at Toulon, on guns for sea service.
4th and 5thly. According to the determination of Mr.
Robins and Dr. Hutton.
Charges of powder. | Velocity from Theory. |
Mean velocity from Theory. |
Velocity from experiment. |
VELOCITIES. |
When t=31 | When t=298 |
| Lombard. | Norbec. | Robins. | Hutton. |
|
| 1 lb. | 622 | 524 | 573 |
575 | 570 | 640 | 500 |
| 2½ | 980 | 836 | 908 |
906 | 940 | 750 | 730 |
| 3 | 1072 | 918 | 995 |
989 | 1020 | 969 | 830 |
| 4 | 1233 | 1057 | 1145 |
1132 | 1245 | 1069 | 940 |
| 6 | 1407 | 1216 | 1312 |
1320 | 1340 | 1215 | 1164 |
| 8 | 1564 | 1351 | 1457 |
1425 | 1560 | 1319 | 1348 |
| 10 | 1581 | 1370 | 1476 |
1475 | | | 1500 |
| 12 | 1631 | 1421 | 1526 |
1530 | | | 1600 |
It is the prodigious celerity of expansion of the flame of
fired gunpowder, which is its peculiar excellence, and the
circumstance in which it so eminently surpasses all other
inventions, either ancient or modern; for as to the momentum
of these projectiles only, many of the warlike machines of
the ancients produced this in a degree far surpassing that of
our heaviest cannon, shot or shells; but the great celerity
given to them cannot be approached with facility by any other
means than the explosion of powder."
Dr. Hutton, in conjunction with several able officers of the
artillery and other gentlemen, made an extensive course of
experiments at Woolwich, at the expense of the British
government, by the direction of the then master-general of
the ordnance, (the late duke of Richmond,) in the years
1783, 1784, and 1785, which demonstrated the following
facts:
1. That the velocity continually increases as the gun is
longer, though the increase in velocity is but very small in
respect of the increase in length; the velocities being in a ratio
somewhat less than that of the square roots of the length
of the bores, but somewhat greater than the cube roots of
the same, and nearly indeed in the middle ratio between the
two.
2. That the charge being the same, very little is gained
in the range of a gun, by a great increase of its length; since
the range or amplitude is nearly as the fifth root of the length
of the bore, and gives only about a seventh part more range
with a gun of double length.
3. That with the same gun and elevation, the time of the
ball's flight is nearly as the range.
4. That no sensible difference is produced in the range or
velocity, by varying the weight of the gun, by the use of
wads, by different degrees of ramming, or by firing the
charge of powder in different parts of it.
5. That a great difference, however, in the velocity, is occasioned
by a small variation in the windage; so much so, indeed,
that with the usual windage of one-twentieth of the
caliber, no less than between one-third and one-fourth of the
whole charge of the powder escapes and is entirely lost; and
that as the windage is often greater, one-half the powder is
unnecessarily lost.
6. That the resisting force of wood to balls fired into it, is
not constant, and that the depths penetrated by different velocities,
or charges, are not as the charges themselves, or,
which comes to the same thing, as the squares of the velocities.
7. That balls are greatly deflected from the direction they
are projected in, sometimes, indeed, so much as 300 or 400
yards in a range of a mile, or almost a fourth part of the
whole range, which is nearly a deflection of an angle of 15
degrees.
The observations of Glenie, (History of Gunnery, 1776,)
show the theory of projectiles in vacuo by plain geometry,
or by means of the square and rhombus; with a method of
reducing projections on inclined planes, whether elevated or
depressed below the horizontal plane, to those which are
made on the horizon.
This author, in his treatise, after stating in page 48, the
two following positions of Mr. Robins, namely, "that till the
velocity of the projectile surpasses that of 118 feet in a second;
the resistance of the air may be estimated to be in the
duplicate of the velocity;" that "if the velocity be greater
than that of 11 or 1200 feet in a second, the absolute quantity
of the resistance will be nearly three times as great
as it should be by a comparison with the smaller velocities;"
says, that he is certain from some experiments, which he and
two other gentlemen tried with a rifle piece properly fitted
for experimental purposes, that the resistance of the air to a
velocity somewhat less than that mentioned in the first of
these proportions, is considerably greater than in the duplicate
ratio of the velocity; and that to a celerity somewhat
greater than that stated in the second, the resistance is less
than that which is treble the resistance of the same ratio.
He observes, also, that some of Mr. Robins's own experiments
come to this conclusion; since to a velocity no quicker
than 200 feet in a second, he found the resistance to be somewhat
greater than in that ratio, and remarks, therefore, that
"after ascertaining the velocities of the bullets with as much
accuracy as possible, I instituted a calculus from principles
which had been laying by me for some time before, and
found the resistance to approach nearer to that, which exceeds
the resistance in the duplicate ratio of the velocity, by
that which is the ratio of the velocity, than to that, which is
only in the duplicate ratio."
The experiments of Mr. Dalton, confirm the premises of
Mr. Robins, that the elasticity of the gases produced from
a given quantity of powder, is equally increased by heat
and diminished by cold as that of atmospheric air. Hence,
as we before remarked, and from direct experiments, he concludes
that the elastic fluid produced by the firing of gunpowder,
is nearly three-tenths of the weight of the powder
itself, which, expanded to the rarity of common air, is
about 244 greater than the elasticity of common air, or in
other words, than the pressure of the atmosphere. To this,
however, must be superadded the increase of expansive
power produced by the heat generated, which is very intense.
The mere conversion of confined powder into elastic
vapour, would exert against the sides of the containing vessel,
an expansive force 244 times greater than the elasticity
of common air, or, in other words, than the pressure of the
atmosphere. If the heat, for the expansion of the gases,
should be equal to that of red-hot iron, this would increase
the expansion of common air, (and also of all gases) about
four times, which in the present instance would be as we
stated in the preceding pages, 244 to nearly 1000; so that in a
general way it may be assumed, that the expansive force of
closely confined powder at the instant of firing, is 1000 times
greater than the pressure of common air; and as this latter
is known to press with the weight of 143/4 pounds on every
square inch, the force of explosion of gunpowder is 1000
times this, or 14750 lbs. or about six tons and a half upon
every square inch. This enormous force diminishes in
proportion as the elastic fluid dilates, being only half the
strength when it occupies a double space, one-third of the
strength when in a triple space, and so on.
There is one more fact worthy of notice, that Mr. Robins
found the strength of powder to be the same in all variations
of the density of the atmosphere, but not so in every state
of moisture, being much impaired by a damp air, or with
powder damped by careless keeping, or any other cause; so
that the same powder which will discharge a bullet at the
rate of 1700 feet in a second in dry air, will only propel it
about 1200 feet when the air is fully moist, and a similar
difference was observed between dry and moist powder. The
sum of these remarks, with the necessary illustrations, may
be found in the extract we have given from Gregory's Mechanics.
Before we mention the different modes of proving powder,
we will offer some remarks respecting the use of sulphur in
gunpowder. The conclusions on this head are drawn from
the experiments made at Essonne, near Paris.
The sulphur is not (properly speaking) a necessary ingredient
in gunpowder, since nitre and charcoal alone, well mixed,
will explode; but the use of the sulphur seems to be to
diffuse the fire instantaneously through the whole mass of
powder. But, if the following experiments are correct, it
should seem that the advantage gained by using sulphur in
increasing the force of explosion only applies to small charges;
but in quantities of a few ounces, the explosive, or at least the
projecting force of powder without sulphur, is full as great
as with sulphur.
The following are a few out of many trials made at the
Royal Manufactory at Essonne, near Paris, in the year 1756,
to determine the best proportions of all the ingredients. Of
powder made with nitre and charcoal alone, 16 of nitre and
4 of charcoal was the strongest, and gave a power of 9 in
the eprouvette. With all three ingredients, 16 of nitre, 4 of
charcoal, and 1 of sulphur, raised the eprouvette to 15, and
both a less and a greater quantity of sulphur produced a
smaller effect. Then diminishing the charcoal, a powder of
16 of nitre, 3 of charcoal, and 1 of sulphur gave a power of
17 in the eprouvette, which was the highest produced by any
mixture. This last was also tried in the mortar-eprouvette
against the common proof powder, and was found to maintain
a small superiority. The powder made without sulphur
in the proportions above indicated was also tried in the mortar-eprouvette,
and with the following singular result: when
the charge was only two ounces it projected a sixty pound
copper ball 213 feet, and the strongest powder with sulphur
projected it 249 feet; but in a charge of three ounces, the
former projected the ball 475 feet and the latter only 472 feet;
and on the other hand the great inferiority of force in the
smaller eprouvette of the powder without sulphur has been
just noticed.
It is a fact, known from time immemorial, that by the combustion
of bodies caloric is generated, or chemically speaking,
is given out in a free state; but the cause was not known
until the anti-phlogistic theory of chemistry was established,
which abolished as untenable the old doctrine of phlogiston;
The quantity of caloric, which passes from a latent to a free
state in combustion, as combustion is nothing more than the
phenomena occasioned by this transition, is variable; and depends
therefore on the substances burnt, and the nature of
what is denominated the supporter of combustion.
The experiments of MM. Lavoisier and Laplace have
shown the quantity of caloric produced by the combustion
of different substances by the calorimeter, a table of which
may be seen in Thenard. (Traité de Chimie, &c. t. i, p. 81).
From this table it appears, that while a mixture of one
pound of saltpetre with one pound of sulphur liquefied, by
its combustion, thirty-two pounds of ice, one pound of hydrogen
gas melted 313 lbs. phosphorus 100 lbs. and the same
quantity of charcoal 96.351 lbs.; and by the detonation of a
mixture of one pound of saltpetre with 0.3125 lbs. of charcoal
(French weight) melted only 12 lbs. of ice.
In the table of the elevation of temperature by the combustion
of different substances, the caloric being communicated
to water, (Thenard, Traité de Chimie, vol. i, p. 82), it
appears, that by the combustion of equal weights of hydrogen
gas, phosphorus, charcoal, and oak, the caloric produced
was as follows:
| Hydrogen | 23,400° |
| Phosphorus | 7,500 |
| Charcoal | 7,226 |
| Oak wood | 3,146 |
The reader may find some interesting calculations on this
subject in Biot's Traité de Physique, &c. tome iv, p. 704,
and 716.
It appears also, that in the combustion of one pound of hydrogen
gas, six pounds of oxygen were consumed, and according
to Crawford's experiment the caloric given out melted
480 lbs. of ice. One pound of phosphorus requires for
combustion one and a half pounds of oxygen gas; one pound
of charcoal, 2.8; and one pound of sulphur, 1.36. See Thomson's
System of Chemistry, vol i, p. 133.
While noticing this subject we may remark, that in combustion
heat and light, according to the Lavoiserian doctrine,
are given out from the oxygen gas, while the oxygen unites
with the combustible body: which has since been modified
by supposing, that while caloric is evolved from the gas, the
light is emitted from the burning body. There are some
facts contrary to the received theory of combustion; that of
gunpowder furnishes one. We have also another instance in
the combustion of oil of turpentine by nitric acid.
Gunpowder will burn with great avidity in close vessels, or
under an exhausted receiver, and we know that the oxygen
is already combined with azote in the nitric acid of the nitrate
of potassa, and consequently not in a gaseous but a solid state;
yet we also know that a great quantity of caloric and light
are emitted during the combustion, and nearly all the products
are gaseous. The other anomaly is, that as combustion
is produced by pouring nitric acid on spirit of turpentine,
the oxygen being already combined with azote, caloric and
light are evolved by the mixture of the two fluids, from which
it is inferred, that oxygen is capable of giving out caloric and
light, not only when liquid, but even after combustion. In
the instance of gunpowder, in order to explain the combustion
which takes place independently of atmospheric air, or
any aeriform supporter, "the caloric and light," in the opinion
of Dr. Thomson, (Chemistry, i, 128) "must be supposed to
be emitted from a solid body during its conversion into gas,
which ought to require more caloric and light for its existence
in the gaseous state than the solid itself contained."—Mr.
Lavoisier (Elements of Chemistry, p. 157,) observes,
that he and M. De la Place deflagrated a convenient quantity
of nitre and charcoal in an ice apparatus, and found that
12 lbs. of ice were melted by the deflagration of one pound
of nitre. After giving the proportions of acid and alkali in
nitre, and the quantity of oxygen and azote in the acid, he
observes, that during the deflagration, 1451/3 grains of carbon
have suffered combustion along wit 3738.34 grains of
oxygen; and as 12 lbs. of ice were melted, one pound of
oxygen burnt in the same manner would have melted 29.5832
lbs. of ice. To which, if we add the quantity of caloric retained
by a pound of oxygen, after combining with carbon to
form carbonic acid gas, which was already ascertained to be
capable of melting 29.13844 lbs. of ice, we shall have for the
total quantity of caloric remaining in a pound of oxygen when
combined with nitrous gas in the nitric acid, 58.72164; which
is the number of pounds of ice, the caloric remaining in the
oxygen in that state is capable of melting. In the state of
oxygen gas it contains at least 66.66667. M. Lavoisier infers
then, that the oxygen in combining with azote to form
nitric acid, only loses 7.94502, and that "this enormous
quantity of caloric, retained by oxygen in its combination
into nitric acid, explains the cause of the great disengagement
of caloric during the deflagration of nitre; or, more strictly
speaking, upon all occasions of the decomposition of nitric
acid." This view of the subject may enable us to explain
the production of caloric, in those cases of combustion which
cannot be explained on the ordinary principles; and, with
regard to gunpowder, the accension of oil of turpentine by
nitric acid, and similar cases, we may conclude, as the only
rationale which seems applicable, that it is nothing more than
the transition of caloric from one state to another, from a
latent to a free state. Be this as it may, the combustion in
such instances furnishes an anomaly to the already established
doctrine, of the absorption of oxygen, or the base of the
supporter, and the evolution of caloric from the gas, and not
from the combustible; or, in other words, the change of caloric
in the supporter from a combined to an uncombined state.
The idea of latent heat may be had from Dr. Black's own
expression (Black's Lectures by Robinson:) "By this discovery,"
says the doctor, "we now see heat susceptible of fixation—of
being accumulated in bodies, and, as it were, laid
by till we have occasion for it; and are as certain of getting
the stored-up heat, as we are certain of getting out of our
drawers the things we laid up in them." Murray's System
of Chemistry, 2d edition, p. 398, and Watson's Chemical Essays,
vol. iii, &c. may be consulted on this subject with advantage.
See Introduction.
We will consider, in the next place, the subject of gunpowder
proof. The first examination of gunpowder is by
rubbing it in the hands, to find whether it contains any irregular
hard lumps. If it is too black, it is a sign that it is
moist, or else, that it has too much charcoal in it; so, also, if
rubbed upon white paper, it blackens it more than good
powder does; but, if it be of a kind of azure colour, it is a
good indication. If on crushing it with the fingers, the
grains break easily, and turn into dust, without feeling hard,
it is a criterion, that it has too much coal; or, if in pressing
it under the fingers upon a smooth hard board, some grains
feel harder than the rest, it is inferred that the sulphur is not
well mixed with the nitre. By blasting two drachms of each
sort on a copper plate, and comparing it with approved
powder. In this proof it should not emit any sparks, nor
leave any beads or foulness on the copper. The method of
burning, which is commonly employed, Mr. Robins observes,
is to fire a small heap on a clean board, and to attend nicely
to the flame and smoke it produces, and to the marks it
leaves behind on the boards.
Another trial of powder is to expose it to the atmosphere.
One pound of each sort, accurately weighed, is exposed
to the atmosphere for 17 or 18 days; during which
time, if the materials are pure, it will not increase any thing
material in weight, by attracting moisture from the air. One
hundred pounds of good powder should not absorb more
than twelve ounces, or somewhat less than one per cent. See
Mr. Coleman's account of the manufacture of powder in
England, page 110.
To determine the strength of powder in the easiest manner,
is by comparing its effect with improved powder; as,
for instance, by using a given weight of powder, as two
ounces, and discharging a ball of a known weight, say 64
pounds, from an 8 inch mortar. The best cylinder powder
generally gives about 180 feet range, and pit 180, with a ball
and charge of the above weights; but the weakest powder,
or powder that has been reduced, &c. only from 107 to 117
feet.
The practice adopted in England, we are told, is, that the
merchant powder, before it is received into the king's service,
is tried against powder of the same kind made at the king's
mills, and it is received if it gives a range of 1/20 less than
the king's powder, with which it is compared. In this comparison,
both sorts are tried on the same day, and at the same
time, and under exactly the same circumstances.
James (Mil'y Dictionary, p. 348) remarks, that the proof
of powder as practised by the board of ordnance, besides
that of comparing it by combustion on paper, is that 2
drachms, when put into the eprouvette, must raise a weight
of 24 pounds to the height of 31/2 inches.
According to Bottée and Riffault, before gunpowder is received
into the arsenals of France, for service, it undergoes
a variety of proofs; and the instructions for that purpose are
contained under forty-two heads, embracing, at the same
time, the specific duties of the officer employed for that service.
The principal points, however, refer to a standard
proof, made with the eprouvette, and differ, in no essential
part, from the methods practised elsewhere. There is a
uniformity in the French service, which cannot but be admired.
In every thing which relates to the ordnance especially,
even in the most minute details, the French, without
doubt, exceed any other nation.
Having examined the different kinds of proof, not only
for gunpowder, but for cannon and small arms, as established
by an act of parliament, it appears, that musket powder
undergoes another description of proof. A charge of four
drachms of fine grain or musket powder in a musket barrel,
should perforate, with a steel ball, a certain number of half
inch wet elm boards, placed 3/4 inch asunder, and the first
39 feet 10 inches from the barrel. The powder manufactured
at the Royal Powder Mills generally passes through fifteen
or sixteen, and restored powder, from nine to twelve.
There are other contrivances made use of, such as powder-triers,
acting by a spring, commonly sold at the shops, and
others again that move a great weight, throwing it upwards,
which is an imperfect kind of eprouvette.
Dr. Hutton is of opinion, that the best eprouvette is a
small cannon, the bore of which is about one inch in diameter,
and which is to be charged with two ounces of powder,
and with powder only; as a ball is not necessary; and the
strength of the powder is accurately shown, by the arc of the
gun's recoil.
The whole machine is so simple, easy, and expeditious,
that, as Dr. Hutton remarks, the weighing of the powder is
the chief part of the trouble; and so accurate and uniform,
that the successive repetition, or firings, with the same quantity
of the same sort of powder, hardly ever make a difference
in the recoil of the one-hundredth part of itself.
Gregory (Treatise of Mechanics, vol. ii, p. 178) has given
a more particular description of the eprouvette of Dr. Hutton;
namely, that it is a small brass gun, 21/2 feet long, suspended
by a metallic stem, or rod, turning, by an axis, on a
firm and strong frame, by means of which, the piece oscillates
in a circular arch. A little below the axis, the stem divides
into two branches, reaching down to the gun, to which
the lower ends of the branches are fixed, the one near the muzzle,
the other near the breech of the piece. The upper end
of the stem is firmly attached to the axis, which turns very
freely by its extremities in the sockets of the supporting
frame; by which means, the gun and stem vibrate together
in a vertical plane, with a very small degree of friction.
The charge is the same we have mentioned, usually about
two ounces, without any ball, and then fired; by the force of
the explosion, the piece is made to recoil or vibrate, describing
an arch or angle, which will be greater or less, according
to the quantity or strength of the powder.
To measure the quantity of recoil, and consequently the
strength of the powder, a circular brazen or silver arch of
a convenient extent, and of a radius equal to its distance below
the axis, is fixed against the descending two branches of
the stem, and graduated into divisions, according to the purpose
required by the machine: viz.
1st. Into equal parts, or degrees, for the purpose of determining
the angle actually described in the vibration.
2nd. Into equal parts, according to the chords, being, in
fact, 100 times the double sines of the half angles, and running
up to 100, as equivalent to 90 degrees.
3d. Into unequal parts, according to the versed sines; they
are, in truth, 100 times the versed sines of our common tables,
1411/2 corresponding with 90 degrees. These serve to
compare the forces.
The divisions in these scales are pointed out by an index,
which is carried on the arch during the oscillation, and then,
stopping there, shows the actual extent of the vibration.
Two ounces of powder, give, on an average, according to
the experiments of professor Gregory, about 36 on the
chords, or about 21° on the arch. A more detailed account,
with diagrams, may be seen, by consulting Hutton's Tracts,
vol. iii, p. 153.
The eprouvette constructed by the late Mr. Ramsden, differs
from the preceding simply by the gun's recoiling in a direction
parallel to itself, instead of its vibrating as a pendulum.
The gun is suspended by two hanging frames, which
serve to make it rise and fall, during its recoil and return,
so as always to retain the horizontal direction. The degrees
are measured upon a fixed arch, by means of a moveable index,
nearly as in Dr. Hutton's eprouvette.
We remarked, that the common powder-triers are small
strong barrels, in which a determinate quantity of powder is
fired, and the force of expansion measured by the action
excited on a strong spring, or a great weight. The French
eprouvette is usually a mortar of seven inches (French) in
caliber, which with three ounces of powder should throw a
copper globe of sixty pounds weight to the distance of 300
feet. No powder is admitted that does not answer this trial.
This eprouvette, however, has been improved, as we shall
mention hereafter. These methods have been objected to,
the former because the spring is moved by the instantaneous
stroke of the flame, and not by its continued pressure, which
is somewhat different; and the other, on account of the tediousness
attending its use, when a large number of barrels
of powder are to be tried.
J. Bodington of London, invented a machine to try the
force of gunpowder. M. the chevalier d'Arcys made an
eprouvette on the principle of Mr. Robins. M. Le Roy
proposed to employ the different elastic forces of inflammable
air, but his method has never been used. M. Tresnel
also proposed an eprouvette, which was announced in the
French journal, entitled Nouvelles de la République des Lettres
et des Arts, par M. de la Blancherie, for 1782, p. 190.
It is hardly necessary to observe, that the eprouvette has
undergone some improvements: thus, the eprouvette of Darcy
consists of a cannon suspended at the extremity of a bar
of iron, and the graduated arc measures the recoil; the
eprouvette of Regnier is nearly the same, and the arc determines
the force of the powder.
A description of mortar-eprouvettes generally, may be
seen in the work of MM. Bottée et Riffault, (Traité sur l'art
de Fabriquer la poudre à canon,) and in the Memoirs of Proust
(Journal de Physique, tome lxx, et suiv.), &c.
I saw a model of an improved eprouvette, which appeared
to possess every advantage, at the Ordnance Arsenal near
Albany; an index hand moved in an arc.
Quicklime is said to increase the force of powder. Dr.
Baine says, that three ounces of pulverized quicklime being
added to one pound of gunpowder, its force will be augmented
one-third; shake the whole together, till the white colour
of the lime disappears.
The preservation of gunpowder in properly constructed
magazines, of which we will have occasion to speak hereafter,
is a subject that should claim our attention. The
greatest difficulty, if any, exists at sea, and on this head we
have a variety of opinions.
Mr. James (Military Dictionary, p. 348) says, that it has
been recommended to preserve gunpowder at sea by means
of boxes lined with sheet-lead. M. D. Gentien, a naval officer,
tried the experiment by lodging a quantity of gunpowder
and parchment cartridges in a quarter of the ship which
was sheathed in this manner. After they had been stowed
for a considerable time, the gunpowder and cartridges were
found to have suffered little from the moisture; whilst the
same quantity, when lodged in wooden cases, became nearly
half destroyed.
It has been recommended to line powder magazines with
lead, as a mean for preserving the powder from dampness.
The lead, it seems, so far attracts moisture, as to condense
it. In the last volume of the Transactions of the American
Philosophical Society, is a memoir on leaden cartridges, by
Wm. Jones, Esq. the late secretary of the navy, which, besides
preserving the powder, has advantages over either paper
or flannel. See Magazine.
What is termed the analysis of gunpowder, is nothing more
than the separation of its component parts, and determining
the relative proportions of its respective ingredients. We
may indeed examine the quality of the nitrate of potassa, by
dissolving a portion of powder in distilled water, and employing
the reagents mentioned under the head of nitre; but
for the purpose of separating, as well as determining the proportion
of saline matter, charcoal and sulphur, it may be
readily accomplished in the following manner: Take a given
quantity of gunpowder and affuse it in distilled water sufficient
to dissolve the salt; after suffering it to remain for some
time, applying heat to assist the solution, decant the whole
upon a filter of unsized paper. The saltpetre and other saline
matter will pass through, and the sulphur and charcoal
remain on the filter. By evaporating the solution to dryness,
and weighing it, the quantity of saltpetre will be found;
or, after drying the mass on the filter, and weighing it, by
subtracting its weight from that of the original, it will give
the loss sustained, which of course is the saltpetre. By exposing
the mass to a heat sufficient to evaporate the sulphur,
it will be expelled; the loss sustained will indicate its quantity,
and the weight of the residue the proportion of
charcoal. The sulphur may be even separated by subjecting
gunpowder itself to the action of a well regulated heat;
it will sublime, and leave the nitre and charcoal. It takes a
much higher temperature to inflame gunpowder than is required
to volatilize sulphur. The method of extracting the
nitre from damaged powder, we have already noticed. See
nitre. This process also depends on the solubility of the
nitre, and the insolubility of the charcoal and sulphur.
Bishop Watson, in his Chemical Essays, proposed the examination
of gunpowder by solution and sublimation; a process
sufficiently accurate. If it should be our object to ascertain
the presence and quantity of foreign substances, in
the saltpetre, this may be accomplished by following the process
already given, viz: by collecting the precipitates, &c.
determining their weights, and making the necessary allowance,
for the new compounds, as the carbonates of lime, sulphate
of barytes, muriate of silver, and the like.
Baumé proposed the analysis of powder by sublimation,
in order to separate the sulphur, using however a graduated
heat. Another mode consists in distilling the powder in a
retort with water, and collecting the sulphur and sulphuretted
hydrogen gas, and then separating the charcoal, &c. A
third process was recommended by Pelletier, after the separation
of the nitre, by subliming a mixture of the residue
with mercury, which, however, presents no advantages. The
use of nitric acid has also been recommended, in order to
acidify the sulphur. For this purpose nitric acid is poured
on the residue, and the whole is digested for some time, renewing
the acid as it is decomposed. By this means the
carbon, as well as the sulphur, is acidified, and carbonic acid
gas with deutoxide of azote are disengaged, leaving the
sulphuric acid formed by the union of oxygen with the sulphur,
in the remaining fluid, from which it is separated by
nitrate of barytes, and its quantity ascertained by the sulphate
of barytes produced. The proportion of sulphur, in
the sulphuric acid, is then calculated.
Caustic potassa has been employed for the separation of the
sulphur from the charcoal. It unites with the sulphur, forming
a sulphuret; and as sulphuretted hydrogen gas is also
produced, the sulphuret must likewise contain the hydroguretted
sulphuret of potassa. The charcoal is not acted upon.
M. Vito Caravelli, professor of chemistry at Naples, (Elements
d'Artillerie, 1773,) has given a more simple process
for the separation of these substances, which depends on their
specific gravity. When mixed with water, the sulphur
will deposite, and the charcoal float on the fluid.
Vauquelin directed his attention to this subject, and has
recommended various processes, not only for the separation
of the sulphur and charcoal, but also the nitre.
The process of Smithson Tennant is nearly of the same
nature.
The separation of sulphur from charcoal may be effected
more perfectly, according to Brande, by introducing the
mixture into a small retort furnished with a stop cock, exhausted,
and filled with chlorine gas; the chlorine will unite
with the sulphur, forming a chloride, and leave the charcoal,
which may be washed, dried, and weighed.
Baumé found, that when all the sulphur is expelled which
will be driven off in the heat, a certain portion will still remain,
and not burn away at a lower temperature than will consume
the charcoal; so that to the last the burning residue will
smell strongly sulphurous. This retained portion of sulphur
he finds, by the results of many other experiments, to be very
uniformly about one-twenty-fourth part of the whole sulphur
employed; whence, for all common purposes, an adequate
correction may be made, by estimating that the slow weak
combustion of the residue, after the nitre has been extracted,
destroys only 23/24ths of the sulphur instead of the whole.
On trying to separate them by an alkaline solution, he found
some of the sulphur to remain undisturbed, and still adhering
to the charcoal. In consequence of this circumstance,
it is recommended, to insure a perfect analysis, to separate
the nitre in the first place from gunpowder, by hot water,
and to treat the residue with nitric acid. After the sulphur is
acidified, the addition of nitrate or muriate of barytes
will separate, effectually, the sulphuric acid from the fluid,
and form a sulphate of barytes; this being collected, washed,
dried, and weighed, will give the quantity of sulphuric acid,
and of sulphur in the acid, by the well known proportion of
acid in the salt, and of sulphur in the acid. One hundred
parts of sulphate of barytes, when perfectly dry, indicate
fourteen and a half parts of sulphur; or, which is the same,
according to Chenevix, one hundred and fifty-five grains denote
twenty-two and a half grains of sulphur.
The observations of M. Champy and professor Proust on
humid powder, seem to place the quantity of water absorbed,
at 8, 10, and 14 per cent. These proportions, it is evident,
depend greatly on the quality of the nitre; and if deliquescent
salts exist in any quantity, the absorption, and consequently
the increase of weight must be greater. Chemical
examination will readily determine this fact.
The different sorts of gunpowder are usually distinguished
by marks on the heads of the barrels. Gunpowder
marks are various. All gunpowder for service is mixed in
proportions according to its strength, so as to bring it as
much as possible to a mean and uniform force. This sort
of powder, says Adye, (Bombardier and Pocket Gunner,) is
marked with a blue L. G. and the figure 1/2; or with F. 1/2
G. and the figure 3, whose mean force is from 150 to 160
of the eprouvette. This is the powder used for practice, for
experiments, and for service. The white L. G. or F. G. is
a second sort of powder of this quality. It is sometimes
stronger but not so uniform as the L. G. It is, therefore,
generally used in filling shells, or such other things as do not
require accuracy. The red L. G. F. G. denotes powder in
the British service, made at the King's mills, with the coal
made in cylinders, and is used at present only in particular
cases, and in comparisons, and to mix with other sorts to
bring them to a mean force. The figures 1, 2 or 3 denote
that the powder is made from saltpetre, obtained from the
rough. Other marks are also in use to designate the rifle,
musket, cannon powder, and the like.
Powder merchants recover damaged gunpowder, by putting
a part of the powder on a sail cloth, and adding an equal
quantity of good powder, which is well mixed with it, and
the mixture is then dried.
Sec. VIII. Of Lampblack.
Lampblack, which is nothing more than a finer kind of
coal, is so named from its being produced and originally
made by the combustion of oil in lamps. It is hardly necessary
to say, that it is formed in the combustion of turpentine,
various species of the pinus, tar, pitch, rosin, &c. as all these
substances yield it more or less, and of different qualities.
It is the result of imperfect combustion; for, if the combustion
were rapid, and the smoke itself consumed, we
would then have only carbonic acid. This fact is exemplified
in the argand lamp, which, on account of the glass cylinder,
consumes its own smoke. The process of forming lampblack
is conducted in lampblack houses. After the combustion has
ceased, the soot or lampblack is swept down, as it collects
above and on the sides of the room. When it is obtained
by burning the dregs and coarser parts of tar, furnaces of a
particular construction are used. The smoke is conveyed
through tubes into boxes, each covered with linen, in the form
of a cone. Upon this linen the soot is deposited, from which
it is, from time to time, beaten off into boxes, and afterwards
packed in barrels for sale. There is also a very fine black,
superior in many respects to lampblack, especially in making
the ink for copperplate printers, prepared by carbonizing
grape stalks, &c. in close iron vessels.
There are two kinds of lampblack in common use. One is
the light soot, from burning wood, of the pine and other resinous
kinds, usually made in Sweden. In Sweden the impure
turpentine is also burnt for this purpose. It is collected
from incisions made in pine and fir-trees, and the turpentine
is boiled down with a small quantity of water, and strained,
while hot, through a bag; and while this part is used for
another purpose, the dregs and pieces of bark remaining in
the strainer, are burnt in a low oven, whence the smoke is conveyed
through a long passage into a square chamber, which
contains a sack, as above stated, where the greater part of the
lampblack collects, and the remainder is caught in the chamber.
The other kind of lampblack is formed by carbonization,
a process similar to that for preparing the black, called blue-black,
from grape stalks, or for preparing the German black,
a pigment made by charring principally the lees of wine and
husks of grapes.
The lampblack made in Philadelphia, for the purpose of
printers' ink, is prepared by the combustion of tar. One barrel
of Carolina tar will produce forty pounds of soot or
lampblack.
A patent was granted 1798 to a Mr. Row, (Repository of
Arts, vol. x.) for a newly invented mineral lampblack. It is
nothing more than the smoke obtained by the combustion of
pit coal. In the county of Sarrbrook on the Rhine, are some
establishments for making coke and lampblack at the same
time; and from 100 lbs. of coal, 33 lbs. of coke, and 31/2 of
lampblack are obtained. Jeanson (Archives des Découvertes,
&c. i, p. 21) has described a process for carbonizing oil.
Lampblack has the same chemical properties as charcoal,
and being remarkably fine, and containing sometimes a portion
of oil, is used on that account in the composition of some
fire-works. Its quality may be known by its colour, and,
when burnt, leaving no residue. It may be sufficient to remark,
that like charcoal, it decomposes nitric acid; and the
nitrates, when mixed with it, and projected into a red-hot
crucible, will deflagrate or produce a vivid combustion. It
may therefore be used in all kinds of fire-works, in which
charcoal is employed. Concentrated nitric acid, when poured
on lampblack, previously dried, will produce combustion. It
is to the carbon, as well as the hydrogen, in oil of turpentine,
that turpentine inflames when brought in contact with nitric
acid; and although much charcoal is deposited, yet a considerable
part passes off in the state of carbonic acid gas. By
a proper treatment, lampblack like charcoal may be converted
into artificial tannin by nitric acid. It has also antiseptic
qualities; but to be used for this purpose it should first be
exposed to heat, in order to drive off any oil which it may
have contracted, or with which it might be contaminated.
The quality of lampblack may, we suspect, be improved by
bringing it to a state of ignition in close iron vessels. If required
intensely black, as for the making of printers' ink,
this process might be advantageously used. Mixed with
gum water, it makes a durable writing ink, or, according to
Mr. Close, by mixing it with a solution of copal in oil of lavender.
This ink is not, like the common kind, acted upon
by acids.
Sec. IX. Of Soot.
Soot, or that substance formed by the combustion of wood,
&c. which collects in chimnies, is used in some of the pyrotechnical
preparations, partly to assist the flame, and partly to
modify its appearance. It is found, that soot, produced by
the combustion of wood, is formed by the condensation of
the carbon evolved in the smoke. It also contains volatile
products, the nature of which, depends on the kind of combustible.
Wood-soot is considered a good manure, on account
of the carbon and some volatile salts, it is said to contain.
That it contains ammonia, is evident, since it may be
detected by experiment; and that this alkali is combined with
carbonic acid, and sometimes with muriatic acid, a number
of facts prove. Soot, then, when used in fire-works, may,
like sal ammoniac, but in a lesser degree, produce a particular
coloured flame. When soot is well washed in water, in order
to free it from saline and other soluble matter, and probably
from pyroacetic acid, and then pulverized, it forms the
pigment called bistre. It is a fact, that the excrement of
some animals, the camel for instance, which feed on saline
vegetables, when burnt, will yield a soot, which contains
an abundance of muriate of ammonia, or sal ammoniac.
Hence, by re-subliming this soot, sal ammoniac was originally
prepared in Egypt. The quantity of muriate of ammonia,
contained in the soot of camels' dung, is considerable. It is
found that 26 lbs. of soot yield on an average 6 lbs. of that salt;
See Sal Ammoniac. Camels' dung, and in fact the dried excrement
of animals, furnish a very good fuel. In Egypt it
is used with advantage. The soot of oil, &c. is of a different
kind; it is the substance, which forms our lampblack.
Sec. X. Of Turpentine, Rosin, and Pitch.
All these substances enter into the composition of fire-works,
either to increase the rapidity of combustion, as in incendiary
fire-works, or, in some cases, as with rosin, to produce
a coloured flame. That they contain carbon and hydrogen,
as their principal ingredients, is well known; to
which we may attribute their rapid combustion, and the facility
with which they decompose nitrous salts. The Greek
fire, for example, owed, it is said, its powerful effect to turpentine,
which, with other substances employed, made the
composition remarkably inflammable, and the decomposition
of the nitre, (which some say it contained) so rapid, as even
to defy the action of water.
All of the turpentines are obtained from different species
of pinus. Common turpentine is the resinous juice, which
exudes chiefly from the Pinus Sylvestris, or Scotch fir, and
is obtained by boring holes into the trunks of the trees, early
in the spring, and placing vessels beneath for its reception.
This turpentine, and in fact all others, are composed of rosin
and a volatile oil. The latter is obtained by distilling the turpentine
with water. It passes over with the water, from which
it is afterwards separated, and is then known by the name of
the essential oil, or spirit of turpentine. The substance, remaining
in the still, is common rosin, or yellow rosin, known
likewise by the names of fidlers' rosin and colophony. Tar
is also obtained from the roots and refuse parts of the fir
tree, by cutting them in billets, piling these in a proper manner,
in pits or ovens, formed for the purpose, covering them
partly over, and setting them on fire. During the combustion,
a black and thick matter, which is tar, falls to the bottom,
and is conducted into barrels.
Pitch is nothing more than tar boiled down to a solid
consistence; it is usually made, however, by melting together
coarse hard rosin, and an equal quantity of tar. The
ancient pitch possessed a flavour and fragrance. White
pitch is the same as the white turpentine.
Melted pitch, sulphur, and camphor, mixed, when nearly
cold, with pulverized saltpetre, and afterwards thinned with
spirit of turpentine, will form a composition, that is very
inflammable, and will almost resist the action of water. A
similar composition must have formed the Greek fire, of
which, according to Beckman, there were several kinds.
The turpentine trees furnish various products: Thus, the
Pinus Abies, or spruce fir, yields the Burgundy pitch, and its
branches produce the Essence of Spruce; but other species
of pinus are used for the same purpose, which are nearly
allied to it, and which grow abundantly in Canada. From
the Pinus laryx, or larch, Venice Turpentine is obtained;
but that sold, is usually made by melting rosin, and adding
the spirit of turpentine. From the sap of the larch, the
Russians prepare a gummy substance, known in Russia by
the name of Orenburg gum. Turpentine is extracted in
France, in great quantity, from the pinus maratima. Gallipot,
colophony, tar, pitch, &c. are likewise obtained from it.
The turpentine of cedar, according to Dr. Pocoke (Travels
through Egypt) was employed by the Egyptians for embalming,
the operation being performed in several ways. It
was injected, and used with salt, nitre, &c.
Pitch, tar, and turpentine all enter into sundry compositions,
used in war. The different incendiary preparations,
noticed in the last part of the work, are composed, in general,
of either one or all of these substances. Their use is obvious.
Being very inflammable, and brought in contact with
gunpowder, nitrate of potassa, &c. they burn with great rapidity,
and consume every thing before them. Hence the
tourteaux of the French, tarred links, and fascines, carcasses,
&c. owe their effect to the presence of these substances.
Rosins are considered to be volatile oils, saturated with
oxygen.
Thus, or frankincense, of which there are several varieties,
has been long used in fire-works; it is frequently employed
in the composition of odoriferous fire. It is obtained from
the pinus abies, and appears in tears. During winter, the
wounds made in fir trees become incrusted with a brittle
substance, called barras or gallipot, consisting of rosin united
with a small portion of oil. All rosins, according to the
experiments of Gay-Lussac, and Thenard, (Recherches
physico-chimiques) are composed of a great quantity of carbon
and hydrogen, united with a small quantity of oxygen.
To this, we attribute their great inflammability, and it enables
us to account for the rapid decomposition of nitre, in
those preparations, in which nitre and resinous substances are
employed. See General Theory of Pyrotechny, sec. ii.
For the accension which takes place by mixing oil of turpentine
and nitric acid, see the properties of nitric acid, under
the head of nitre.
Morey (Silliman's Journal, vol. ii, p. 121) observes, that
a small quantity of spirit of turpentine being added to a
mixture of iron-filings, sulphuric acid, and water, the hydrogen
gas produced, will burn with a very pleasant white
flame, and without smoke. He also observes, that, if the vapour
of spirit of turpentine be made to pass through a tube,
covered at the upper end with a fine wire gauze, it burns
with much smoke; but, if a quantity of atmospheric air be allowed
to mix with it, the smoke ceases, and the flame continues
white. If more still be added, the flame lessens, and
becomes partly blue. By adding still more and more, it will
burn with a very small flame, entirely blue, and with a singular
musical sound. If still more be added, the flame, and
every ray of light cease; but that the combustion still continues,
is certain, from the explosive detonating noise, continuing
to be distinctly heard.
Mr. Morey further remarks, that, if tar, containing a
considerable proportion of water, is dropped on brick or
metal, at a temperature, which will readily evaporate them,
the vapours will burn with white shooting streaks, much
flame, and without smoke, while the water lasts. Inflamed
drops of tar, burn, while falling, with a red flame, and much
smoke; but, on reaching boiling water, the smoke instantly
disappears, and streaks of a white flame shoot up. He also
says, that, if water in one cylinder be made to boil, and the
steam be led to the bottom of another, containing rosin, or
tar, at a high temperature, after passing up through it, the
water, together with the vapourized portion of the rosin or
tar, will, when the preparations are properly regulated, burn
with an intense white flame, and no smoke; much the greater
part of which appears, (by alternately shutting the steam out,
or letting it in) to be derived from the water; and also, that
if steam be led over the surface of tar in a cylinder, and
made to force out a small stream of it through a pipe, into
which a quantity of steam is also admitted, and made to mix
intimately with it, they burn, with a great body of flame and
intense heat, and without smoke, provided the proportions are
well regulated. These facts are remarkable, and may probably
lead to some useful applications. That water is decomposed,
appears more than probable. If water is thrown, in considerable
quantities, on oil or tar, in a state of inflammation,
as Morey observes, the flame is greatly increased; and if
ever so small a drop of water fall into oil at a temperature
near boiling, an explosion will take place. He draws the following
conclusion, from these circumstances; that we have
only to pass the steam of water through oil, heated to the
temperature, at which it boils, or takes fire, to produce combustion.
Sec. XI. Of Common Coal, or Pitcoal.
All the variety of coals, belonging to the coal family, are
composed principally of charcoal and bitumen, with small
quantities of earthy, and metallic matter. Whether we consider
the formation of coal, the localities or situation in which
it occurs, whether in beds or strata, accompanying other
minerals, such as clay-slate, bituminous schistus, sandstone,
&c. is of no moment, except so far as the situation in which
it is found, indicates or determines its character and qualities.
The different kinds of coal owe their variety to the presence
or absence of bituminous matter, whether great or small,
the quantity of the carbonaceous ingredient, and the presence
or absence of anthracite, and other foreign substances. Coal,
which is, or ought to be preferred in fire-works, should contain
the greatest quantity of bituminous matter; and, while
it contains the due proportion of carbon, should be entirely
free from anthracite. Coal, and all other inflammable fossils,
are characterized by their inflammability, insolubility in
water, alcohol, and acids, and by their specific gravity,
which scarcely exceeds 2, unless loaded with foreign matter.
Coal surcharged with bitumen, burns with a bright flame,
and, by distillation, affords more carburetted hydrogen gas,
which is used for gas light. Common coal, or pitcoal, burns
in cakes, more or less, during combustion. Besides charcoal
and bitumen, it contains sometimes pyrites, sulphate of iron,
and earth. Slate-coal, however, contains more clay.
The collieries, from which pitcoal is obtained, are more
or less extensive in England, and elsewhere. Immense beds
of coal are found near Pittsburgh, and Richmond. The Lehigh,
and other localities in the United States, produce it also
in abundance, but of various qualities. Coal districts, or places
in which it is found, may be considered a valuable acquisition
to a country; and as coal is so essential in many
manufactories, it is a satisfaction to know, that our resources
in this particular, are almost inexhaustible;—a fact, which
shows, that, while our national industry is the main pillar of
national independence, in its true acceptation, the arts, which
require a supply of coal, will, for centuries to come, be abundantly
furnished with it.
When coal is exposed to the action of heat, in iron retorts
or cylinders for the preparation of coal gas, or when it is
exposed to heat in coke-ovens, the bitumen, &c. are disengaged,
and there remains a coal called coke. Coke, therefore,
is nothing more than charred pitcoal.
Mr. Mushet made some valuable experiments on the carbonization
and incineration of coals. He found that the
Scotch cannel-coal afforded 56.57 volatile matter, 39.43
charcoal, and 4 ashes; while the stone-coal, found under basalt,
gave 16.66 volatile matter, 69.74 charcoal, and 13.6
ashes, and oak wood, 80.00 volatile matter, 19.5 charcoal,
and 0.5 ashes. The quantity of gas, however, depends entirely
on the quality of the coal. A temperature of about 600°
to 700° is sufficient to disengage it. A pound of good
cannel coal, properly treated in a small apparatus, will yield
five cubic feet of gas, equivalent in illuminating power to a
mould candle, six in the pound. One pound of coal, on a
large scale, affords only 31/2 cubic feet of gas. A gas jet,
which consumes half a cubic foot per hour, gives a steady
light equal to that of a candle of the above-mentioned size.
The cannel coal, known in Scotland by the name of parrot
coal, is very inflammable, takes fire immediately, and produces
a brilliant flame. It is used by the poor as a substitute for
candles. This coal, we have seen, furnishes an abundance of
carburetted hydrogen gas. It has the appearance of jet, and
admits of being turned in a lathe.
Stone coal, Kilkenny coal, Welch coal, and glance coal consist
almost entirely of charcoal; and hence, when laid on
burning coals, they become red-hot, emit a blue lambent
flame, in the same manner as charcoal, and at length are
wholly consumed, leaving behind a portion of red ashes.
They burn without smoke or soot.
The pitch coal, which has a brownish-black colour, and is
generally found massive in plates, the bovey coal, called
brown coal, and bituminous wood, with the anthracite coal,
and some others of lesser note, form the remaining varieties
of coal.
When coal is employed in fire-works, it is to be pulverized,
and sifted in the usual way. For some purposes it is preferred
to charcoal, in consequence of the bitumen it contains,
which appears to contribute to the rapidity of the combustion.
It is to be observed, that, as the base of coal is carbon, its action
is the same as charcoal, and therefore, by producing the
same effects, or nearly so, as charcoal itself, the phenomena
it presents are analogous. As 12.709 parts of carbon, according
to Kirwan, are required to decompose 100 parts of
nitrate of potassa, we may readily ascertain the quantity of
real carbon in any specimen of coal. According to Kirwan,
50 grains of Kilkenny coal will decompose 480 grains of nitrate
of potassa, from which it is inferred, that ten grains
would have decomposed 96 of nitrate of potassa, precisely
the same quantity of charcoal, which would have produced
the same effect. Therefore, Kilkenny coal is composed almost
entirely of carbon. Cannel coal, when treated in the
same manner with nitrate of potassa, left a residuum of 3.12
in the hundred parts of earthy ashes; and 66.5 of it were required
to decompose 480 grains of nitrate of potassa, but 50
of charcoal would have been sufficient. From this experiment,
it appears, that 66.5 grains of cannel coal contain 50
grains of charcoal, and 2.08 of earth; the remaining 14.42
grains must be bitumen. In a similar manner, by knowing
the quantity of coal required to decompose a given quantity
of nitrate of potassa, when melted in a crucible, the quantity
of carbon in any variety of this substance may be ascertained.
With respect to the earthy and metallic ingredients of
coal, we may ascertain them by burning the coal, with free
access of air. What remains unburnt must be considered an
impurity. Its weight may be ascertained, and its nature by
analysis. As the object, however, is generally to determine
the relative proportion of combustible matter, or carbon,
which different species of coal are capable of yielding, that
point may be determined in the manner already stated.
That coal originates from vegetables, whatever opinion
may be formed to the contrary, we may fairly infer from a
variety of vegetable remains, and impressions of animals
that are both found in the strata of coal, and in earthy strata
above and below them. Of its submarine origin, there can
also be no doubt; or why do we find in it shells, the impression
of fish, and other productions of the ocean? That coals
grow like vegetables, an opinion with the uninformed, is contrary
to fact, and the nature of things.
We may notice, in this place, another substance which
sometimes is found partially carbonized; we mean turf.
Turf or peat, obtained from morasses, consists of a multitude
or congeries of vegetable fibres, partly in a decomposed
state, and is frequently so inflammable as to inflame by a
spark. Very extensive morasses are found in some countries
from which the inhabitants are supplied with fuel. Some
improvements in the manner of preparing turf for use, have
been made; that of charring it in kilns is one. By this process
it kindles sooner, burns with less air, and forms a moderate
and uniform fire, without much smoke, though it is
not so lasting as that produced by turf. The method of reducing
turf to coal is still practised in some parts of Bohemia,
Silesia, and Upper Saxony, which was first proposed in
1669, by John Joachim Becher, who also recommended, at
that time, a process for depriving coals of their sulphur, by
burning them in an oven, and the use of the oil procured from
them. What are our modern patents on this subject? What are
lord Dundonald's coke ovens and coal tar? Are they original?
Boyle (Usefulness of Natural Philosophy,) speaks of Becher's
invention. Anderson, (History of Commerce,) however,
observes, that something of the kind was attempted before
Becher's time; for in the year 1627, John Hacket and Octavius
Strada obtained a patent for their invention of rendering
coals as "useful as wood for fuel in houses, without hurting
any thing by their smoke."
With respect to turf, it appears that Hans Charles von
Carlowitz, to save wood, introduced the use of it in Saxony,
in the smelting houses, in 1708.
Turf has been known for a long time. It was used from the
earliest periods, in the greater part of Lower Saxony, and
throughout the Netherlands; as is fully proved by Pliny's
account of the Chauci, who inhabited that part of Germany.
Pliny (Hist. Nat. lib. xvi, c. i.) observes, that they pressed
together with their hands, a kind of mossy earth which they
dried by the wind rather than by the sun, and which they
used, not only for cooking their victuals, but also for warming
their bodies. We also read that a morass in Thessaly, having
become dry, took fire, and the same thing ensued in some part
of Russia, where a morass burned several days and did much
damage. Very dry turf is nearly as inflammable as spunk,
and when prepared with nitre, has been used for the same
purpose. See Pyrotechnical sponge.
Ure (Chemical Dictionary) observes, that "turf has been
charred lately in France, it is said by a peculiar process, &c."
The truth is, that the charring of turf is by no means a recent
invention, as we stated above. Sonnini (Journal, &c.)
says, that it is superior to wood. It kindles slower than charcoal
of wood, but emits more flame and burns longer. In a
gold-smith's furnace, it fused eleven ounces of gold in eight
minutes, while wood charcoal required sixteen.
Turf frequently contains phosphoric acid; for bogs or morasses,
and bog-iron ores abound, more or less with it, in
different states of combination. The siderite of Bergmann
which he supposed to be a peculiar metal, and found in bog-ore,
is a phosphate of iron. The native Prussian blue, which
also occurs in such localities, is generally admitted to be a
combination of phosphoric acid iron and alumina.
Sec. XII. Of Naphtha, Petroleum, and Asphaltum.
Naphtha, petroleum, and asphaltum are all modifications of
bituminous oil; and as they are all inflammable, naphtha
being the most so, they have been used in the preparation of
fire-works.
It will be sufficient to remark, that naphtha or rock oil is
a yellow or brownish bituminous fluid, of a strong, penetrating
odour, and so light as to float on spirits of wine. By
exposure to the air, it acquires the consistence of petroleum.
It takes fire on the approach of a lighted taper, and burns
with a bluish flame, yielding a thick smoke. Plutarch and
Pliny both affirm, that the substance with which Medea destroyed
Creusa, the daughter of Creon, was naphtha. She
sent a dress to the princess, which had been immersed in,
or covered over with the oil, and which burst into flames as
soon as she approached the fire of the altar. Plutarch relates
that Alexander the great, was amused and astonished
with the effects of naphtha, which were exhibited to him at
Ecbatana. On the shores of the Caspian sea, it is burnt in
lamps, instead of oil. There are copious springs of this oil
in that neighbourhood, and it is sometimes obtained by distilling
bituminous substances.
Hanway (Travels through Russia into Persia, i, 263,)
mentions the naphtha of Baku, and remarks that the earth
is strongly impregnated with it; for, he adds, by taking up
two or three inches of the surface, and applying a live coal,
the part which is so uncovered, immediately takes fire, almost
before the coal touches the earth. Eight horses were consumed
by the fire from naphtha, being under a roof where
the surface of the ground was turned up, and, by some accident
took fire. A cane, or tube, even of paper, set two inches
in the ground, and the top of it touched with a live coal, and
blown upon, immediately emits a flame, without hurting either
the cane or paper, provided the edges be covered with
clay. Three or four of these lighted canes will boil water
in a pot.
Pinkerton, (Petralogia ii, p. 148,) speaks of the naphtha
of Baku, which exists on the western side of the Caspian sea,
being carried to Constantinople, "where it formed the chief
ingredient of the noted composition called the Grecian Fire;
which, burning with increased intensity under water, became
a most formidable instrument against an inimical fleet." See
Greek fire.
Naphtha is obtained of several qualities by suffering it to
remain in pits or reservoirs. The Persians, who use it in their
lamps, and to boil their food, find it to burn best with a
small mixture of ashes. They keep it at a small distance
from their houses, in earthen vessels, under ground, to prevent
any accident by fire, of which it is extremely susceptible.
Hanway speaks also of what is called the everlasting fire,
about ten miles from Baku, which is an object of devotion to
the followers of Zoroaster. Near the altar of their temple,
he observes, is a large hollow cane, from the end of which issues
a blue flame, which the Indians pretend has continued
to burn ever since the flood, and which, they fancy, will last
to the end of the world.
We have no hesitation in believing, that the ancients made
use of this oil in their exhibitions; and, from its properties,
that when mixed with other substances, it would make a
brilliant fire-work.
Petroleum, called also mineral tar, is less fluid and less
transparent than naphtha. It has an oily consistence, more
or less viscid. It occurs of a black or brown colour. It
burns rapidly, but not so readily as naphtha, and exhales a
black smoke. By distillation, it forms a liquid like naphtha,
and leaves a thick tar in the retort.
It exudes from rocks, is found in wells, &c. In Pegu,
the wells furnish annually 400,000 hogsheads. It is used
there in the place of oil for lamps. When boiled with rosin,
it is used for painting houses, and the bottoms of vessels.
In the embalming of dead bodies, it was employed by the
ancient Egyptians; and, in some countries, clay, soaked in it,
is used as fuel.
It is found in the United States, in Kentucky, Ohio, the
western parts of Pennsylvania, in New York at the Seneca
lake, &c. The Seneca or Genessee oil is the same bitumen.
When petroleum is exposed to the atmosphere, it acquires
a greater degree of consistence, and passes into another bituminous
substance, called maltha. This has the properties,
and frequently the appearance of pitch. When burnt, it
yields more smoke and soot than petroleum. According to
its original meaning, it signifies a kind of cement; and the
maltha mentioned by Pliny, Heineccius, Festus, and others,
which was employed in the same manner as our modern sealing
wax, was a mixture of pitch and wax, and was also used
to make reservoirs, pipes, &c. water-tight. Maltha also
sometimes resembles wax. Mr. Kirwan, however, gave it
the name of mineral tallow.
Mineral or Barbadoes tar is somewhat thicker than petroleum,
and nearly of the consistence of common tar. It is
used for the same purposes as the ordinary petroleum. Elastic
bitumen, a variety between the softer and harder bitumens,
resembles caoutchouc. It burns with a bright flame,
and bituminous odour.
Asphaltum, or solid bitumen, is much harder than pitch,
brittle, and of a brownish-black colour. It burns freely, and
leaves but little residue. In Judea, it is found on the waters
of the Dead sea, or the lake of Asphaltes. It is also called
Jews' pitch. It was employed by the Egyptians for embalming
under the name of mumia mineralis.
Both maltha and asphaltum were used by the ancients as a
cement. The walls of Babylon were cemented with these
substances, as obtained from the river Is, which falls into the
Euphrates. It may be observed, that those countries, which
yield bitumen, contain salt springs, and it frequently accompanies
pyrites. Limestone, particularly the black, contains
it, and the colour is often owing to its presence. The stink
stone, or bituminous carbonate of lime, is of this kind. The
retinasphaltum, a combination of bitumen and earth, having
a yellow colour, burns with a bright flame, and fragrant
odour, which at last becomes bituminous. Many stones,
and particularly some of the black marbles, owe their colour
to bitumen; hence they burn white. The bituminous schistus,
or bituminous shale, sometimes contains so much of
this substance as to burn in the fire. Jet is a mineral of a
black colour, and resembles the cannel coal. It is inflammable,
producing a green flame, with a strong bituminous
odour.
With respect to bitumens, we may observe, that they all
possess one character, that of being inflammable; and that
they are more or less so in proportion as they partake of the
principle of naphtha; or, at least, the rapidity of their combustion
depends upon the presence of this oil. The following
additional facts, therefore, with respect to naphtha, may
be interesting: Certain liquids have the property of uniting
with naphtha, which has also the property of dissolving and
combining with solid substances, of which the following examples
may be stated:
At the degree of ebullition, it dissolves sulphur, which, on
cooling, is in part deposited in needle-form crystals. At the
same temperature, it also dissolves phosphorus, part of which
is again separated.
It unites also with iodine. With camphor, it also combines,
and in large quantity. It takes up a much larger proportion
of pitch. In the cold, its action on wax is feeble,
but assisted by heat, it unites with it in all proportions. On
lac and copal, its action is feeble. In the cold, it does not
dissolve caoutchouc; but when assisted by heat, it dissolves
this substance, though not completely. These facts may
determine its action in certain mixtures.
According to Theodore de Saussure's Analysis, (Bibliot.
Universelle, iv, p. 116), it appears, that naphtha is composed
of 87.60 carbon, and 12.78 hydrogen.
Sec. XIII. Of Oil of Spike.
This oil is principally used as a vehicle for mixing the ingredients
of some kinds of fire-works; and, although it is employed
in that way, yet it has also an effect in combustion,
having similar properties with liquid bitumen. It enters into
the composition of some of the preparations, and perhaps is
equally good as liquid bitumen. Indeed, the oil of spike, as
sold in the shops, and used principally by farriers as an embrocation
for horses, is an artificial preparation, made by mixing
together about five ounces of Barbadoes tar, with a pint
of the spirit of turpentine.
Sec. XIV. Of Amber.
Amber, succinum, karabe, the electron of the ancients,
which are synonimous terms, is very inflammable. A piece
of it, put on the point of a knife, and set on fire, will burn
entirely away, emitting, at the same time, a white smoke, and
a somewhat agreeable odour. It is used in the composition
of fire-works, and particularly in some kinds of rockets. All
the preparation it undergoes, when thus used, is to reduce
it to powder in a mortar, and to pass it through a fine sieve. It
also forms a part of the composition of odoriferous fire; but
the formulæ for the latter are various.
Amber is of various colours, either yellowish, white, or
honey-yellow. It is translucent, and sometimes transparent.
It may be turned or polished. It occurs in grains or in irregular
masses. Alluvial deposites of sand, gravel, &c. frequently
contain it. It is also found with bituminous wood,
brittle lignite, or jet, and with other substances. It has been
discovered in New-Jersey, near Trenton, in alluvial soil.
Naturalists believe, that amber was once a resinous juice.
Masses weighing 20 lbs. have been found. Sometimes it
contains insects. It is formed into beads and the like. As
amber becomes electric by friction, and the ancients called it
electron, the term electricity is derived from it. By distillation,
it yields both an acid, (the succinic), and an oil. Jet is
usually considered black amber.
We may introduce here a few remarks respecting ambergris:
Ambergris is a substance, which has a peculiar fragrance,
and for that reason is used as a perfume, and may be employed
like similar substances in odoriferous fire. As to its origin,
we have no certain account; but it seems, from its general
properties, to be formed in the same manner as bituminous
substances, although it is mostly found on the sea-shore,
where it has been probably washed up from the sea.
Ambergris is found principally on the shores of Ceylon,
and is known to be good, by laying some of it on a very hot
knife, when, if pure, it will not only melt and run like wax,
but entirely evaporate, leaving no residue.
Ambergris, on account of its price, (the retail price in
London being a guinea per ounce), is frequently adulterated
with various mixtures of benzoin, labdanum, meal, &c.
scented with musk. But pure ambergris, when heated, has a
greasy feel, and appearance, and is soluble in hot ether and
alcohol.
Sec. XV. Of Camphor.
Camphor is a resinous substance, although generally called
a gum, which has a peculiar, and powerful smell. It is obtained
principally from the Laurus Camphora. It is extracted
from this, and other trees in the East Indies. We
are informed, that, in Borneo and Sumatra, the larger pieces
which contain the most camphor, are picked out with sharp
instruments. The Chinese cut off the branches, chop them
small, and place them in spring water. They are then boiled,
and stirred with a stick. As soon as the camphor is observed
to adhere to the stick, the fluid is strained. It is
then poured into a basin, and the camphor separates, in
Japan, the roots and the extremities of the branches are
steamed. It is also obtained by sublimation. The roots,
wood, and leaves are all boiled in large iron pots, and the
camphor is collected on straw, placed in a tubular head.
With respect to the refining of crude camphor, in order
to produce heads, as they are called, and to free it from impurities,
the operation is nothing more than sublimation.
Sublimers made of glass are used; and into each, the camphor,
along with a small portion of lime, is introduced, and
they are then placed in a sand bath. Heat is applied, and the
pure camphor rises and attaches itself to the upper part
of the vessel, forming the refined camphor.
The general properties of camphor are the following: It
is not altered by the atmospheric air, but is volatilized during
warm weather. It is insoluble in water; is soluble in
alcohol, forming the spirit of camphor, and also in volatile
and fixed oils. It is not acted upon by the alkalies. It is dissolved
in acids without effervescence, and by some it is decomposed.
Nitric acid converts it into a peculiar acid, called
the camphoric. It melts between 300 and 400 degrees. It
takes fire, and burns with a white flame, and, generally,
while it presents the character of a resin, it shows, by its
combustion, like other inflammable bodies, that it contains,
in its composition, a large quantity of carbon and hydrogen.
There are several species of camphor, which have been
examined by chemists and which differ in their properties.
These are, common camphor, the camphor of volatile oils,
and the artificial camphor, formed by treating oil of turpentine
with muriatic acid.
The base of camphor forms a constituent part of some
volatile oils, which are in a liquid state; and for its separation,
it appears to require a combination with oxygen.
Camphor may be apparently set on fire by means of water,
an experiment, which is nothing more than producing chemical
action by it, in the following manner: Put a portion of
nitrate of copper on some tin-foil, along with camphor; then
by adding some water, and quickly wrapping the foil up,
pressing the edges close, it will inflame, and sparks of fire be
produced.
Camphor has been used in the manufacture of candles.
For this purpose, it is dissolved in brandy, and the wick,
composed of equal parts of cotton and linen, is dipped in.
It is then dried, and covered, in the usual manner, with
tallow or wax. The tallow, recommended as the best for
candles, is a combination of equal parts of mutton and beef
suet.
Camphor is very soluble in acetic acid, which is highly
inflammable. This solution is decomposed by water. When
combined with essential oils, it forms aromatic vinegar.
Romieu has observed that small pieces of camphor floating
on water have a rotary motion.
Camphor enters into a composition, which is used to determine,
like a barometer, the state of the weather, and the
changes it undergoes. According to the Journal de Pharmacie,
1815, some experiments were made in France on the
fluid taken out of one of the English weather gauges. The
liquid contained water and alcohol, was strong with camphor,
and reddened litmus paper. The tube contained 31/2
ounces. On analysis, its contents were found to be, 24 grains
of alum, 120 grains of camphor, and enough water to dissolve
the former, and alcohol to dissolve the latter. A similar
composition was made, and put into a tube, which, it
seems, had the same effect. The tube is hermetically sealed.
M. Cadet observes, that the prognosticator, made in Paris
many years ago, was a similar preparation.
Although, according to Cadet, this contrivance cannot be
depended upon, as the appearances it presents are not regular;
yet, as the effect is produced by heat, as well as
light and electricity, the following summary may be added:
1. In fair weather, the composition remains at the bottom,
and the liquor is clear.
2. Before rain, it will rise a little; the liquor will be clear,
having merely a star floating in it.
3. Before a storm, it will rise to the surface, the liquor
will appear troubled. These appearances may be seen 24
hours before the change in the weather takes place.
4. In winter, it is higher than common. During a snow,
it will be very white, and pieces are seen in motion.
5. In settled weather in summer, and when warm, the
composition will be low.
6. To know from what quarter wind will come, the composition
will remain attached on the opposite side of the
bottle to that from which it is expected.
Camphor has been burnt, like ether and alcohol, by platinum
wire, previously heated. Dr. Ure observes, that a cylinder
of camphor may be used for both wick and spirit, in
the aphlogistic lamp; and the ignition is very bright, while
an odoriferous vapour is exhaled. By adding various essential
oils in small quantities to the alcohol of the lamp, various
aromas may be made to perfume the air of an apartment.
See Scented Fires for rooms.
Camphor is employed in those fire-works chiefly, which
are exhibited in rooms; its expense being an objection to its use
in large exhibitions. In what are termed perfumed pastes, or
mixtures, scented fire, or odoriferous fire-works, it is used in
abundance: in fact, it enters into nearly all the compositions
of this kind. Camphor, besides producing, alone, a white
flame, gives a brilliant light, and, when mixed with other
substances, adds greatly to the appearance of the flame; and,
giving out a powerful odour, destroys, in a measure, the disagreeable
smell arising from the combustion of the sulphur
and nitre.
By referring to the article on Greek fire, and some incendiary
preparations used in war, it will be seen, that camphor
is an important constituent. As camphor is very combustible,
and will even burn on the surface of water, it is well
adapted for all those purposes. We have already spoken of
the Greek fire; and it seems, that the peculiar character of
that fire, of burning in water, was owing to the presence of
camphor. This opinion appears plausible, when we consider,
that some preparations have been made with camphor,
which had the property of burning on water.
Camphor may be pulverized by the assistance of, and
brought into intimate mixture with, nitre and sulphur; because
the former, in particular, tends to divide it. But it may
be pulverized separately, and afterwards added to the composition,
by rubbing it in a mortar with a small quantity of
alcohol, or spirit of wine; or, if this cannot be had, with
fourth proof brandy. As camphor is very inflammable, its
effects, when mixed with saltpetre and fired, are much the
same as those produced by other resins, or concrete oils. A
combustion, more or less rapid, ensues, and, while the nitre
itself is decomposed, the camphor also undergoes the same
change, producing both water and carbonic acid, from the
union of two of its elements, the hydrogen and carbon, with
the oxygen of the nitric acid. In all cases, in which camphor
is employed in artificial fire-works, although its own
flame is white, it may assist in increasing the flame,
which, however, is modified, according to the substances,
which enter into the composition. These may not retard its
combustion, but, nevertheless, may change the appearance of
the flame; as is the case, when we employ the filings of iron,
steel, brass, or zinc, sal ammoniac, rosin, saw-dust, and other
substances, which usually form a part of such mixtures.
Upon the whole, then, we may consider, that camphor acts
in fire-works; 1st, as an inflammable body; 2ndly, that, besides
being in a great measure decomposed, a portion of it
is evaporated, and communicates, to the surrounding atmosphere,
a peculiar smell, which is recognised in the odoriferous
fire-works; 3rdly, that, while it acts in taking a part of
the oxygen from the nitric acid of the nitre, it assists in the
decomposition of this salt, more especially if it be mixed
separately with the nitre; 4thly, that, in all instances of its
combustion, while it acts primarily on the nitre, with the
oxygen of which it forms both water and carbonic acid, it,
at the same time, increases the flame, which may be either
white, red, or yellow, according to the other substances employed;
and, finally, it may be thrown out in the state of combustion,
and receive, for the further support of its combustion,
the oxygen of the air, and hence produce a white exterior
flame, while that in the immediate vicinity of the composition
may be more or less coloured. But its application,
the proportions in which it is used, as well as the kind of fire-works
to which it is applicable, will be considered at large in
other parts of the work.
The great inflammability of camphor is to be ascribed to
its containing a large quantity of carbon and hydrogen, and
a small quantity of oxygen.
There is a preparation, called artificial camphor, that is
formed by passing muriatic acid gas through spirit of turpentine.
It inflames with facility, and burns, without leaving
any residue. Might not this preparation be economically
employed, in lieu of camphor, for incendiary fire-works?
Sect. XVI. Of Gum Benzoin, and Benzoic acid.
Gum Benzoin, or Benjamin, is considered a solid balsam,
and is the production of a tree, which grows in Sumatra, &c.
called the styrax benzoe. It is obtained from this tree by
incision, a tree yielding three or four pounds. It is a brittle
substance, sometimes in the form of yellowish-white tears
and called, from that circumstance, almond benzoin. Besides
a resinous substance, it contains an acid, called the benzoic
or flowers of benzoin, a substance similar to balsam of Peru,
being a peculiar aromatic principle, soluble in alcohol and
water. By heating it, or by combustion, it evolves a very
agreeable smell, and is, therefore, used in those fire-works
which are exhibited in rooms, theatres, &c. and also in the
composition of odoriferous fire-works. Besides being in itself
inflammable, it produces a peculiar smell, arising, in all
probability, from an essential oil, aided, in some degree, by
the separation of benzoic acid.
It has been examined by Bucholz and Brande. Its general
properties are: that it is insoluble in water, although
hot water takes up a part of it, said to be the benzoic
acid. It is soluble in alcohol, from which it is separated by
muriatic and acetic acids, but not by the alkalies. It is also
soluble in ether.
The benzoic acid, or flowers of benzoin, are obtained from it
by sublimation. A quantity of the powdered gum, put into
an earthen basin, a thick paper cone being tied round the
rim, and heat applied, the acid will leave the resin, and be
condensed on the inner side of the cone. Bucholz (Bulletin
de Pharmacie, v. p. 177) has given a process for obtaining
it by means of alcohol, and some others have been adopted.
By boiling four ounces of the gum in powder in a sufficient
quantity of water, with three drachms of carbonate of soda,
the acid will unite with the alkali, and form a benzoate of
soda, which, when filtered and decomposed by sulphuric acid,
will yield the benzoic acid. Five drachms of acid will be
thus obtained. Lime has been used in the same manner as
soda, and the acid separated by the addition of muriatic
acid.
Flowers of benzoin may be used in the place of the gum;
using, however, but a small quantity. They will communicate
the same odour to fire as the benzoin. The flowers, or acid
of benzoin, are so inflammable, as to burn, with a clear yellow
flame, without the assistance of a wick. It is soluble in ardent
spirits, in oils, and in melted tallow. The compounds,
which it forms with them, are also inflammable. Benzoic
acid is considered to be an oily acid, and contains, no doubt,
a very large proportion of hydrogen.
Sect. XVII. Of Storax Calamite.
Storax is the most fragrant of all the balsams. It is afforded
by the styrax officinalis, a tree which grows in the
Levant. It is sometimes in red tears. Common storax is
in large cakes, and brittle and soft to the touch. This is
more fragrant than the other sort, but is frequently adulterated
with saw-dust. It is soluble in alcohol, and is said to
yield some benzoic acid.
Styrax is a different substance; a semi-liquid juice obtained
from the liquidambar styraciflua. Its odour is less agreeable
than that of storax calamite. It is used in odoriferous fire,
in pastes, in the composition for scented vases, and the like.
Sect. XVIII. Of Essential Oils.
Essential or volatile oils, as well as the raspings of red
cedar, dried rosemary, and other fragrant plants, are all used
in the preparation of odoriferous fire. In some preparations,
the oil of roses is employed; in others, the essence of bergamot,
of lemon, &c. which, being very volatile, evaporate
in a moderate heat, and, being also inflammable, may assist
in the combustion. In the case of the raspings of cedar in
particular, it also communicates a peculiar appearance to the
flame.
Oils, whether essential or fixed, when passed through ignited
tubes, are decomposed, and furnish an inflammable gas
called olefiant gas. Wax, tallow, &c. produce the same gas,
the hydroguret of carbon. Messrs. Taylor and Martineau
contrived an ingenious apparatus for generating gas from oil
on the great scale, as a substitute for candles, lamps, and coal
gas, it being much preferable for burning, as it contains no
sulphur, and does not injure furniture, books, plate, paint, &c.
Oil gas contains more hydroguret of carbon than coal gas,
which is a great advantage, enabling one cubic foot of oil gas
to go as far as four of coal gas. An elegant apparatus was
erected by Taylor and Martineau at the Apothecaries' Hall,
London, a drawing of which may be seen in the 15th number
of the "Journal of Science and the Arts."
It is to be observed, that odoriferous fire-works are intended
for exhibition in close apartments; so that the smell of
certain gases, produced by the nitre, charcoal, and sulphur,
according to the preparation used, will be more or less destroyed.
Such preparations are, nevertheless, expensive, and
for that reason seldom used.
Sect. XIX. Of Mastich.
This resin, obtained, from the pistacia lentiscus, by making
transverse incisions in the tree, is first in a fluid state, and
gradually concretes into yellowish semi-transparent brittle
grains. In Turkey, great quantities of it are used for sweetening
the breath, and strengthening the gums. It is from the
use of the resin as a masticatory, that its name is said to be
derived. It is not completely soluble in alcohol, a soft elastic
substance separating from the solution. When exposed to
heat, it melts, and exhales a fragrant odour: for which reason,
principally, it enters into the composition of some fire-works,
as the scented paste. In ordinary fumigations, mastich is
commonly used.
Sect. XX. Of Copal.
Gum copal, by which name it is known, is a resin, obtained
from a tree, called thus copallinum. It is often in the
form of a beautiful white resin; but sometimes it is more or less
coloured. It is frequently opaque. It may be dissolved in alcohol,
spirit of turpentine, and oils, by a peculiar management,
(by using camphor, previously melting it, and the like,) and
then it forms the various copal varnishes, which are more or
less perfect, as the copal is transparent, and the solution properly
formed. When heated, it melts like other resins, and
in this, and many other properties, it partakes of the character
of resins in general. It is used in some of the formulæ for
fire-works.
Sect. XXI. Of Myrrh.
Myrrh is obtained from a plant, supposed to belong to the
genus mimosa, which, as Bruce informs us, (Travels, &c.)
grows in Abyssinia and Arabia. It is in the form of tears,
of a reddish-yellow colour; sometimes transparent, and at
other times opaque. It possesses a peculiar odour, and a
bitter and aromatic taste. It burns with difficulty, and does
not melt when heated. With water, it forms a yellow opaque
mixture. It dissolves in alcohol, and the solution is decomposed
by the addition of water, the whole becoming opaque.
According to Braconnot, myrrh is composed of 23 resin,
and 77 gum, in the 100 parts. Pelletier, whose analysis
differs from Braconnot's, observes, that, besides resin, it contains
some volatile oil, to which, no doubt, its fragrance is
owing. The gum, extracted from it, had the character common
to all gums, with the exception, that, instead of forming
the mucous or saclactic acid, by the action of nitric acid, it
produced only oxalic acid.
That myrrh burns with difficulty, is owing entirely to the
presence of so much gum, and, comparatively speaking, the
small quantity of resin, which enters into its composition.
But, notwithstanding this property, as it partakes of a fragrant
oil, it is used in some compositions for fire-works.
The gummy part may retard, as is sometimes required in
particular preparations, the rapidity of the combustion, and
therefore have a two-fold effect when employed in fire-works.
Sect. XXII. Of Sugar.
Refined sugar is sometimes used in pyrotechno-mixtures.
As it is a vegetable oxide, (composed of carbon, hydrogen,
and oxygen), which is decomposed by heat, and has the property
of decomposing nitric acid, and some of its combinations;
its operation in such mixtures may be readily perceived.
We have seen, when treating of chlorate of potassa,
that, when this salt and sugar are mixed together, and sulphuric
acid poured on the mixture, a rapid combustion ensues,
which is owing as well to the decomposition of the sugar,
as to that of the salt. The matches, likewise, which inflame
by immersion in sulphuric acid, are covered with a similar
mixture. That sugar, therefore, has the property of decomposing
those salts, which are composed of acids, that have
their oxygen but feebly combined, and thereby producing
combustion, according to the temperature employed, or other
agents made use of, is evident from a variety of experiments.
By its action, then, in such cases, the products of combustion,
arising from the elementary parts of the sugar alone,
uniting with oxygen, must be carbonic acid and water. Sugar,
submitted to destructive distillation, affords a variety of
new substances; among which we may notice caromel, or
that peculiar odour, which is recognised in the burning of
sugar. Sugar may, therefore, besides assisting in part in the
decomposition of saline bodies, and particularly nitre, and
perhaps giving rise to new products, with which we are unacquainted,
have another effect, that of destroying the offensive
smell of other substances, by means of the caromel
formed. Sugar, also, when mixed with various bodies, and
struck with a hammer, will produce detonations.
Sugar, when used in compositions of fire, should be pure;
and it may be known to be so, by producing invariably a
phosphorescence in the dark, when two pieces are rubbed
together. At a red heat, it bursts into flame with a kind of
explosion. This flame is white, with blue edges.
Sugar is obtained from the sugar-cane; from the sap of the
sugar-maple; from beets and grapes; and from various other
saccharine bodies. It is formed also artificially, by the action
of sulphuric acid on starch.
Mr. Kirchoff, a Russian chemist, accidentally discovered
that starch may be changed into sugar by diluted sulphuric
acid. One hundred parts of starch yield one hundred and ten
of sugar. It appears, that, by the abstraction of a little hydrogen
and carbon, starch will be converted into sugar. Potatoes,
digested with diluted sulphuric acid, Dr. Ure found,
would also form sugar, and very abundantly. The sulphuric
acid may be removed by the addition of chalk, and, as the
sulphate of lime is but slightly soluble, the pure saccharine
fluid may be obtained by filtration. The sugar is procured
in a solid state by evaporation, and may be clarified like other
sugar. Dr. Ure observes, that good beer has been made
from starch-sugar, but recommends potato-sugar. To obtain
the latter, the potatoes are washed, grated down, and treated
with the dilute acid for a day or two, at a temperature of 212°.
The observations of Braconnot are interesting. He has
succeeded in converting a variety of vegetable substances
into gum and sugar. The conversion of wood into sugar,
however remarkable it may seem, has been effected; and
a pound weight of rags will, by the same process, make
more than a pound weight of sugar. Rice, as it contains a
large quantity of fecula, may, we have no doubt, be converted,
in the same manner, into saccharine matter.
When sugar is first obtained, it is impure, containing a variety
of foreign substances, and more or less brown, as the
Muscovado of the West India islands. It is refined, and
formed into loaves, by treating its solution in water with bullocks'
blood, the serum of which coagulates by heat; and, finally,
by pouring the sugar, when sufficiently boiled, into
conical earthen moulds, where it concretes. It is clayed, by
putting a mixture of white clay and water on the sugar in each
of the cones; the water from which passes through, and renders
it beautifully white. The same process may be repeated;
hence the single and double refined sugar. The molasses
passes out from the sugar at the apex of the cone, and is received
in vessels.
From twenty to thirty-five per cent. of molasses are separated
in the refining of raw sugars; and it is supposed, that a
considerable part of it, probably two-thirds, are formed by the
high heat used in the concentration of the sirup. In order
to prevent so great a quantity of molasses, different plans
have been recommended. That of Howard is highly spoken
of. It consists in surrounding the sugar-boiler with oil
or steam at a high temperature, instead of exposing it, as
heretofore, or the mode usually adopted, to the naked fire.
The boiler is covered at top, and, by means of an air-pump,
the air is exhausted, and the pressure of the atmosphere being
removed, ebullition takes place at a lower temperature.
No blood is used in Mr. H.'s process, instead of which, the
clarification is performed by means of canvass filters, adding
previously a pasty mixture of gypsum and alumina, made by
saturating a solution of alum with quicklime. He does not
employ clay, as is done in whitening the sugar; but, in its
place, makes use of very pure saturated sirup. He uses animal
charcoal, (bone black), which has the property of destroying
vegetable colouring matter. Wilson's process for refining
sugar possesses some advantages. It will be found in
the 34th volume of the Repertory of Arts. The patent filtering
apparatus of Sutherland is highly approved.
The chemical properties of sugar are the following: It is
very soluble in water, both hot and cold; it forms with water
a sirup, which on standing will crystallize, forming the candied
sugar. It is not acted upon by oxygen gas. It is capable
of combining with, and, according to some chemists, of neutralizing
acids and alkalies. It is decomposed by nitric acid
with effervescence, being converted into oxalic and malic
acids. Tartaric, acetic, and oxalic acids prevent it from crystallizing.
It unites with lime and strontian, but is partially
decomposed by barytes. It combines also with oxide of lead,
which it precipitates from its solution, forming, as it is called,
a saccharate of lead. Alcohol has some action on it, and
also hydrosulphurets, sulphurets, and phosphurets of alkalies
and alkaline earths. On the application of heat, it melts,
swells, becomes brownish-black, and exhales a peculiar odour,
which we have mentioned, and, at a red heat, takes fire.
Lastly, though possessed of some general and specific characters,
it differs, in some of its properties, according to the
substance from which it is obtained.
Sect. XXIII. Of Sal Prunelle.
This salt is nothing more than nitrate of potassa, melted in
a crucible, and poured into moulds, whence it receives the
form under which it is found in the shops. The saltpetre,
when merely fused, is not decomposed, as it is when exposed
to a red heat in an iron retort. In the former case, the water
only which it contains is separated; but, in the latter, the
salt itself is decomposed, and oxygen gas evolved. Sal prunelle,
therefore, is fused saltpetre. Combustible bodies, as
charcoal, sulphur, phosphorus, oils, resins, &c. have the same
effect on it as on ordinary nitre. The only advantage it has
over the common refined saltpetre, in the preparation of some
fire-works, is, that it is free from water, and more readily acted
on by combustible substances. In preparing it, care must
be taken in the application of the heat; which, if too powerful,
would, besides fusing it, decompose, and convert it into
nitrite of potassa. It may be readily pulverized and sifted.
For the properties of nitre, see that article.
Sect. XXIV. Of Alcohol.
Alcohol, or rectified spirit of wine, is used for a variety of
purposes in pyrotechny, and, when it cannot be procured,
strong brandy is substituted. In assisting the pulverization
of some substances, as camphor, in forming the mixture of
certain pastes, and in acting as a vehicle for the intimate union
of some bodies, it is considered a necessary article. Alcohol
may be made to form variously coloured flames, by
mixing with it certain saline substances. Thus, boracic
acid will form a green flame; muriate of strontian, a carmine
red; muriate of lime, an orange; nitrate of copper, an emerald
green; nitre, common salt, and corrosive sublimate, a yellow,
&c. As alcohol has the property of dissolving essential oils,
camphor, &c. it may be used as a menstruum for certain oils
in the preparation of odoriferous fire-works. See Articles
on coloured flame, and odoriferous fire.
Alcohol constitutes a part of all ardent spirits, wine, cider,
beer, &c. in which it is combined with water, or with water
and mucilaginous and colouring matter. It is formed in the
vinous fermentation, and always results from the union of
carbon and hydrogen. During the process, carbonic acid gas
is liberated. Fermented liquors, therefore, or those which have
passed through the vinous fermentation, always contain alcohol
in more or less abundance, but mixed with water in many
instances. In some it is accompanied with water, and saccharine,
mucilaginous, and extractive matter. The different
kinds of beer is an example of this fact. When liquors,
which contain spirit, are submitted to distillation, the product
is alcohol and water; for the volatile parts evaporate,
and the fixed substances remain in the still. The spirit partakes,
more or less, of a peculiar taste and flavour, by which
liquors are distinguished from each other. On this subject,
however, it will be sufficient to add, that brandy is procured
by the distillation of wine; rum, from the fermented juice of
the sugar-cane; gin, from fermented grain and juniper-berry;
whiskey, from the fermented mash of grain, cider, &c. and,
generally, the ardent liquors, from pears, peaches, and other
substances, by the same process.
Alcohol, therefore, exists in all these distilled liquors, in a
greater or smaller quantity, combined with water; and the
proportion it bears to the water is known by a standard, as
either proof, above proof, or under proof, according as its
strength is shown by the hydrometer.
The process of obtaining alcohol in a pure state, (usually
called rectified spirit of wine), by which the water is separated
from the alcohol, consists in repeated distillations, either
alone, or mixed with certain substances, which have the property
of uniting with, and keeping down the water, in the
act of distillation. These substances are usually potash, and
dry muriate of lime, both of which substances have a great
affinity for water. The specific gravity of highly concentrated
alcohol, at 60° is .820, but that of common alcohol,
only .837, at the same temperature.
The properties of alcohol are the following: It is a transparent
liquor of an agreeable flavour, and may be changed in
this particular, by essential oils. It may be exposed to a
low temperature without freezing. It boils at 106°, when of
the specific gravity .820, and in a vacuum at 56°. It has a
strong affinity for water, with which it combines in any proportion;
and the specific gravity varies according to the proportion
of the mixture and the temperature, on which are
founded the tables of Blagden, Gilpin, and others.
Neither common air, nor oxygen, has any action on alcohol
at moderate temperatures, whether in a liquid or aeriform
state. On hydrogen, carbon, and charcoal, it has little or no
action, but on phosphorus it acts, a portion of which it dissolves.
With sulphur, it may be made to unite, as also with
the alkalies, but not with the earths, except strontian and
barytes. It is decomposed by sulphuric and nitric acids, with
both of which it forms ether. It dissolves some salts, and
has scarcely any effect upon others. Lastly, it dissolves resins
and essential oils; but it neither acts upon gums, properly so
called, nor on fixed oils. It is a compound of hydrogen,
carbon, and a small proportion of oxygen, and may be decomposed,
by passing its vapour through an ignited porcelain
tube.
Alcohol, by its combustion, as it is used in spirit-lamps
for chemical and other purposes, produces no smoke, in consequence
of the carbon it contains being totally converted,
during that process, into carbonic acid; and its hydrogen,
uniting with another portion of the oxygen of the atmospheric
air, passes off in the form of aqueous vapour. Alcohol,
used in this way, is preferable to oil; for the latter produces
a large quantity of smoke, unless it is burnt in the Argand
lamp. Alcohol is inflamed, when it is brought in contact
with an ignited body. The combustion is rapid without any
residue, and the flame white.
As to the strength of alcohol, the best means of determining
it, is with the hydrometer; but usually its proof is ascertained
by means of gunpowder. A portion of powder, put
into a cup, and alcohol poured on it and inflamed, will, if the
latter be strong, be set on fire; if, however, the powder should
not take fire, but the flame of the alcohol be extinguished, we
infer the existence of water, and that the alcohol is not of the
proper strength. This experiment is founded on this circumstance,
that, if the alcohol contains water, after the alcoholic
portion is all consumed, the water will not only extinguish the
flame, but also prevent the inflammation of the powder. The
hydrometer, however, is the best experiment, as it determines
at once the fact of the strength of the liquor.
Alcohol is used in the preparation of certain fulminating
substances, as fulminating mercury and silver in particular;
the preparation of which, we will give in the two next sections.
It may not be improper to mention another application of
alcohol, that of forming the aphlogistic lamp, or lamp that
burns without flame. The following description of it, is
given by Accum, in his Chemical Amusements, Am. Ed.
p. 355. "In a common lamp, with a wick of about half a dozen
common threads of cotton wick, used for lamps, put some
good spirit of wine. Dispose the threads of wick, not intertwined,
but straight and parallel to each other. Take platina
wire of the thickness of 1/100th part of an inch; coil it round
the wick, about nine coils below, and six coils standing above
the top of the wick; the diameter or width of the coils should
not be more than 3/20th, or 1/7th of an inch wide. Light the
wick; and, when the coil of platina above the wick is red-hot,
blow out the flame. There will then be a current of pure
alcohol, gradually rising from the reservoir below, through
the wick, sufficient to keep the upper coil of platina red-hot,
until the whole of the alcohol is consumed. This lamp has
kept constantly lighted during sixty hours. By means of it,
a match, a bit of spunk, or candle may be lighted when
wanted. The quantity of alcohol consumed is not much:
about an ounce, or an ounce and a half during the night, from
bed-time until morning will suffice." This article was added
to Accum by Dr. Cooper. A figure of the lamp is in Brande's
Chemistry. Dr. Comstock has a paper on the aphlogistic
or flameless lamp, in Vol. IV. p. 328, of Silliman's Journal
of Science and Arts, which contains some judicious and useful
remarks. Sir H. Davy (Journal of the Royal Institution)
has discovered, that the vapour of camphor answers the
same purpose as alcohol. If a platinum wire be heated and
laid upon camphor, it will continue to glow as long as any
remains, and the wire will frequently light it up into flame.
Davy found, that, in the slow combustion of alcohol, &c. an
acid was generated, to which he gave the name of Lampic
acid. Faraday and Daniel (Journal of Science and the Arts)
have confirmed his conclusions.
Dr. Marcet has proposed a method of producing an intense
heat, by causing a current of oxygen gas to pass through the
flame of alcohol. The construction of the lamp and gas-holder
may be found in the Archives des Découvertes, Vol. vii,
p. 61.
Sect. XXV. Of Fulminating Mercury.
As the fulminating mercury of Howard consists principally
of the oxalate of mercury, the oxalate of this metal may be
employed for the same purpose. Oxalic acid does not act on
mercury, but dissolves its oxide, and forms with it a white
powder. I formed various fulminating metallic powders,
(See Coxe's Medical Museum), and prepared one in particular
by merely digesting a solution of the salt of sorrel (superoxalate
of potassa) on red precipitate. The effect is that the
oxalic acid unites with the oxide of mercury, and forms an
oxalate of mercury, which, when struck with a hammer, produces
a detonation. Oxalate of mercury, possessing the same
effects, may be formed, very expeditiously, by pouring the
oxalate, or the superoxalate of potassa into a solution of
nitrate of mercury. The oxalate of mercury will be precipitated,
which is to be caught on a filter, washed, and dried in
a gentle heat.
Howard's fulminating mercury is less dangerous than either
fulminating silver, or fulminating gold. The extreme force
of detonation which it possesses is remarkable. The temperature
required for its explosion is 360 degrees. Friction,
percussion, electricity, and the flint and steel will produce this
effect. It gives rise to a stunning disagreeable report, and its
force is sufficient to indent both the hammer and the anvil.
Four or six grains are sufficient for an experiment. It is
rather singular, as Mr. Cruikshank first observed, that this
powder will not inflame gunpowder; as may be shown by
spreading some of the former on paper, and shaking gunpowder
over it, and then firing the mercurial powder. The
grains of the gunpowder may be collected entire after the
explosion.
From the experiments of Howard, it appears, that this
powder is composed of oxalate of mercury, and nitrous etherised
gas. Fourcroy, however, has shown, that it varies in
its nature, according to the mode of its preparation.
There is also a preparation of mercury, which is likewise
explosive, discovered by Fourcroy. This compound may be
formed by digesting the red oxide of mercury in liquid ammonia
for the space of eight or ten days. The oxide assumes
a white colour, and at last appears in crystalline scales. Upon
ignited coals, it detonates loudly like fulminating gold, which
see below. In a few days, however, it loses its fulminating property,
and undergoes spontaneous decomposition. Exposed
to a low heat, the ammonia is disengaged, and an oxide of
mercury remains.
As ammonia forms several detonating compounds with metallic
oxides, the theory of their explosive effects is the same;
viz. that, while the hydrogen of the ammonia unites with the
oxygen of the oxide, forming water, the azote is disengaged
in the state of gas.
The process for preparing Howard's fulminating mercury
is the following, dissolve one hundred grains of mercury in an
ounce and a half (by measure) of common nitric acid, assisting
the solution by heat. When cold, pour the solution upon
two ounces (by measure) of strong alcohol, and apply a moderate
heat, until the mixture begins to effervesce. A white
fume then begins to undulate on the surface of the liquor, and
a white powder precipitates, which is the fulminating mercury.
This powder is to be immediately washed with cold
water, and dried at a heat, not much exceeding that of boiling
water. One hundred grains of mercury, will give, on an
average, one hundred and twenty-five grains of the powder.
The products of its combustion are carbonic acid gas,
azotic gas, water, and mercury. Besides by percussion, it is
inflammable when brought in contact with sulphuric acid. It
is supposed, that fulminating mercury sometimes contains
ammonia, and that the products of combustion, according to
the mode of preparation, are therefore different. The reader
may consult some interesting observations on this powder in
the Journal de l'Ecole Polytechnique.
M. Bayen, an apothecary, in 1779, (Journal de Physique),
announced a process for preparing fulminating mercury. His
process, however, is different from that described. A solution
of mercury is made in nitric acid, and precipitated by
caustic alkali. The precipitate (oxide of mercury) is then
caught on a filter, washed, and dried. Thirty grains of this
powder, mixed with four or five grains of sulphur, and struck
with a heavy hammer, or heated on an iron, will explode
with violence. The oxide of mercury, obtained from its
solution by lime-water, has the same effect, when treated in
the same manner. Another process recommended is, to precipitate
a solution of the perchloride of mercury (corrosive
sublimate) by lime-water, and treat the precipitate with sulphur,
as above described.
Sect. XXVI. Of Fulminating Silver.
This compound, which is more powerful than fulminating
mercury, is prepared also with alcohol. Descostils (Annales
de Chimie, LXII. p. 198,) Cruikshank, and Brugnatelli, have
all written upon it.
Fulminating silver explodes without much heat. By the
slightest friction it is inflamed, and detonation follows.
Hence it is used in the form of toys, in fulminating balls, bombs,
crackers, &c. which explode by falling on the ground. Torpedoes,
pulling crackers, &c. are formed of this powder.
The fulminating balls are made of glass, and contain a grain
or two of fulminating silver, mixed with sand. The same
mixture, put on the ends of two strips of paper, and the ends
pasted, forms the pulling crackers; for the moment they are
pulled asunder, the friction produced sets the fulminating
silver on fire, and causes a detonation.
The same preparation placed on a wafer, and the wafer put
between paper, as in the sealing of a letter, will explode, when
the paper or the wafer is broken. Fulminating bombs are
balls of the size of a hazle nut, containing about three grains
of the fulminating silver. Their explosive effects are said to
be violent. See Detonating Works.
This powder, in consequence of its powerful action, is dangerous;
and, as it explodes so readily, it should never be put
into a phial, nor should it be touched or handled in any way
that can produce friction. Even when made to approach the
flame of a candle, it will explode with extreme violence.
The preparation of Brugnatelli's fulminating silver consists
in reducing 100 grains of nitrate of silver (lunar caustic) to
powder; and, when put into a basin, pouring over it one
ounce of alcohol, and the same quantity of nitric acid. The
mixture will become hot, effervescence will ensue, while the
whole will assume an opaque or milky appearance.
When the gray powder of the nitrate has become white,
and the mixture acquires consistency, distilled water is to be
added, to suspend the action. The white precipitate is then
to be washed by repeated affusions of cold water, and dried
in the open air, but in a dark place, so as to seclude it from
the light.
In fact, this process is similar to that for preparing fulminating
mercury; for it is nothing more than treating silver
with nitric acid and alcohol. Cruikshank employs forty
parts of silver, sixty parts of nitric acid, and sixty parts of
alcohol, from which sixty parts of the powder are obtained.
Berthollet considers this powder to be composed of ammonia,
and oxide of silver, and the theory of its detonation to
be the same as that of fulminating gold. In its explosion, the
oxygen of the oxide of silver unites with the hydrogen of the
ammonia, and the nitrogen is disengaged.
Berthollet's fulminating silver, which he discovered in
1788, is another preparation, which fulminates powerfully.
It is prepared by precipitating nitrate of silver by lime-water.
The precipitate is placed on filtering paper, which absorbs the
water, and the nitrate of lime. Pure caustic ammonia is
then added, which produces an effect somewhat similar to
that attending the slaking of lime. The ammonia dissolves
only a part of this precipitate. It is left at rest for ten or
twelve hours, and at the expiration of this time, there is formed,
on the surface, a shining pellicle, which is re-dissolved
with a new portion of ammonia, but which does not appear,
if a sufficient quantity of ammonia has been added at the
first. The liquid is then separated, and the black precipitate,
found at the bottom, is put, in small quantities, on separate
papers. This powder explodes even when moist, if struck
with a hard body. When dry, the slightest friction will explode
it. Its detonation is owing to the same cause as that
producing the explosion of the other preparation of this metal,
as it is also composed of oxide of silver and ammonia.
The fulminating silver of Chenevix explodes only by
a slight friction in contact with combustible substances. It
is nothing more than chlorate of silver. It is formed by passing
chlorine gas through alumina, diffused in water, and afterwards
digesting, in the liquor, some phosphate of silver.
The whole is to be evaporated slowly. A single grain of this
powder, with three grains of sulphur, will explode by the
slightest friction.
For the preparation of fulminating silver, the formula given
by professor Silliman of Yale College, appears to possess some
advantages. To an ounce of alcohol and as much nitric acid,
he adds 100 grains of pulverized lunar caustic. A gentle heat
is applied to excite the action between them, which must be
removed, the moment they begin to act. When a thick white
precipitate appears, cold water must be added to check the
action. The precipitate is then to be collected, washed, and
carefully dried. A grain or two will explode over a candle.
Sect. XXVII. Of Fulminating Gold.
The preparation, called by some aurate of ammonia, is
formed by dissolving gold in nitromuriatic acid, diluting the
solution with water, and adding gradually liquid ammonia,
until the precipitation ceases. The precipitate is then to be
caught on a filter, well washed with water, and dried in the
air. The fulminating gold, thus produced, exceeds the
weight of the original gold employed by thirty-three per cent.
Three or four grains of this powder, heated on a knife, will
explode with a loud report. The temperature required for
its explosion is between 230° and 300°. Ten or twelve
grains will penetrate a copper-plate, of the thickness of a
playing card. The facility with which this powder explodes,
is increased by drying. If it be heated until it becomes
black, the slightest touch will cause a detonation. This powder
is composed of oxide of gold, ammonia, and a portion of
chlorine; and, during its detonation, water, nitrogen and chlorine
are evolved, the gold being revived.
The presence of ammonia is necessary to give to gold the
property of fulminating. Fulminating gold accordingly loses
this property, the moment the ammonia is separated. Concentrated
sulphuric acid, melted sulphur, fat oils, and ether
have this effect.
The discoverer of fulminating gold was a German Benedictine
Monk, who lived about the year 1413. Basil Valentine
has described the preparation of it very accurately. He recommends,
however, mixing sal ammoniac with aqua fortis,
the old mode of making aqua regia, and distilling the mixture;
then putting in the gold in leaf. After the acid is saturated,
he adds oleum tartari, or sal tartari (carbonate of potassa)
dissolved in water; and the precipitated calx, thus obtained,
when collected, washed, and dried in the open air, will
fulminate. In this process, it is evident, that the aqua regia,
prepared with sal ammoniac, contains ammonia, and, when the
gold is dissolved, and the potash added, the oxide of gold
separates, and, from the composition of the powder, must
combine with a portion of ammonia, and hence produce fulminating
gold. He remarks, that distilled vinegar digested
on fulminating gold, destroys its fulminating properties, and
observes also, that care must be taken to prevent its explosion.
He also knew that sulphur would have the same effect.
Bergman (Treatise on Pulvis Fulminans) describes the
process employed by Valentine; and Beckman (History of
Inventions, v. iii. p. 132,) observes, that, after the time of
Valentine, Crollius, who lived in the last half of the 16th century,
was well acquainted with fulminating gold, and made
its preparation more generally known. In the Oswaldi
Crollii Basilica Chymica, 4to, p. 211, published at Frankfort,
in 1609, the process is also to be found. He calls it
aurum volatile, and speaks of its being useful in medicine.
Beguin, however, appears to have given it the appellation of
aurum fulminans, if we judge from his Tyrocinium
Chymicum, 12mo, printed in 1608.
Sect. XXVIII. Of Fulminating Platinum.
While noticing explosive compounds, it may not be improper
to mention that of platinum, lately discovered by Mr.
E. Davy. It explodes, when heated to 400 degrees, with a
sharp report, similar to that produced by fulminating gold;
but neither friction nor percussion will decompose it. It is
formed by making a solution of platinum in nitromuriatic
acid, and passing through it, sulphuretted hydrogen gas,
until no further precipitation ensues. This precipitate, when
collected, and digested in nitric acid, is converted into sulphate
of platinum. This is dissolved in water, and liquid
ammonia then added. The precipitate, now formed, is washed,
and boiled in a solution of potassa, and, after having freed
it from the adhering potassa, is suffered to dry. All fulminating
ammoniacal compounds are analogous; and fulminating
platinum, being composed of oxide of platinum, ammonia, and
water, is decomposed in the same manner as these compounds.
Fulminating platinum is composed as follows:
| Peroxide of platinum | 82.5 | nearly | 2 primes. |
| Ammonia | 9.0 | | 1 —— |
| Water | 8.5 | | 2 —— |
Sect. XXIX. Of Detonating Powder from Indigo.
That indigo produces a detonating powder by treating it
with nitric acid, is evident from experiment. As it produces
a purple light, it might, perhaps, be used advantageously in
small fire-works.
The process described by Dr. Thomson, (System of Chemistry,
VOL. IV. p. 80, Amer. edit.) is to boil one part of indigo
in four parts of nitric acid. The solution will become
yellow, and a resinous matter appear upon its surface. The
boiling is to be stopt, and the liquor cooled. The resinous matter
is then to be separated; and the solution evaporated to the
consistence of honey. This is to be re-dissolved in hot water,
and filtered, and a solution of potassa added, which will
throw down yellow spicular crystals, consisting of bitter
principle, combined with potassa. When the resin is again
treated with nitric acid, the same bitter principle is produced.
The spicular crystals, when wrapped up in paper, and
struck with a hammer, detonate with a purple light.
Sect. XXX. Of the Fulminating Compound, called
Iodide of Azote.
Iodine is a particular substance, which has the property not
only of combining with oxygen and hydrogen, forming iodic
and hydriodic acid, but also with various bases constituting a
class of bodies, called iodides. Its union with azote produces
a singular substance, which detonates with great violence,
when slightly touched or heated. It may be formed, by putting
a quantity of iodine into the water of ammonia. It will
be gradually converted into a brownish-black matter, which
is the iodide of azote. It is formed in this process by the
iodine, in the first instance, decomposing a part of the ammonia;
the hydrogen of which combines with a portion of
the iodine, and produces hydriodic acid, which then unites
with the undecomposed part of the ammonia, and forms the
hydriodate of ammonia; whilst the azote the other constituent
of the ammonia, unites with another portion of the
iodine, and forms the compound in question.
When exposed to the air, iodide of azote gradually flies off
in vapour, without leaving any residue. The products of its
detonation are iodine and azotic gas.
The iodide of azote was discovered by M. Courtois, and
subsequently examined by M. Colin. Iodine, brought in
contact with ammoniacal gas, a combination taking place, produces
a viscid shining liquid of a brownish-black colour,
which, as the saturation goes on, loses its lustre.
This liquid does not detonate, and is considered to be an
iodide of ammonia; but, when it is added to water, it is decomposed,
as well as the water, and we obtain two new compounds,
as before observed, the hydriodate of ammonia, and
iodide of azote. This iodide detonates. Hence it is evident,
that hydrogen united with azote, in ammonia, prevents explosion;
for the moment it is taken away, by the formation of
hydriodic acid, and the azote itself combines with the iodine,
a fulminating compound is formed. The elements of this
powder are feebly united.
It is found, that hydriodate of ammonia has the property of
dissolving a large quantity of iodine, and, if suffered to remain
with the iodide of azote, of decomposing it also, and
setting the azote at liberty. Water is said to have the same
effect, although feebly.
Iodate of potassa, a salt composed of iodic acid and potassa,
when mixed with sulphur, and struck with a hammer, will
detonate, in consequence of the decomposition of the iodic
acid. The iodate of potassa may be formed very readily by
agitating iodine with a solution of caustic potassa. The water
is decomposed, and the hydriodate of potassa is also formed,
which, being very soluble, remains in solution, whilst the
iodate separates, on concentrating the liquor, and suffering it
to stand.
Chlorate, as well as nitrate of silver, form with sulphur
fulminating powders.
Iodic acid, called also oxy-iodine, (prepared by exposing
iodine to the action of euchlorine,) when heated in contact
with inflammable substances, and the more combustible metals,
will produce detonations.
It appears, however, that sulphur has a stronger affinity for
oxygen than iodine has, and iodine a stronger affinity than
chlorine for the same element. Hence chloric acid is more
readily decomposed by inflammable bodies than iodic acid,
and iodic acid, sooner than sulphuric acid.
The acids, which chlorine, iodine, and sulphur form respectively
with oxygen, Gay-Lussac remarks, have their
elements more strongly condensed, than the same substances
united with hydrogen.
Sect. XXXI. Of Detonating Oil, or Chloride of Azote.
This oil is produced by the action of chlorine on ammonia,
by using some of the salts of this alkali. A small jar of chlorine
gas is transferred into a basin, containing a solution of
nitrate or muriate of ammonia, a little heated: an absorption
will gradually take place, and the gas be condensed. An oily
film will now appear on the surface of the ammoniacal solution,
which, as it increases, will form globules and fall through
the liquor. This substance is the detonating oil, composed,
according to analysis, of chlorine, azote, and hydrogen. It is
supposed by Messrs. Wilson, Porret, and Kirk, that the
hydrogen serves as a medium of union between the chlorine
and azote, and that, in detonation, the powerful effect is owing
to the chlorine.
Detonating oil explodes violently at 212 degrees; and even
when touched with cold inflammable substances, as a portion
of olive oil, about the size of a pin's head, the detonation is
also violent, and the vessel, in which the experiment is made,
will, in most cases, be broken into fragments.
Detonating oil is considered, however, a chloride of azote.
In order to prevent the decomposition of the chloride by the
ammoniacal salt, a thin stratum of muriate of soda, put into
the bottom of the vessel, is recommended. Its specific gravity
is 1.653. Warm water, put into a vessel containing it,
will change it to an aeriform fluid of an orange colour. "I
attempted," says Sir H. Davy, "to collect the products of
the new substances, by applying the heat of a spirit-lamp to a
globule of it, confined in a curved glass tube over water: a
little gas was at first extricated; but, long before the water had
attained the temperature of ebullition, a violent flash of light
was perceived, with a sharp report; the tube and glass were
broken into small fragments, and I received a severe wound
in the transparent cornea of the eye, which has produced a
considerable inflammation of the eye, and obliges me to make
this communication by an amanuensis. This experiment
proves what extreme caution is necessary in operating on this
substance; for the quantity I used was scarcely as large as a
grain of mustard seed." Phil. Trans. 1813, Part I.
In vacuo, it expands into vapour, which still possesses the
power of exploding by heat. In water, it gradually disappears,
the water becoming acid, and azote being evolved.
Mercury decomposes it, and a white powder (calomel) is
formed, while the azote is set at liberty.
Dr. Ure (Chemical Dictionary, Art. Nitrogen,) observes,
that the mechanical force of this compound, seems superior to
that of any other known substance, not even excepting the
ammoniacal fulminating silver. The velocity of its action
appears to be likewise greater.
The Doctor touched a minute globule of it, in a platina
spoon, resting on a table, with a fragment of phosphorus at
the point of a pen-knife, and the blade was instantly shivered
into fragments by the explosion.
Messrs. Porret, Wilson, and Kirk (Nicholson's Journal,
Vol. XXXIV,) employed 125 different substances, by bringing
them in contact; and out of that number the following
caused it to explode:
Supersulphuretted hydrogen,
Phosphorus,
Phosphuret of lime,
Phosphuretted camphor,
Camphoretted oil,
Phosphuretted hydrogen gas,
Caoutchouc,
Myrrh,
Palm oil,
Ambergris,
Whale oil,
Linseed oil,
Aqueous ammonia,
Olive oil,
Sulphuretted oil,
Oil of Turpentine,
---- Tar,
---- Amber,
---- Petroleum,
---- Orange peel,
Naphtha,
Soap of silver,
---- Mercury,
---- Copper,
---- Lead,
---- Manganese,
Fused Potassa,
Nitrous gas.
See Detonating Works.
According to Mr. Davy, chloride of azote contains
| 4 vols. of chlorine | = 10 + |
| or | |
4 primes | = 18.0 + |
| 1 —— azote | = 0.9722 |
| |
1 —— | = 1.75, |
| or very nearly 10 by weight of chlorine to 1 of azote. |
Sect. XXXII. Of Pyrophorus.
Pyrophorus is a black substance, which takes fire spontaneously,
when brought into contact with air. It is the
luft-zunder, or air-tinder of the Germans. It first emits sulphuretted
hydrogen gas, and in a few seconds becomes red-hot,
burning with a bluish flame. Pyrophorus consists of
alumina, charcoal, and sulphuret of potassa, and also, according
to some, of potassium, which is alleged to be formed in
its preparation. Be this as it may, it seems, that water is
decomposed in its combustion, that sulphuretted hydrogen
gas is emitted, which is inflamed by the oxygen gas of the
atmosphere, and that, during the combination of oxygen, a
degree of heat is produced, which causes the ignition of
the charcoal, as well as the inflammation of the remaining
sulphur.
Pyrophorus may be formed in several ways, all of which
produce the same result. The usual process is the following:
Take equal parts of brown sugar and alum, and melt them in
a ladle. Continue the heat, stirring them constantly until a
spongy black mass is formed. Let this mass be reduced at
once to powder, and introduced into a common green glass
phial, of the capacity of about six ounces, previously coated
outside with a mixture of pipe-clay and solution of borax.
Immerse the phial in a crucible, filled with sand, closing the
mouth of the former with a piece of charcoal, or a glass tube
inserted in it. Upon the crucible being exposed to a red heat,
an inflammable gas will escape, which will take fire.[21] When
this effect ensues, the heat must be continued for about twenty
minutes longer, at the expiration of which time, the crucible
must be removed from the fire, and the phial taken out
and closely stopt. The pyrophorus is to be preserved in a
ground stoppered bottle. The addition of one-sixteenth part
of sulphate of soda, or Glauber's salt, to the alum and sugar,
is said to make the pyrophorus with more certainty. Various
vegetable substances, besides sugar, as flour, starch, &c.
may be used. Three parts of alum, and one part of wheat
flour will make a good pyrophorus.
Homberg discovered this substance, in the year 1680.
Hence it is sometimes called Homberg's pyrophorus. He
was operating upon a mixture of human excrement and
alum; and, when he examined the contents of his vessel, in
three or four days after, he was surprised to see it take fire
spontaneously, when brought to the air. Soon after Lemery,
the younger, discovered, that honey, sugar, flour, or almost
any animal or vegetable matter, could be used in lieu of human
fæces; and, as Macquer informs us, M. Lejoy de Suvigny
showed, that other salts, containing sulphuric acid, may
be substituted for alum. Mr. Scheele (Treatise on fire, &c.)
found by experiment, that, when alum was deprived of potassa,
it was incapable of forming pyrophorus, and that vitriolated
tartar (sulphate of potassa) may be used in the place of
alum. The experiments of Mr. Proust prove, that a number
of neutral salts, composed of vegetable acids and earths, when
submitted to heat, leave a residuum that inflames spontaneously.
This statement agrees with the experiments of M. Chenevix.
From the experiments and observations of sir H.
Davy, and Dr. J. R. Coxe, late professor of chemistry, but
now of materia medica, &c. in the University of Pennsylvania,
it is rendered very probable, that pyrophorus owes its
property of inflaming spontaneously to a small portion of potassium,
which is formed in the process.
The preparation of pyrophorus is explained on the principle,
that the vegetable matter is first decomposed; that the
hydrogen and a part of the carbon decompose the sulphuric
acid of the alum, by uniting with its oxygen; that water, carbonic
oxide, and carburetted hydrogen are disengaged, along
with a part of the sulphur; and that, while the excess of charcoal
remains intimately mixed or divided with the alumina,
the sulphur and the sulphuret of potassa, form together a
compound, which has the property of inflaming spontaneously
in the open air. Some suppose, as alum is a triple salt, having
potassa, as well as alumina, for its base, that the potassa is decomposed
in the process, and potassium, as we remarked,
produced; to the presence of which they ascribe the singular
property of inflaming in the open air.
The spontaneous combustion of charcoal, in several instances,
is supposed by some to have been owing to the presence
of pyrophorus, by others to phosphorus, and by others again
to nascent hydrogen. To the presence of this substance, is
attributed the explosion of gunpowder mills. (See Gunpowder.)
Several different mixtures, and torrefied substances, form a
kind of imperfect pyrophori, and have more than once occasioned
fires, from no suspicion of their properties being entertained.
Besides pyrophorus, other compositions, which, in like
manner, take fire on exposure to the open air, have been by
degrees made known to us: 1. The scoria of the martial regulus
of antimony, or antimony freed from sulphur by the intervention
of iron and nitre, as well crude as also after being
dissolved, have been observed to take fire spontaneously,
when laid upon a hot stone, or in the sun. Of the truth of
the latter case, Wiegleb says, he is assured by his own experience.
2. The residuum of the acetate of copper is another
pyrophorus. 3. Some assert, that they have observed an inflammation
ensue from honey and flour, calcined according to
the rules laid down. 4. According to Geoffroy, a calcined
mass of three parts of black soap, and one of diaphoretic antimony,
has been known to take fire spontaneously. 5. Meuder
has observed, that a pyrophorus is obtained, when equal
parts of orpiment and iron-filings are sublimed together, and
ten parts of this sublimate are triturated in a mortar along with
twelve of nitrate of silver. 6. A pyrophorus is produced,
according to Penzky, when two drachms of white sand, three
of common salt, one of sulphur, two of sulphuric acid, and
half an ounce of muriatic, are mixed together and distilled in
a glass retort. In this operation, a sublimate is said to be
obtained, which bursts out in flames, as soon as it comes into
contact with the air. 7. The spontaneous precipitate of osteocolla,
from a solution of it in sulphuric acid, after having been
separated by means of a filter, and dried, took fire in a warm
place. S. Pott observed the same phenomenon in the earth of
the residuum, after the distillation of urine, that had been
putrid for a considerable time. 9. To these may also be referred,
a mass composed of equal parts of sulphur and iron-filings;
which, when thoroughly moistened with water, after
some time, grows hot, swells, and at last breaks out into vapour,
smoke, and flame. (See Artificial Volcano.)
Cadet's fuming liquor, prepared by distilling equal parts
of acetate of potassa, and arsenious acid, emits a very dense,
heavy, fetid, noxious vapour, which inflames spontaneously
in the open air. Black wadd, an ore of manganese, when
dried by the fire, and mixed with linseed oil, gradually becomes
hot, swells, and then bursts into flame.
M. Chenevix (Annales de Chimie, tom. LXIX,) remarks
that almost all the metallic residuums, which are formed by
the distillation of acetates per se, are pyrophoric, after cooling;
which Mr. C. attributes to the presence of finely divided
charcoal, mixed with the metallic part. He experimented
on several acetates, with the view of ascertaining the quantity
of pyroacetic spirit they would yield, and found, in every
instance, that charcoal existed in the residue, sometimes with
reduced metal, and at other times with metallic oxide. A
table of these experiments may be seen in Ure's Chemical
Dictionary. The residuum of acetate of copper has long
been known to possess pyrophoric properties.
Sect. XXXIII. Of Sal Ammoniac.
This salt enters into the composition of fire-works, to give,
more particularly, a peculiar colour to flame, which is that of
green, or yellowish-green. Sal ammoniac is a salt, composed
of muriatic acid and ammonia, and, when pure, is white, and
capable of being sublimed without decomposition. Its purity
may be known by its complete volatilization. It is readily
pulverized.
The experiment, showing the formation of sal ammoniac
by a direct union of its component parts, may be made by
bringing in contact, in a glass receiver, muriatic acid gas and
ammoniacal gas. White clouds will form, a condensation
take place, and muriate of ammonia be deposited on the sides
of the vessel.
Sal ammoniac was altogether made, at one period, from the
soot of camels' dung, or of other animals, which feed on
saline plants. The excrement was burnt, the soot collected,
and sublimed. This was the process practised in Egypt.
The composition of sal ammoniac being known, the process
for obtaining it was improved; so that, instead of using the
soot of dung, it is now formed by the distillation of bones.
The impure ammoniacal liquor, thus obtained, is combined
with sulphuric acid, by an easy process, and the resulting
sulphate of ammonia is then decomposed by muriate of soda,
by which sulphate of soda and muriate of ammonia are produced.
They are separated, and the latter is formed into
heads by sublimation. In this state, it occurs in commerce.
It was made in great quantity in the vicinity of the temple
of Jupiter Ammon; and hence its name.
Mr. Minish, according to the English writers, is entitled
to this method of converting impure liquid ammonia into sal
ammoniac. The following is an outline of his process. He
suffered the impure ammoniacal liquor to percolate through
a stratum of bruised gypsum, and as carbonate of ammonia
is contained in the liquor, the fluid, which filters, would contain
sulphate of ammonia, the carbonate of lime being insoluble.
This sulphate he evaporated, and the dry mass, mixed
with muriate of soda, was sublimed. If I am not greatly
mistaken, however, although I have not the work to refer to,
this process is described in Dr. John Pennington's Chemical
Essays, a work published in Philadelphia, about 1792. Dr.
Pennington's work, we may observe, is the first chemical
book which was published in the United States, and contains
numerous important facts and observations. That this process
was known in Philadelphia, and used at the Globe works,
or rather Glaub works, (from the circumstance that Glauber's
salt was made there,) is within the recollection of many.
I heard the late professor Wistar speak of this process, and of
the economy in using gypsum.
Mr. Lebanc (Annales de Chimie, vol. XIX.) invented
a process, by which he brought the ammoniacal gas and muriatic
acid gas in contact, in a chamber lined with lead. In
one pot, he put common salt and oil of vitriol; in another pot,
animal matter. Being conducted by pipes into the chamber,
the gases united, and sal ammoniac was formed. Other improvements
have been made, as obtaining ammonia from coal
soot, &c.
Ammonia is generated in artificial nitre beds, and is at first
united with nitric acid; which compound is subsequently decomposed,
as the process of putrefaction goes on, by the potassa,
calcareous earth, &c. present in nitre beds. See Nitrate
of Potassa.
Sal ammoniac is ready formed in the soot of animal feces,
twenty-six pounds of which yield six of the salt. According
to Siccard, who published, in 1716, an account of the fabrication
of sal ammoniac in Egypt, which Geoffroy, in the
same year, proved to be a compound of the spirit of sea salt
and volatile alkali, sea salt and urine were used in that country.
The account, however, given by Lemery, in 1719,
makes no mention of either sea salt or urine.
Sal ammoniac is found native. It occurs in the vicinity
of burning beds of coal, both in Scotland and England, and
is met with in volcanic countries. When triturated with
quicklime, it exhales ammonia, which is a characteristic of
all ammoniacal salts.
Sal ammoniac is often found in crusts of lava. Sir William
Hamilton observes, that, in the fissures formed by the lava,
this salt sublimes. He found, in the same locality, common
salt.
Sal ammoniac is decomposed by a variety of substances.
Sulphuric acid will disengage the muriatic acid from it, while
lime, potassa, &c. liberates the ammoniacal gas, which, when
combined with water by distillation or other means, forms
the common spirit of sal ammoniac, or water of ammonia.
Mixed with carbonate of lime and sublimed, it produces the
carbonate of ammonia, usually called mild volatile alkali, or
pungent smelling salts. Ammonia, in a separate state, unites
with some metallic oxides, giving rise to certain fulminating
powders, which have been already noticed. That iodine decomposes
ammonia, we have shown, when on the preparation
of iodide of azote, or fulminating powder.
Sal ammoniac enters into the composition of candles, to
prolong their duration. The process recommended in the
Archives des Découvertes is the following: Dissolve, in
half a pint of water, a quarter of an ounce of sal ammoniac,
two ounces of common salt, and half an ounce of saltpetre,
and add the solution to three pounds of mutton tallow, and
eight pounds of beef tallow, previously melted. Continue
the heat until all the water is evaporated. It is then suffered
to cool, and, when used, is to be melted with a quarter of
an ounce of nitre, and formed into candles in the usual manner.
This preparation of tallow is highly recommended on
account of its economy, as well as the improvement itself.
A candle, made of this tallow, will burn two hours longer
than one of the ordinary kind.
Another process for making candles, in which sal ammoniac
is used, is mentioned in the Annales des Arts et Manufactures,
Nos. 142 and 146. Eight pounds of suet are melted,
and a pint of water is added. The tallow is again submitted
to heat, and the same quantity of water, holding in solution
half an ounce of saltpetre, half an ounce of sal ammoniac, and
one ounce of alum, is added. It is then suffered to stand, and
when used is re-melted. The wick is first dipped in a mixture
of camphor and wax. Care must be taken, before the tallow is
used, to evaporate the water. Equal parts of beef and mutton
tallow are recommended.
Sect. XXXIV. Of Corrosive Sublimate.
Corrosive sublimate, known in chemistry by the names of
corrosive muriate, and perchloride of mercury, is made use
of in some preparations of fire-works, and particularly in the
composition of stars, in which it is mixed with a variety of
substances, such as steel filings and antimony, in order to
vary the appearance of the flame, and to communicate to it
particular colours. Corrosive sublimate is formed by various
processes, among which we may enumerate the following:
Take five parts of sulphuric acid, four parts of mercury, four
parts of muriate of soda, and one part of black oxide of manganese.
Boil the mercury in the sulphuric acid, until it forms
a dry sulphate, which is to be reduced to five parts. Mix the
sulphate thus formed, with the muriate of soda, previously
dried, and the oxide of manganese, and sublime the mixture.
By this process the sulphuric acid of the sulphate unites with
the soda, and forms sulphate of soda; while the muriatic acid
of the muriate of soda combines with the oxide of mercury,
(which receives an addition of oxygen from the oxide of manganese,)
and forms the perchloride, called by Thenard the
deutochloride of mercury. The same process is used without
the addition of manganese. By exposure to heat, the
sublimate sublimes, and the sulphate of soda forms the residuum.
The same salt, if re-sublimed with an addition of crude
mercury, will be changed into the protochloride of mercury,
or calomel. Or, if the sulphate of mercury and muriate of
soda be mixed with crude mercury, and sublimed, calomel
will be formed at one operation. It is sufficient to observe,
that corrosive sublimate is one of the most virulent of poisons
when swallowed; and therefore should be used with caution.
It is soluble in water, and capable of crystallizing. It is
also soluble in alcohol, to the flame of which it communicates
a yellow colour, and in sulphuric, nitric, and muriatic acids.
It is decomposed by alkalies, forming with ammonia a triple
salt, (Sal Alembroth,) by the alkaline earths, and the metals
or their sulphurets; and, when distilled with arsenic,
bismuth, antimony, or tin, the mercury is separated.
The proper antidote for corrosive sublimate, is the white of
egg or albumen, which converts it into calomel. Sulphuretted
hydrogen water may also be employed along with emetics.
The effect of albumen, in this way, may be relied on.
Sect. XXXV. Of Orpiment.
Orpiment, or the yellow sulphuret of arsenic, which is
either native or artificial, is principally used in fire-works for
the composition of stars. Orpiment is divided by some into
two kinds; viz. the red, called realgar, and the yellow, called
yellow arsenic.
Arsenic combines readily with sulphur. When they are
mixed together, and put into a crucible and fused, the product
will be a red vitreous mass. This red sulphuret may also
be formed, by melting sulphur with arsenious, or arsenic
acid. Sulphurous acid gas will be evolved, evidently showing
that a portion of the sulphur unites with the oxygen of
acid employed.
When arsenious acid, known in commerce by the name of
white arsenic, and called by some oxide of arsenic, is dissolved
in muriatic acid, and a solution of sulphuretted hydrogen
in water is added, a yellow precipitate will be obtained
which is orpiment. The hydrogen, in this case, unites with
the oxygen of the arsenious acid, by which the metal is reduced,
and the sulphur then combines with it. A mixture of
sulphur and arsenic, exposed to a heat not sufficient to melt
them, will sublime into a yellow sulphuret.
Both the yellow and red sulphurets are employed in fire-works.
They are not, however, required, except in particular
cases. In the composition of Bengal lights, given in the
Bombardier or Pocket Gunner, by R. W. Adye, orpiment is
used. According to the same author, it is also used in Chinese
white lights. Both the yellow and red sulphuret of arsenic
will detonate with chlorate of potassa.
Sect. XXXVI. Of Antimony.
The antimony, which enters into the composition of many
fire-works, is not to be understood to be the metallic, or regulus
of, antimony, unless so expressed; but the crude antimony
of the shops. Crude antimony is a combination of
antimony and sulphur, and is usually met with in fine powder.
That both antimony and its sulphuret have a powerful effect
in modifying the flame of gunpowder, and all compositions,
in which nitre and inflammable substances form a part, is evident
from the many cases, in which it is employed, and from
the effects that thereby result.
The different substances in any inflammable compound, intended
to produce particular colours, should be so mixed, as
that, from a knowledge of the proportions which produce
such colours, the effect may be retained, even when it is mixed
with other bodies. For this reason, the artist should know
the different effect of each ingredient. Some may show themselves
in the flame, some in sparks, some in stars, others in
fire-rain, and the like, as the case may be. Antimony, for
instance, produces a reddish flame, if it be in a proper proportion,
and not altered by the presence of other substances.
Hence, when antimony is mixed with nitre, the flame will be
more or less a whitish-green.
This modification, or change in the appearance of flame, is
apparent in certain compounds, of which antimony constitutes
a part. Thus, antimony is used in the preparation of the common
rocket stars, in drove stars, in the fixed pointed stars,
in some of the gold and silver rains, in the slow and dead fire
for wheels, in tourbillons for crowns or globes, in the composition
of serpents, lances for illumination, Bengal lights, and
many other kinds of fire-works. According to Adye, (Pocket
Gunner,) it enters into the composition of carcasses, Chinese
lights, &c.
When it is as one to sixteen of nitre, the gunpowder being
as four, and the sulphur, eight, the composition will produce
a white flame; but when it is in the proportion of eight to
sixteen of nitre, without any addition, the flame will be blue.
By substituting, in its place, eight of amber to sixteen of
nitre, with sixteen of sulphur, and eight of meal powder, this
change will produce a yellow flame. It is obvious, however,
that these and similar changes are owing to the proportions,
as well as to the substances used.
Antimony, in the state of a sulphuret, when mixed with
chlorate of potassa, &c. will form detonating compounds.
Antimony is a grayish-white metal, more or less brilliant
and laminated. It is brittle, and may be easily reduced to
powder. It melts at a red heat, and evaporates at a higher
temperature: on cooling, it crystallizes. It undergoes no
change by exposure to the air, except the loss of its lustre.
When steam is made to pass over ignited antimony, the decomposition
of the water is so rapid, as to produce a violent
detonation. At a white heat, it burns, and forms a white
coloured oxide, called the argentine flowers of antimony.
Its oxides are various, some of which, possessing acid properties,
are called acids. The protoxide is gray, the antimonious
acid, white, and antimonic acid, of a straw colour.
The crocus of antimony, and the glass of antimony are oxides
of this metal, but in particular states of combination.
It unites with several of the acids. Its oxide, with tartaric
acid, and tartrate of potassa, forms tartar emetic. With
chlorine, it constitutes the butter of antimony.
The artificial sulphuret may be formed, by melting sulphur
and antimony together. The native sulphuret is almost
the only ore of antimony, and is the mineral from which
the regulus is obtained. It unites with the metals, forming
alloys of different kinds.
Sect. XXXVII. Of Carbonate of Potassa.
Potassa, either pure or carbonated, retards the progress
of combustion; and, therefore, may prevent, according to
the proportion employed, the action of combustible bodies on
nitre. Combustion may be retarded by using those substances,
which are not in themselves inflammable, and which,
if used in too large a quantity, would effectually prevent it.
Clay, wood ashes, &c. as in the blind fuse, act on this principle;
and serve, also, in particular cases, to produce that
succession of explosions, which renders the effect of some
fire-works, more grand and impressive. Rope, soaked in a
solution of saltpetre and dried, would burn rapidly, were it
not for the after immersion in potash ley, or urine, either of
which acts by retarding the progress of combustion. The
same thing may be said of other bodies, the use of which will
claim our attention hereafter. Potassa, although not generally
used for the purposes mentioned, as it is apt to deliquesce,
or absorb water, and thus destroy the effect altogether, may
be more advantageously employed in a liquid state, as in the
preparation of slow match in the way stated under that head.
But as match rope is now generally superseded by the port-fire,
as a more certain method of firing cannon, it would be
unnecessary, as it is irrelevant, to enlarge on this head. The
use, also, of the priming fuse, which conveys the fire to the
powder in the gun, with certainty and with rapidity, is an
improvement of no small moment.
Alum has also been used for the purpose of checking the
rapidity of combustion, in some particular fire-works. In
one of the formulæ for the preparation of fire-balls, to be
thrown with the hand, or fired from a gun, given in the Memoir
on Military Fire-works, as taught at Strasburg, in
1764, there is, besides sulphur, mutton suet, saltpetre, and
antimony, nitre of alum, equal to one-fourth of the weight
of the compound. That this salt, the supersulphate of alumina
and potassa, is used to make paper, as cartridge paper,
&c. incombustible, is a fact, with which every one is acquainted.
We might, also, enumerate the uses of glue, isinglass, gum
arabic, &c. for similar purposes; and also of wood-ashes, in
the composition of the, so called, blind fuse. Light twisted
white rope, when soaked in strong ley, or a strong solution
of potash, we are informed, will form a slow match that will
burn only three feet in six hours.
Potash is obtained from wood-ashes, by lixiviation with
water, and evaporation. It contains more or less impurities;
and always carbonic acid, from which it is separated by quicklime,
the alkali being rendered caustic. Some of the foreign
ingredients are burnt off by exposing it to heat in an oven.
It then assumes a white, somewhat pearly appearance, and
takes the name of pearl-ash, but is still the same alkali.
Wood-ashes, when mixed with quicklime, and lixiviated,
produce caustic ley, the strength of which depends on the
quantity of alkali held in solution. It is this ley, when boiled
with oils, fat, &c. that produces soft soap. Hard soap is
a combination of oil or fat, and soda. The quantity of real
alkali in potash may be known by the proportion of acid required
to saturate a given weight of it. Potash, pearl-ash,
salt of tartar, and salt of wormwood are all carbonates of potassa.
This alkali is called the vegetable alkali, because it is
obtained from vegetables. It is considered to be the hydrated
deutoxide of potassium, and when decomposed will furnish
potassium.
Table of the saline or soluble products of one thousand
pounds of ashes of the following vegetables.
| SALINE PRODUCTS. |
| Stalks of Turkey wheat, | 198 lbs. |
| Stalks of sun-flower, | 349 |
| Vine branches | 162.6 |
| Elm | 166 |
| Box | 78 |
| Sallow | 102 |
| Oak | 111 |
| Aspen | 61 |
| Beach | 219 |
| Fern, cut in August, | 116, | or 125 according to Wildenheim. |
| Wormwood | 748 |
| Fumitory | 360 |
| Heath | 115 |
The observations of Mr. Kirwan on potash may be seen in
Aikin's Chemical Dictionary.
When a piece of hydrated potassa is placed between two
disks of platinum, which are brought in contact with the poles of
a galvanic battery, consisting of upwards of 200 pairs of plates,
four inches square, the oxygen will separate at the positive surface,
and small metallic globules of potassium will be formed at
the negative surface. The potassa, in the mean time, will
undergo fusion.
Sir H. Davy discovered potassium, in 1807. It may be
obtained by means of iron turnings, in the following manner:
Heat the iron turnings to whiteness in a curved gun barrel,
and suffer potassa, in a state of fusion, to fall upon them very
gradually, air being excluded: potassium will form, and collect
in the cool part of the tube. For the different facts respecting
this metal, consult Sir H. Davy's communications
on the subject, and the memoirs of Gay-Lussac and Thenard,
Curadeau, &c. See also, Davy's Chemical Philosophy, and
Thenard's Traité de Chimie.
Potassa unites with, and neutralizes, acids, and forms salts;
the principal of which are the sulphate, muriate, and nitrate
of potassa. It unites also with sulphur, phosphorus, &c.
Potassa, in the state of carbonate, is very soluble in water,
for which it has so strong an affinity, that, when exposed to
the atmosphere, it deliquesces and becomes fluid. Caustic
potassa undergoes the same change, in a more remarkable degree.
It is on account of its great avidity for water, that
the carbonate is used in the preparation of alcohol from
spirituous liquors; it retaining the water, while the alcohol
may be distilled over.
Potassa has a stronger affinity for the acids, than either the
earths or metals; hence it decomposes earthy and metallic salts,
the earth or metallic oxide being precipitated, while it unites
with the acid of the salt. It is on the same principle, that earthy
and metallic salts decompose soap; and waters which are hard,
and owe that property to the presence of earthy salts, will
curdle, or, in other words, decompose soap. Such waters,
for this reason, are called hard. Acids have the same effect
in decomposing soap.
The use of potassa is very apparent in the manufacture of
saltpetre. When the nitric acid is combined with an earthy
base, as in the calcareous nitre of the nitre caves of the western
country, potassa from wood-ashes will decompose it, on
the principle already stated; and, by combining with the nitric
acid, form nitrate of potassa. It is used also in refining
saltpetre, where earthy salts are present, besides common
salt. The effect of this alkali, for that purpose, will be more
obvious, by referring to the processes for the extraction and
refining of saltpetre, in the article on that subject.
Potassa acts as a flux for siliceous substances and forms
glass. These are its prominent characters.
Sect. XXXVIII. Of Wood-Ashes.
Wood-ashes, the product of the combustion of wood, contain
potassa, some foreign salts, and earthy and sometimes
metallic substances, insoluble in water. The quantity of
alkali, which ashes, obtained from different woods, furnish,
is greater or less, according to the nature of the wood. The
ashes of the oak are generally used in pyrotechny; but it
seems to us, that ashes in common will have the same effect.
The ashes, for this purpose, should be dry, and passed
through a fine sieve. They enter into the composition of
blind fuse.
In some instances, the leached, or lixiviated ashes might be
used. The residue, after the separation of alkali and saline
matter by the action of water, is nothing more than the insoluble
part of the ashes. Caustic ley is always obtained
from wood-ashes, by mixing them with about a fiftieth part
of quicklime, and putting them into a barrel or tub, and adding
water. The lime takes up the carbonic acid, and the
ley comes off in a caustic state. If the solution should not
contain a sufficient quantity of potassa, or not bear an egg,
as that is the usual criterion of its strength, (which depends
on its specific gravity,) its strength may be increased by evaporation;
and, if too strong, simple dilution with water, is all
that is necessary.
While the ashes of some plants, as the upland plants, generally
yield potassa; others, as many marine plants, the salicornia
europea, salsola tragus, salsola kali, &c. afford soda
by incineration. It will be sufficient, however, to observe,
that the ashes of all plants contain alkali, in more or less
quantity, which depends on various circumstances; and that
the alkali may be extracted by lixiviation, and, in some instances,
may even be seen among the ashes, in a semivitrified
mass. The white ashes, which are formed by the combustion
of animal matter, as osseous or bony substances, we
may remark, do not afford potassa or soda, but only phosphate
of lime, and some uncombined earths. Bones, nevertheless,
may, like wood, be carbonized, although the charcoal
formed is of a different nature. For the preparation of
phosphorus from bone-ash, see the article Phosphorus.
Sec. XXXIX. Of Clay.
Clay is an argillo-siliceous substance, of a colour more or
less yellow, and containing a variable quantity of silica and
alumina, with oxide of iron. There are a variety of clays;
the common potter's clay, pipe clay, porcelain clay, &c.
Some contain, and others are free from iron. Those that contain
this metal burn red; while those which remain, or become
white in the process of burning, are free from it.
The use of clay in fire-works is confined nearly altogether
to rockets. In the driving of sky-rockets, &c. the charge
must always be driven one diameter above the piercer, and
on it there is sometimes rammed one-third of a diameter of
clay, through the middle of which a hole is bored to the
composition, so that, when the charge is burnt to the top, it
may communicate its fire through the hole, to the stars in the
head. This, however, is not always the case. See Rockets.
The clay for fire-works, is usually prepared of the common
kind, which contains neither stones nor sand. It must
be first baked in an oven, until perfectly dry, and then pulverized,
and sifted through a common hair sieve. In China,
the Chinese mostly employ, for this purpose, their white porcelain
clay.
Sec. XL. Of Quicklime.
Lime, as it is found in nature, is combined with carbonic
and sulphuric acids, and less frequently with some of the
other acids, as the nitric, fluoric and phosphoric. Calcareous
carbonates are the most abundant; in which we include marble,
limestone, and chalk; and the sulphate, or gypsum, may
be considered the next. Lime constitutes the basis of marine
shells; for, when burnt, they furnish quicklime. Its
union with nitric acid is well known, forming the calcareous
nitre of the saltpetre caves of Kentucky, &c. We have mentioned
this combination under the head of nitre.
Without enumerating all the chemical properties of lime,
it will be sufficient to remark, that it is composed of calcium
and oxygen, and, when slaked with water, will evolve
caloric in a free state, while the water solidifies or combines
with the lime; that it forms with water, a solid hydrate, an
example of which combination is afforded by the preparation
of mortar; that it dissolves in water, and forms lime-water,
and is slaked by exposure to the air, absorbing, at the same
time, carbonic acid; that it unites with acids, like other salifiable
bases, and forms salts, some of which are soluble in
water, and others not; that it deprives the alkalies of carbonic
acid, and renders them caustic, being itself changed
into a carbonate; and, that it unites with sulphur and phosphorus,
forming a sulphuret and phosphuret, and, also, with
hydroguretted sulphur, and sulphuretted hydrogen, forming
a hydroguretted sulphuret, and a hydro-sulphuret.
When limestone, marble, &c. are burnt in a kiln, the carbonic
acid is expelled, and quicklime formed. Quicklime
and lime, chemically speaking, are synonimous terms.
The fluor, or Derbyshire spar, is a fluate of lime. When
this substance is distilled in a leaden retort, with sulphuric
acid, we have sulphate of lime, and fluoric acid gas, called
by some hydro-fluoric acid. This acid, when received in water,
is used to etch on glass, in the same manner as nitric
acid on copper; and while applied in a liquid state, or in
that of gas, it acts on the glass, by combining with the silicon,
and is changed from the hydrofluoric, into the silicated
fluoric acid. If, instead of employing a leaden vessel, we
make use of a glass retort, or introduce powdered glass or
silica, into the leaden vessel, in either case, we obtain another
acid, which we have just mentioned, the silicated fluoric
acid; in consequence of the union of silicon with the supposed
radical of the fluoric acid, known by the name of fluorine.
Quicklime is occasionally, though but rarely, employed in
fire-works. That it increases the strength of powder, is asserted
by Dr. Bayne. See Gunpowder. Its use in making
slow match, along with other substances, is given in the article
on that subject.
Sec. XLI. Of Lapis Calaminaris.
That some of the ores of zinc are employed in fire-works,
is evident from the use of lapis calaminaris, or calamine
stone, which is an impure carbonate of zinc. Calamine should
be finely pulverized and sifted. As zinc gives a particular
colour to flame, (see zinc), its carbonate may also communicate
a colour, and, under particular circumstances, may produce
a great variety, and, therefore, in such cases, be preferable
to the zinc itself. It is one of the ingredients in the
dead fire for wheels, which is composed of lapis calaminaris,
saltpetre, brimstone, and antimony.
The modifications, to which particular bodies are subject,
as to their respective effects, depend very greatly on the
presence of other bodies, and frequently on the chemical action,
which ensues throughout; so that, as we had occasion
to observe, the effect which one body would produce on the
flame, maybe completely changed, modified, or varied by the
presence of a second, third, or fourth substance. The art,
therefore, of uniting various bodies, in kind, as well as in
proportion, so as to produce a given effect, can be acquired
only by a series of experiments. Zinc, as a metal, when finely
divided, produces a peculiar effect; when mixed with other
metals, and with certain salts, as sal ammoniac, another; and,
when combined with some acids, as the carbonic in lapis calaminaris,
a third effect; and these effects may be governed,
as it appears, by the presence or absence of certain bodies.
This fact will appear more striking, when we consider the various
mixtures, and their respective properties. For the uses
of zinc, see that article.
Sec. XLII. Of Zinc.
Zinc, commonly called spelter, is a metal, obtained from
blende, or sulphuret of zinc, and calamine, or carbonate of
zinc. The ore is first roasted, and then mixed with some
carbonaceous flux, and submitted to the action of heat in
close vessels. The metal is volatilized, and passes over, and
is usually caught in water. It is then fused, and cast in
moulds.
Zinc possesses many remarkable properties, some of which
are the following. It is of a brilliant white colour, with a
shade of blue, and is composed of a number of thin plates,
adhering together. Its specific gravity is more than six times
that of water. It is brittle, but, when heated to 212 degrees,
may be hammered out, or made into sheets. At 400° it
becomes very brittle. Its tenacity is so feeble, that a wire of
1/10th of an inch in diameter, will support a weight of only
26 pounds. At 680° it melts, and above that temperature,
evaporates. It soon oxidizes, and its lustre is therefore tarnished.
At common temperatures, it soon decomposes water;
and, when the vapour of water is passed over it at a
high temperature, the decomposition is very rapid, the oxygen
of the water being absorbed. Zinc is soon oxidized
when melted and exposed to the air, forming a gray oxide.
At a red heat, zinc inflames, and the product of combustion
is the white oxide of zinc, or flowers. The oxide of
zinc is reduced by mixing it with charcoal, and exposing the
mixture to a strong heat in close vessels.
Zinc will burn in chlorine gas, and forms a chloride of
zinc. If the perchloride of mercury and zinc-filings be heated
together, the same compound will result. This chloride
melts at 212°, and rises, in the gaseous form, at a heat much
below ignition. It was formerly called the butter of zinc, and
muriate of zinc. With iodine, zinc forms a compound, called
iodide of zinc.
With phosphorus and sulphur, zinc also combines, and
with the latter, it forms the native sulphuret, known by
the name of blende. It unites, also, with acids, and forms
salts. Of these, the sulphate of zinc, or white vitriol, is
the most common. It unites with various metals, forming
alloys. Of these, that with copper, called brass, is the most
known. Zinc, with copper, forms galvanic batteries. With
tin and mercury, it constitutes amalgam for electrical machines.
It forms, besides brass, the yellow copper, or laiton;
commonly called pinchbeck.
Acetic acid readily dissolves zinc. The acetate formed is
not altered by exposure to the air, is soluble in water, and
burns with a blue flame. It may be used, therefore, in fire-works,
to communicate that colour to flame. It may be formed
very expeditiously, by mixing about equal parts of sulphate
of zinc, and acetate of lead, both being in solution. The sulphate
of lead, which is formed, will precipitate, and acetate
of zinc remain in solution. By evaporation, it is obtained in
crystals. This salt cannot injure any composition of fire-work,
in which it enters; as it does not deliquesce, and, for
that reason, may be advantageously employed.
When zinc is used in fire-works, it should be remarkably
fine. The powder may be very readily formed, by heating it,
until it is about to fuse, and pulverizing it while hot, in a
warm mortar. It is generally considered, however, that the
best method of obtaining the powder of zinc, although a
longer time is required, is by filing it; but the filings are
more or less coarse, according to the file which is used. They
may be sifted, and thus obtained of any degree of fineness.
In various blue lights, in the blue flame of the parasol and
cascades, and other descriptions of fire-works, it is used. It
gives a more brilliant light than any other substance used for
this purpose. It is frequently mixed with other substances;
but, as to its peculiar properties, they remain the same. By
the combustion of zinc, which follows in fire-works, it always
produces an oxide. In this state, it is expelled, or
thrown off.
Acetate of zinc appears to possess advantages over zinc-filing,
especially as it produces the same colour, may be more
readily mixed, and with more accuracy, and does not deliquesce
or absorb moisture, a circumstance which must always
be guarded against in artificial fire-works.
Sec. XLIII. Of Brass.
This is a mixed metal, composed of copper and zinc. This
alloy, according to the proportion of the metals, is more or
less yellow, or reddish-yellow. The yellow copper, or laiton
of the French, the similor, Manheim gold, prince Rupert's
metal, &c. are alloys of the same metals.
Zinc readily unites with copper; and the usual manner of
forming brass by brass-founders, is to make a direct union
between the two metals. The process, however, generally
consists in mixing together granulated copper, calamine, or
carbonated oxide of zinc, and charcoal in powder, and melting
them in a crucible. The charcoal reduces the zinc,
which then unites with the copper. The heat is kept up for
five or six hours, and towards the last of the process, is
raised. Zinc, in small proportion, renders copper pale, and
in the proportion of one-twelfth, inclines its colour to yellow.
The yellow colour increases in intensity with the zinc, until
the weight of this metal in the alloy equals that of the copper.
An increase of zinc, afterwards makes the alloy white. English
brass contains one-third of its weight of zinc. In Germany
and Sweden, the proportion of zinc varies from one-fifth
to one-fourth of the copper. Twenty to forty parts of
zinc, with eighty to sixty parts of copper form the cuivre
jaune, laiton, or yellow copper of the French.
Dutch metal, or Dutch gold, is a fine kind of brass, and
comes in leaf, which is about five times as thick as gold leaf.
This brass is made by the cementation of copper plates with
calamine, and hammered out into leaves.
According to Thenard (Traité de Chimie, tome i, p. 478),
the French use 50 parts of calamine, mixed intimately with
20 parts of charcoal, and stratified in a crucible with 30
parts of laminated, or granulated copper. British brass consists
of two parts of copper, and 11/8 parts of zinc, by
weight.
The filings of brass are much employed in fire-works.
They communicate to stars, rains, &c. a flame between a blue
and green. In some, the filings of copper alone are used.
A beautiful green fire, for instance, is produced by 16 ounces
of gunpowder, and 31/4 ounces of copper-filings. Verdigris
is also employed for the same purpose; but the effect
is not so striking, as in that preparation, the copper is already
oxidized. The effect of copper in fire-works, it is to be recollected,
depends, like that of other metals, on its combustion,
and consequent oxidizement. The product of the combustion
of brass, is oxide of copper, and oxide of zinc.
Sec. XLIV. Of Bronze.
The union of copper with tin, in various proportions,
forms gun-metal, bell-metal, the mirrors of telescopes, and
bronze.
The ductility of the copper is diminished by the tin; but
its hardness, and tenacity, as well as its fusibility and sonorousness
are increased.
To form a complete union of the two metals, they should
be continued in fusion for some time, and constantly stirred.
The tin is apt to rise to the surface, unless this precaution
is used.
Bronze is usually composed of 100 parts of copper, and
8 to 12 parts of tin. It is yellow, brittle, heavier than copper,
and has more tenacity.
The same metals, and in the same proportion, constitute
gun-metal. In the brass ordnance made at Woolwich, the
proportion of tin varies from 8 to 12, to the 100 parts of
copper. The purest copper requires the most. That the alloy
is more sonorous than iron, is evident from the report of
brass pieces, being louder than that occasioned by iron
guns.
When the alloy is 78 of copper and 22 of tin, it is chiefly
used for clocks. There is, in the English metal, about five
per cent. of zinc, and four per cent. of lead. The proportion
of tin, in bell-metal, varies. In church bells, less tin is
used than for small bells. In the latter, zinc is sometimes
added.
The Tam-tam, or gong of the Chinese, used for cymbals,
clocks, mirrors, &c. contains, according to analysis, 80 parts
of copper, and 20 parts of tin. The proportions, however,
are not always the same.
The ancients made cutting instruments of an alloy of copper
and tin. A dagger, analyzed by Mr. Hielm, consisted
of 837/8 copper, and 161/8 tin. Vessels of bronze were
frequently covered with silver. Some of this kind were
found in the ruins of Herculaneum.
Pliny observes, that ancient mirrors were made with a
mixture of copper and tin; but that, in his time, those of
silver were so common, that they were even used by the maid
servants. The quantity of tin, to make the most perfect
speculum, depends on the quality of the copper. If the proportion
of tin be too small, the composition will be yellowish;
if it be too great, the composition will be of a grayish-blue
colour. Mr. Edwards casts the speculum in sand with
its face downwards; takes it out while red-hot, and places it
in hot wood-ashes to cool, otherwise it would break in cooling.
The mixture is first granulated, by pouring it into water,
and then fused a second time for casting. Mr. Little
recommends the following proportions: 32 parts of the best
bar copper, 4 parts of brass, or pin wire, 161/2 of tin, and
11/4 of arsenic.
Whether for speculum metal, bronze, or gun-metal, the
metals must be mixed exactly, and for this purpose be kept a
long time in fusion, and constantly stirred; otherwise, the
alloy will not be of a uniform quality, as the greater part of
the copper will sink to the bottom, and the greater part of
the tin rise to the surface. When we speak of brass guns,
as that name is generally applied to them, we are to understand,
that they are not made, like brass, of an alloy of copper
and zinc.
The ancient metallic mirrors, which were in use before
the present mirrors, or the discovery of glass, and the mode
of applying to its surface an amalgam of tin, were composed
of two parts of copper and one part of tin. Mr. Mudge
asserts, that the best proportion for mirrors is 32 parts of
copper and 14.5 parts of tin. Klaproth found a specimen of
ancient mirror to consist of 32 of tin, 8 of lead, and 62 of
copper. The alloys of copper and tin may be decomposed
by dissolving them in an acid, the muriatic for instance, and
immersing a sheet of iron, which will precipitate the copper.
The tin may then be separated by immersing a plate of lead,
or zinc, by either of which metals, it will be precipitated.
Bronze, being a mixed metal, in which the copper forms
the principal ingredient, is sometimes used in fire-works, in
lieu of copper or brass; for its effects are similar. By the
combustion of bronze filings, we have an oxide of copper
and an oxide of tin.
Sec. XLV. Of Mosaic Gold.
This name, or aurum musivum, was given to a preparation
of tin, composed of tin and sulphur. It is considered to be
a persulphuret of tin.
Several methods are recommended for preparing this substance.
The oldest process is to sublime a mixture of 12 parts
of tin, 7 parts of sulphur, 3 parts of mercury, and 3 parts of
sal ammoniac. It may be formed by heating together in a
retort, a mixture of equal parts of sulphur and oxide of tin.
It is used principally for rubbing the cushions of electrical
machines, and for bronzing wood. In fire-works, it is sometimes
employed under the name of gold-powder.
It was supposed to be a combination of sulphur with the
oxide of tin. Dr. J. Davy (Phil. Trans. 1812, p. 199) and
Berzelius, (Nich. Jour. xxxv, 165), have proved, however,
that it is nothing more than metallic tin and sulphur; the proportions
of which, according to the former, are 100 of tin
+ 56.25 of sulphur.
Mosaic gold is of a yellow colour, resembling that of gold.
It is insoluble in water, and is not acted upon by muriatic or
nitric acid. The nitromuriatic, however, decomposes it. A
solution of caustic potassa dissolves it, forming a green solution,
which is decomposed by acids, letting fall a hydrosulphuret
of tin. It deflagrates with nitre.
When it is used in fire-works, it is pulverized, and sifted.
It is more generally employed as a pigment to impart a golden
colour to small statues of plaster-paris. When mixed
with melted glass, it is said to imitate lapis lazuli.
Sec. XLVI. Of Iron and Steel.
Both iron and steel are used abundantly in fire-works. It
would be unnecessary to detail the preparations, in which
they are employed, which may be seen by a reference to the
different kinds of fire, and to their respective formulæ.
Cast iron is more employed in artificial fire than forged
iron or steel, at least in the preparation of some, as gerbes,
white fountains, and Chinese fire.
The filings of iron and steel may be sifted through sieves.
A fine hair sieve will answer for common purposes. Their
fineness depends, in the first instance, on the file, which is
used. Steel or iron filings are more commonly employed in
the compositions for brilliant fire.
The sparks produced by cast-iron are very brilliant; but
the reduction of the iron to powder, or to a degree of fineness
sufficient for use, is a difficult operation. It is of too
hard a nature to be cut by a file.
This operation is generally performed in the following
manner: Procure from an iron foundry, some thin pieces of
cast iron, such as generally run over the mould at the time of
casting, and pound them on a block, made of cast iron, with
an iron hammer of four pounds weight, putting, under the
block, a cloth to catch the pieces of iron, which fly off. They
are beaten with the hammer in this manner, until the whole
is reduced to grains, which are more or less small. It is
then thrown into a sieve, which should be fine, and the dust
separated. This is used, in the place of steel dust, in small
cases of brilliant fire. The remainder is then put into a sieve,
a little coarser, and again sifted. This portion is preserved
separately. The same operation is repeated, but with sieves
of different sizes, till the iron passes through about the bigness
of small bird shot.
The pulverization may be effected in an iron mortar, with a
steel pestle, having the mortar covered in the usual manner,
to prevent the escape of the finer particles of the iron.
According to a writer in the Dictionnaire de l'Industrie,
vol. iii, p. 34, the Chinese prepare their iron-sand for fire-works
by igniting iron, and plunging it in cold water. They
then pulverize the scales thus formed, and pass the powder
obtained, through different sized sieves, which is then called
No. 1, 2, 3, 4, &c. as it is very fine or coarse. This cannot
be a good method, and we doubt whether it is at present employed;
because it is obvious, that the scales, in this case,
consist of the metal in the state of protoxide. D'Incarville,
a missionary at Pekin, obtained the process for making Chinese
fire; and observes, that the pulverized cast iron they
employ is called iron-sand, of which they have six numbers
or varieties.
As the goodness of iron or steel dust, in fire-works, depends
greatly on its being dry, and not oxidized or rusted; its
preservation must be accordingly attended to. The usual
preservative is to put it in a box, lined with oiled paper, and
covered with the same, or in tin cannisters, with their mouths
well closed.
When it is to be used, it is taken according to its size,
and in proportion to the cases, for which the charge is intended.
Large gerbes, of 6 or 8 lbs. require only the coarse
sort.
As the brilliancy of the sparks, produced by the iron and
steel dust, is a desideratum in the formation of some fire-works,
and as this brilliancy depends upon the nature and
quality of the metal, it may not be improper to offer some
remarks on these subjects.
That iron, when finely divided is capable of producing
sparks of fire, is a well known fact; and we see it daily in
the operations of the smith, when ignited iron is hammered
on the anvil. The scintillation produced by the steel, when
struck with a flint, is of the same character. In the latter
case, the metal is actually fused, and, when caught on a
paper, and examined with a microscope, will appear globular,
and partly oxidized. Hence it is, that gunpowder is inflamed
by this spark, which is nothing more than highly
ignited, and inflamed iron, possessing a temperature more
than sufficient to inflame gunpowder.
The effect, therefore, that results from the inflammation of
fire-works, in which iron or steel forms a constituent part, is
nothing more than a vivid combustion of the metal; and
during that process it becomes oxidized, as it does not form
an acid with oxygen, like arsenic, antimony, and some other
metals.
The combustion of iron or steel may be shown by a very
brilliant experiment, that of burning it in oxygen gas. A
steel wire, harpsichord wire for instance, formed into a spiral,
with a small piece of wood dipped in sulphur, stuck on its
end and then set on fire, upon being immediately introduced
into a bottle, containing pure oxygen gas, will burn with
great brilliancy, emitting a number of sparks or scintillations,
which fall like rain. In making the experiment, some
sand should be put into the bottle to prevent the sparks from
breaking it. This experiment illustrates the rapid combustion
of iron, or steel. For the oxygen gas supports the combustion;
and while the oxygen is actually taken up by the metal,
which becomes oxidized, and therefore increased in weight,
in the same manner as it does when inflamed in fire-works,
the caloric, the other constituent of oxygen gas, is given out
in a free state, and, with the light at the same time evolved,
produces the phenomena of combustion.
Many other experiments might be mentioned, in which
the same effects take place, and from which the same conclusions
may be drawn. But with respect to the effect,
whether it be dull, brilliant, or very brilliant, depends more
on the quality of the metal, than perhaps, on its subsequent
mixture with the other materials. Crude iron, usually called
cast iron, seems to possess this property in an eminent degree;
but in the experiment with oxygen gas, steel is always
preferable, as the combustion is more rapid, and the effect
more striking. The difference, which we will not attempt
to explain, may depend on the state, as well as the proportion
of carbon, which enters into crude iron, as well as steel.
In one case, the combustion ensues in contact with nitre, and
in atmospheric air; in the other, in contact only with oxygen
gas. Be this as it may, this inference is conclusive, that,
in all cases of the combustion of iron in fire-works, the metal
itself unites with oxygen, and the result of the combustion
is an oxide of iron; and with respect to the carbon, in both
instances, it is converted alike into carbonic acid. So that
whether the iron receives its oxygen from the nitre, or from
the air, or from both, is immaterial, as the products are the
same.
When iron is exposed to the atmosphere, it tarnishes, and
is gradually changed into a brown or yellow powder, called
rust. This change is owing to its combination with oxygen;
and its affinity for oxygen is such, that, when the vapour of
water is made to pass through an ignited gun-barrel, it is
decomposed, the metal becoming oxidized, and the hydrogen,
the other constituent of the water, being liberated in the
form of gas.
Gun barrels are browned by a process of oxidizement.
There are several processes recommended. One of which
is, to rub the barrel over with diluted nitric or muriatic
acid, and then, to lay it by for a week or two, until a complete
coat of rust is formed. A brush, made of iron wire, is
then applied; afterwards, oil and wax, and the barrel is finished
by rubbing it with a cloth. The gunsmiths in Philadelphia
use a mixed solution of sulphate of copper, tincture of
the muriate of iron, and sweet spirit of nitre. This they apply
by means of a cloth. The object is to form a rust, and to
render it permanent on the barrel by hard friction along
with wax. When sulphate of copper is employed, metallic
copper is precipitated on the barrel. A coat of rust, put on
in this manner, prevents effectually the oxidizement of the
iron; and in point of utility, and the saving of labour in
polishing and keeping muskets in order, the browning of barrels
is certainly advantageous in the land service. At sea, in
particular, where iron is more readily oxidized, this plan
ought always to be adopted. With regard to the use of
dragon's blood, it is entirely too temporary in its effect to be
depended on. I was informed by an intelligent gunsmith,
who followed the practice of browning barrels in Europe, that
he has known the browning to remain very perfect for years,
and that the best mode of insuring its durability is to use
the steel brush, which carries in, as he expressed it, the
rust.
The oxides, which are formed by the union of oxygen
with iron, are two; namely, the black and the red; the first
being the protoxide, and the last the peroxide. The black
oxide, which is formed by the combustion of iron, and by
other processes, contains 56 iron + 16 oxygen. The common
rust of iron is the peroxide of this metal, combined
with carbonic acid. It may be formed by exposing the
protosulphate of iron, or green vitriol, in solution, to the atmosphere,
and then adding an alkali. This oxide contains
more oxygen than the preceding; it consisting of 56 iron +
24 oxygen.
The tempering of cutting instruments, an operation which
requires great delicacy and exactness, after that of hardening,
is intended to obtain a fine and durable edge; and as
this subject may be interesting in a military point of view,
we deem the following remarks of use.
The hardening of steel instruments is performed by heating
them to a cherry-red, and then immersing them in cold
water. The tempering is another process, calculated, as we
observed, to obtain a fine and durable edge. This is performed
by heating oil to a certain temperature, and plunging
the instrument into it, where it remains until the colour appears,
indicative of the particular kind of temper which is
intended to be given. The experiments of Stoddart, (Nicholson's
Quarto Journal, iv, 129,) are conclusive on this subject;
for his experiments prove, that, between 430° and 450°
the instrument assumes a pale yellowish tinge: at 460° the
colour is a straw-yellow, and the instrument has the usual
temper of pen-knives, razors, and other fine edge tools. The
colour gradually deepens as the temperature rises, and at
500° becomes a bright brownish metallic yellow. As the
heat increases, the surface is successively yellow, brown,
red, and purple, to 580°, when it becomes of a uniform deep
blue, like that of watch springs. Before the instrument becomes
red-hot, the blue changes to a water colour, which is
the last distinguishable colour. These different shades are
owing to the oxidizement of the surface of the metal; and
the art of ornamenting sword-blades, knives, &c. long practised
in Sheffield, depends on this principle. The general process
is, that an oily composition is used, with which flowers
and various ornaments are painted. On the application of
the heat required for tempering it, that part which was covered
with the composition, is not altered, whereas, the
uncovered parts of the blade are changed. These ornaments,
when the paint is removed, have the natural colour of polished
steel. When steel is heated in hydrogen gas, no appearance
of the kind takes place, a fact which shows, that it is
owing to the oxidizement of the metal.
Iron is soluble in the acids. By the assistance of water, it
is acted upon by sulphuric acid; the metal being oxidized,
and the oxide dissolved, while hydrogen gas is evolved.
The salt, formed in this case, is the sulphate of iron, green
vitriol, or copperas. With muriatic, nitric, acetic and other
acids, it forms various salts; and with gallic acid, when the
iron is peroxidized, it forms the pergallate of iron, or common
writing ink, and also the bases of black dye.
Iron unites with carbon, sulphur and phosphorus. Of the
sulphurets, there are two kinds, the protosulphuret and persulphuret.
The former is the magnetic pyrites, and the latter,
cubic pyrites, from both of which, green vitriol is obtained
by decomposition. Pyrites, we may observe, was the
original fire-stone, or the feuer-stein of the Germans, which
was used in the place of flint. See Beckman's History of
Invention. Iron also unites with some of the metals, forming
alloys. The white iron of the French, (Fer blanc,) or tin
plate of the English, is found to be any alloy of tin with
iron, as well as a covering of tin on iron.
Sheet tin, or tinplate which is necessary in the construction
of the apparatus for some fire-works, for canister shot,
&c. is made by immersing sheets of iron, previously freed
from rust, into melted tin. The number of dippings it undergoes,
determines, in some measure, its quality and character.
The union of carbon and iron, forming very important
modifications of this metal, is not only interesting in the military
art, as concerns the metal for cannon, small arms, and
fire-works, but also in relation to the many and highly useful
compounds which result.
All the varieties of iron, which are distinguished by artists,
under particular names, we may consider under the following
heads: namely; cast iron, wrought or soft iron, and
steel.
Cast or pig iron is the name of this metal, when first obtained
from the ore. The ores of iron are various, and contain
a greater or less quantity of iron, which is either combined
with oxygen, or found with clay, giving rise to two
important classes of iron ore, the calciform and the argillaceous.
The reduction of the ore merely requires the presence
of charcoal, and occasionally some addition, as limestone,
when the clay iron ores are to be reduced. On the
application of heat in furnaces, constructed for the purpose,
the charcoal unites with the oxygen of the oxide, reducing
it to the metallic state, and escapes in the form of carbonic
acid; and the lime, if the ore be argillaceous, unites with the
clay, forming a kind of glass, which floats on the melted metal.
When the iron is suffered to run into moulds, prepared
for its reception, it usually takes the name of pig iron.
Manufacturers distinguish cast iron by its colour and
other qualities. The white cast iron is hard and brittle, and
can neither be filed, bored, nor bent. Gray mottled iron, so
called from its colour, is of a granulated texture, softer, and
may be cut, bored and turned on the lathe. Cannon are
made of this iron. Black cast iron is the most unequal in
its texture, but the most fusible.
Cast iron melts at 130° of Wedgwood. Its specific gravity
varies from 7.2 to 7.6. It is converted into malleable, usually
called soft iron, by a process called refinement. Several
modes have been adopted for this purpose. It was formerly
done by keeping it in fusion in a bed of charcoal and ashes,
and afterwards forging it. The hammering makes the particles
of iron approach each other, and expels some impurities.
Among the various improvements for expeditiously and effectually
converting crude into malleable iron, the process of
Mr. Cort seems to possess advantages. The cast iron is
melted in a reverberatory furnace, and the flame of the combustible
is made to act upon the melted matter. It is stirred
during this operation, by which means, every part is exposed
to the air. A lambent blue flame begins to appear in about
an hour, and the mass swells. The heat is continued about
an hour longer; and, by this time, the iron acquires more
consistency, and finally congeals. While still hot, it is next
hammered by powerful tilt-hammers. This is called the
puddling process.
Iron, obtained in this way, is not however pure; for it contains
either some of the other metals, or oxygen, carbon, silicon,
or phosphorus.
When small pieces of iron are stratified in a crucible with
charcoal powder, and exposed to a strong heat for eight or
ten hours, they are converted into steel. Steel is brittle, resists
the file, cuts glass, and affords sparks with flint. It
loses its hardness by ignition and cooling. It is malleable at
a red heat. It melts at 130 degrees of Wedgwood. By being
repeatedly ignited in an open vessel, it becomes, by hammering,
wrought iron.
Natural steel is that which is formed, by converting the
ore first into cast-iron, and exposing it to the action of a
strong heat, while the melted scoriæ float on its surface.
This steel is inferior to the others. Steel of cementation is
formed, on a large scale, by stratifying bars of iron with
charcoal, in large earthen troughs or crucibles, the mouths of
which are closed with clay. These troughs are put in furnaces,
and, in eight or ten days, the process is finished. This
is also called blistered steel, on account of the appearance of
its surface. The tilted steel is that which is beaten out into
small bars by the hammer. When broken, and the pieces
again united by welding in a furnace, and made into bars, it
is then called German or shear steel.
Cast steel is considered the most valuable of all the varieties;
and is used for the manufacture of razors, surgeons'
instruments, &c. It is, besides, more fusible than common
steel, and for that reason, cannot be welded with iron. It is
made by melting the blistered steel, in a close crucible, along
with pounded glass, and charcoal powder. It may also be formed
by melting together 30 parts of iron, 1 part of charcoal, and
1 part of glass. Equal parts of chalk and clay, put with
iron in a crucible, will also produce it.
The Celtiberians in Spain had a singular mode of preparing
steel. Diodorus and Plutarch both say, that the iron was
buried in the earth, and left in that situation, till the greater
part of it was converted into rust. What remained, without
being oxidized, was afterwards forged and made into weapons,
and particularly swords, with which they could cut asunder
bones, shields, and helmets. This process is used in Japan,
however improbable it may seem; and Swedenbourg, among the
different methods of making steel, has introduced it. Bishop
Watson, (Chemical Essays 8vo. i, p. 220,) speaks of the
same process. The fact has been verified at Gottingen; for
an anvil, which had been buried in the ground for many years,
was found to be extremely soft; and a part of it, which appeared
in steel-like grains, possessed the properties of steel.
The sabres made in Japan, according to Thunberg, are incomparable.
Without hurting the edge, they can be made
to cut through a nail at one blow.
The art of hardening steel by immersion in cold water is
very old. Homer (Odyssia ix, 301,) says, that, when Ulysses
bored out the eye of Polyphemus with a burning stake,
it hissed in the same manner as water, when the smith immerses
in it a piece of red-hot iron, in order to harden it.
Sophocles, Salmasius, Pliny, Justin and others mention the
use of water in hardening iron; but the most delicate articles
of that metal were not quenched in water, but in oil. As to
the opinion of the peculiar virtue of any particular water, for
the purpose of hardening iron, which many have believed, it
is altogether fallacious, although Vasari asserts, that the archduke
Cosmo, in 1555, discovered a water, that would harden
instruments, to cut, like the ancient tools, the hardest porphyry.
The art of working porphyry, however, was known
in every age. Beckman assures us, when treating of the
processes of making steel, that the invention and art of converting
bar iron into steel, by dipping it into other fused iron,
and suffering it to remain there several hours, although
ascribed to Reaumur, (Art de Convertir le Fer en Acier, p.
145), are mentioned by Agricola, Imperati, and others, as a
thing well known and practised in their time.
Pliny, Diamachus, and other ancient writers mention various
countries and places, which, in their time, produced excellent
steel. The ferrum Indicum and Sericum were the
dearest kinds. The former is the same as the ferrum candidum,
a hundred talents of which were given, as a present,
to Alexander in India.
Beckman thinks, that the ancient ferrum candidum is the
same kind of steel still common in India, and known under
the name of wootz; some pieces of which were sent from
Bombay in 1795 to the Royal Society. Its silver coloured
appearance, when polished, he thinks, may have given rise to
the epithet of candidum.
Mr. Faraday of the Royal Institution has lately examined
wootz, and imitated it very accurately. The experiments
may be seen in Ure's Chemical Dictionary, article Iron. It
appears that the presence of silex and alumina distinguishes
this kind of steel from the English. Four hundred and sixty
grains of wootz gave 0.3 of a grain of silex, and 0.6 of
a grain of alumina. It is highly probable, that the much admired
sabres of Damascus, are made from this steel.
A small portion of silver, melted with steel, improves the
latter very considerably. One part of silver and five hundred
parts of steel were melted together, and every part of
the alloy formed, when tested, indicated silver. The alloy forged
remarkably well, although very hard, and was pronounced to
be superior to the very best steel. This excellence is undoubtedly
owing to its combination with the silver, however small.
The alloy has been repeatedly made, and with the same success.
Various cutting tools have been made from it of the
best quality. The silver is found to give a mechanical
toughness to the steel.
Platinum and steel, equal parts by weight, form a beautiful
alloy, which takes a fine polish, and does not tarnish.
This alloy is said to make the best speculum. Steel, for
edge tools, is improved by this metal. The proportions,
which appear to be most proper, are from one to three per
cent. An alloy of 10 platinum with 80 of steel, after exposure
for many months, had not a speck on its surface.
Would not this alloy, as it is not oxidized, be very useful for
making points for lightning rods, in lieu of iron, gold, silver,
or platinum alone? The experiment is worth a trial; for
nothing adds more to the safety of a magazine, or building,
against the effect of lightning, than a conductor.
Iron and carbon, it appears, are capable of uniting in different
proportions; hence the variety of crude iron, and the
different kinds of steel. When the carbon exceeds the iron,
as in plumbago, or black lead, it forms a carburet. When
the iron exceeds, such compounds are properly speaking sub-carburets;
under which name, we may rank all the varieties
of cast iron and steel.
The hardness of iron, according to the experiments of
Mushet, (Phil. Mag. xiii, p. 138), increases with the proportion
of charcoal, with which it combines, until the carbon
amounts to about 1/60th of the whole mass. This is the maximum,
the metal acquiring the colour of silver. More carbon
diminishes the hardness, according to its quantity. The difference
in iron, whether it be the cold-short, or hot-short iron,
a matter of some consequence to the workers in this metal,
was found to be owing to phosphoric acid in the cold-short,
which exists with the iron. But the substance, called siderum
by Bergman, is a phosphuret, and not a phosphate of iron.
We have gone into this subject more fully, on account of
its importance, and intimate connection with the casting of
guns, and the different qualities of iron. In fire-works, it
will appear obvious, that the various properties exhibited by
iron are owing to the iron and carbon, to the changes which
they undergo, to the combustion which necessarily ensues,
and to the production of oxide of iron, and carbonic acid
gas; effects that invariably take place, whether cast iron or
steel be used, provided it is exposed to the action of agents,
under the same circumstances and conditions.
Sec. XLVII. Of Glass.
Glass, in the form of powder or dust, is used in fire-works.
The pulverization of glass is easily performed. It may be
done in an iron mortar, and passed though fine wire or brass
sieves. It is used in the composition for wheels, in water
balloons, cones, fire-pumps, slow white fire, &c.
Glass is nothing more than fused silica, made by exposing
a mixture of silica and other substances to the action of a
violent heat.
The quality of the glass depends on the proportion of silica,
and the fluxes which are used in promoting its fusion; for
the various kinds of glass, as white glass, green glass, bottle
glass, &c. are all, in one respect, the same, though they differ
in these particulars.
The glass of Saint-Gobin in France is made by fusing
white sand, lime, soda, and broken inferior glass. The white
goblet-glass is made of sand, potash, lime, and old glass; the
quantity of potash is about fifty per cent. If green, or yellow,
the colour is destroyed by the addition of black oxide of
manganese; and hence that oxide is named glass makers'
soap.
The common plate glass, for electrical machines, &c. is
formed of sand, crude soda, old glass, and oxide of manganese.
The bottle glass, made with the soda of marine plants,
consists of sand, soda, common ashes, and old glass. Another
bottle glass is made by melting common sand, black or yellow,
with soda, wood-ashes, clay, and broken glass. It appears
from the use of the substances which enter into, and
compose, glass, that its quality is owing to the materials employed.
The crystal or flint glass is a finer kind. The substances,
with the proportions in which they are used, are the
following:
| | | Parts. |
| White sand, | 100 |
| Red lead, | 80 | to 85 |
| Calcined potash (pearl-ash,) | 35 | to 40 |
| Refined nitre, | 2 | to 3 |
| Black manganese, | 0.06 |
To this composition, there are sometimes added: |
| | Parts. |
| White arsenic, | 0.05 | to 0.1 |
| Crude antimony, | 0.05 | to 0.1 |
The specific gravity of this glass is 3.2. Goblets, lustres, &c. are made of it. |
Flint glass, according to the English formula, is made of |
| Purified Lynn sand | 100 | parts. |
| Litharge or red lead | 60 |
| Purified pearlash | 30 |
To this is added black manganese, to correct the colour, and sometimes nitre and arsenic. |
Plate glass is formed of |
| Pure sand, | 43.0 | parts. |
| Dry carbonate of soda, | 26.5 |
| Pure quicklime, | 4.0 |
| Nitre, | 1.5 |
| Broken plate glass, | 25.0 |
| | ——— |
| | 100. |
Crown, or fine window glass, is composed of |
| Fine sand, | 200 | lbs. |
| Best kelp, ground, | 330 | lbs. |
To this is added, if the vitrification is not complete, some
muriate of soda. Good glass, according to Pajot des
Charmes, may be made by fusing equal parts of carbonate of
lime, sand, and sulphate of soda. The glass is clear, solid,
and of a pale yellow. Professor Scheweigger found, that the
following proportions were the best:
| | Sand, | 100 |
| Dry sulphate of soda, | 50 |
| Dry quicklime in powder, | 17 | to 20 |
| Charcoal, | 4 |
Broad glass is made of a mixture of soap-boilers' waste,
kelp, and sand. Two of waste, one of kelp, and one of sand
are the proportions generally employed. Common bottle
glass is usually made of waste and river sand, to which lime,
and clay, and common salt are occasionally added.
The coloured glasses are produced by various metallic
oxides. The colour and beauty of precious stones are thus
imitated. These colours are communicated by sundry metallic
preparations, as the following: The purple powder of
Cassius, with oxide of manganese, will give a red or purple
according to the proportions used; zaffre, an oxide of cobalt,
a blue; a mixture of oxide of cobalt, muriate of silver, or glass
of antimony, a green; and oxide of manganese, a violet, &c.
The basis of all artificial precious stones, is composed of
what is called glass-paste, a compound of silica, potash,
borax, red lead, and sometimes arsenic. These substances
are melted together. The glass, which forms the body of
the artificial gem, is pulverized, and the colouring substances
are blended with it by sifting; and then the whole must
be carefully fused, being left on the fire for from 24 to 30
hours, and cooled very slowly. The following proportions
are used for this purpose:
| Pastes. | 1. | 2. | 3. | 4. |
| Rock crystal, | 4056 | gr. —— | 3456 | 360 |
| Minium, | 6300 | —— | 5328 | —— |
| Potash, | 2154 | 1260 | 1944 | 1260 |
| Borax, | 276 | 360 | 216 | 360 |
| Arsenic, | 12 | 12 | 6 | —— |
| Ceruse of clichy, | — | 8508 | —— | 8508 |
| Sand, | — | 3600 | —— | —— |
| Topaz. | No. 1, | No. 2. |
| Very white paste, | 1008 | 3456 |
| Glass of antimony, | 43 | —— |
| Cassius purple, | 1 | —— |
| Peroxide of iron, (saffron of Mars,) | — | 36. |
Ruby. Paste 2880, oxide of manganese 72.
Emerald. Paste 4608, green oxide of copper 42, oxide of
chrome 2.
Sapphire. Paste 4608, oxide of cobalt 68, fused for 30
hours.
Amethyst. Paste 4608, oxide of manganese 36, oxide of
cobalt 24, purple of Cassius 1.
Beryl. Paste 3456, glass of antimony 24, oxide of cobalt
11/2.
Styrian garnet, or ancient carbuncle. Paste 512, glass of
antimony 256, Cassius purple 2, oxide of manganese 2.
The following recipes are given by M. Lancon:
Paste. Litharge 100, white sand 75, potash 10.
Emerald. Paste 9216, acetate of copper 72, peroxide of
iron 1.5.
Amethyst. Paste 9216, oxide of manganese from 15 to 24,
oxide of cobalt 1.
The ancient coloured glass has been much admired. The
art was carried to a very great extent. Even in Pliny's time,
the highest price was set upon glass entirely free from colour.
He, as well as others, mentions that hyacinths and
sapphires were imitated very exactly.
The emperor Adrian received as a present from an
Egyptian priest, several glass cups richly ornamented with
various coloured glass. Seneca speaks of the knowledge of
Democritus in this art. Porta, Neri, and others, in modern
times, have treated the subject in a more enlarged manner.
Coloured glass was used for ornament; but Pollio relates,
that Gallenius punished an impostor for selling to his wife
a piece of glass for a jewel. In the Museum Victorium at
Rome, are several ancient artificial gems, such as the chrysolite
and emerald. What materials the ancients used for colouring
glass is not known. Gmelin, however, observes,
that it is probable they made use of iron, by which, he
adds, not only all the shades of red, violet and yellow, but even
a blue colour might be communicated. Cassius discovered
the powder which bears his name. He was a physician, and
resided at Lubec.[22] This powder was employed by the German
artists. While noticing this subject, it may be proper
to state, that Libavius (Alchemy, 1606,) gives a process for
making ruby glass. Neri, (ars vitraria by Kunkel,) was
acquainted with the gold-purple and its use. Glauber (Furnus
Philosophicus, 1648) mentions the use, and gives the preparation
of the powder. Kunkel made artificial rubies in
great abundance, and a cup of ruby glass for the elector of
Cologne. In 1679, he was inspector of the glass houses at
Potsdam; and, in perfecting the art, he expended 1600
ducats, which the elector of Brandenburgh gave him for the
purpose.
M. Brongniart has lately made many experiments on the
subject of staining glass. The colours, however, are the same
as we noticed. A green glass may be made by putting on
one side of the glass a blue, and on the other a yellow. A
black glass may be made by a mixture of blue with the oxides
of manganese and iron. Painting on glass is an ancient
art. When pieces of old painted glass are examined, they
have always on one side a transparent red varnish burnt into
them. The moderns, however, excel in this art.
Glass is not acted upon by the acids, except the fluoric or
hydrofluoric. Hence the acid of Derbyshire spar, which is
a fluate of lime, is used for etching on glass, in the same
manner as nitric acid is, on copper. Fluoric acid, a compound
of fluorine and hydrogen, is decomposed during this
action, and is changed, by the union of its fluorine with silicon,
into the silicated fluoric acid.
When a quantity of alkali is used just sufficient to fuse
silica, glass is the result; but when the quantity is greater, as
three or four to one, the fused mass is soluble in water, and
then forms the silicated alkali, or liquor of flints. From
this the silica is obtained in a pure state, by the addition of
an acid.
Glass, when melted and dropped into water, assumes an
oval form, with a slender projection, called a tail. This is
called Prince Rupert's drop. If a small part of this tail be
broken off, the whole bursts into powder, with a kind of explosion.
The Bologna, or philosophical phial, is a small
cylindrical vessel of glass, rounded at the bottom, but open
at the upper end. It is made thick at the bottom, so as not
to be easily broken; but if a pebble be dropped into it, it immediately
cracks, and the whole falls into pieces. In both
these, (the drop and the bottle,) the glass is unannealed.
When the external part of glass is suddenly cooled, the inner
part is kept, as it were, contracted. Now annealing, the process
of tempering glass in an oven, renders the glass uniformly
alike, and capable of sustaining the variations of
temperature, without breaking. By a crack or fissure,
the internal parts which remained in a state of tension, endeavour
to recover the full state of expansion, and consequently
the glass is rent asunder.
Sec. XLVIII. Glue and Isinglass.
Both glue and isinglass are animal products. They are used
in fire-works, but always in the state of solution, as vehicles
to mix up compositions in order to make them unite, and to
preserve them from falling to powder. The quantity, however,
is never large, or either would destroy the effect. The
proportions are generally prescribed. A solution of glue is
employed in the old process for refining saltpetre. See Nitre.
In making priming paste, isinglass dissolved in brandy is
sometimes used.
Glue and isinglass owe their adhesive quality to the presence
of gelatin; the most remarkable property of which is, that it
unites with, and precipitates the tanning principle from its
solution in water. For this reason, the use of oak bark and
other astringent substances, in the tanning of leather, is obvious,
the gelatin of the hide or skin, uniting with the tannin
and forming tanned leather. Gelatin exists in bones,
muscles, tendons, ligaments, membranes and skins. Skins,
especially those of old animals, furnish the best and strongest
glue.
For the preparation of glue, the parings and offals of
hides, pelts, and the hoofs and ears of horses, oxen, calves,
sheep, &c. are first digested in lime-water to clean them;
then steeped in fresh water, which is suffered to run off; and
being previously inclosed in a strong linen bag, are boiled in
a copper cauldron with pure water. The impurities are removed
as they rise. To the solution, alum, or finely powdered
lime, is added. It is then strained through baskets and
allowed to settle; after which, the clear fluid is again boiled.
When it becomes thick, or of a proper consistence, it is poured
into moulds or frames, when it concretes into jelly. It
is cut into pieces by a spade, and then into thin slices by
means of wire, and finally dried on coarse net-work.
The goodness of glue is known by its brittleness, and equal
degree of transparency, without black spots. It swells up in
cold water, and becomes gelatinous, but does not dissolve.
It is a mark of want of strength, when glue dissolves in cold
water.
Size is also a gelatinous substance, and is colourless and
transparent. Eel skins, vellum, parchment, &c. are used in
its preparation. They are treated in the same manner as
hides. Isinglass, or fish glue, is a finer kind of gelatin, obtained
from the air bladder and sounds of different kinds of
fish of the accipenser genus; as the sturio stellatus, huso ruthenses,
&c. The bladder, when taken from the fish, is
washed and stripped of its exterior membrane, and then cut
lengthwise and formed into rolls, or cut into strips. Isinglass
dissolves in water with more difficulty than glue. A
coarser kind of fish glue is made from sea wolves, porpoises,
sharks, cuttle fish, the sturgeon, &c. The head, tail, fins, &c.
are boiled in water, and the solution evaporated. Isinglass
is used for a variety of purposes, as the making of court
plaster and size, the clarification of liquors, &c.
Isinglass is almost wholly gelatin. One hundred grains
give ninety-eight of soluble matter.
Gelatin constitutes the greater part of the solid parts of
animals, such as bone, ligament, muscle, membrane, skin, &c.
and is always extracted by boiling them in water. We need
hardly remark, that it constitutes the chief part of soup,
which owes its nutritive qualities principally to its presence.
The portable soup is nothing more than concrete gelatin, with
other substances, as spices, salt, &c.; for it contains, in a
small compass, the nutritive parts of beef, veal, and other animal
substances, from which it may have been prepared.
Besides the use of water for extracting, or otherwise separating,
the gelatin from bone, we may separate the phosphate
of lime entirely from the latter, (as these two substances constitute
the greater part of bone), by the action of dilute muriatic
acid, which will dissolve the phosphate of lime, and
leave the gelatin.
Sect. XLIX. Of Wood.
Of the kinds of wood, used for the preparation of coal, for
the purpose of gunpowder, those should be preferred, which
are light, and will give a tender charcoal. This subject was
fully considered under that head.
But our intention, in noticing wood at this time, is, that it
is employed in the composition of some fire-works in the
form of saw-dusts, or raspings. Its use in fire-works may be
considered, 1st, as producing a particular coloured flame:
2dly, as varying the character of the flame, and likewise the
degree of the combustion; and 3dly, as communicating an
agreeable odour along with other substances; as in odoriferous
fire-works. To this, we may add its use in smoke-balls
along with nitre and sulphur.
The raspings of wood are sometimes required to be extremely
fine. This can only be done by employing sieves of
different degrees of fineness. They should be preserved from
the action of moisture.
In the composition of the new priming powder, of which
chlorate of potassa is the basis, very fine raspings of a particular
kind of wood are employed. So is also lycopodium for
the same purpose.
By the distillation of wood, as in the process of carbonization
in iron cylinders, we obtain some volatile products,
the chief of which is the pyroligneous, now called the pyroacetic
acid, while the ligneous fibre is converted into coal;
but, in the combustion of wood, all the volatile products are
expelled, some being consumed in the flame, and others,
with some carbon, condensed in the form of soot, while the
residue is an ash which furnishes common potash.
Ovid in his Metamorphoses, fable xvi, says—"Adomitis
Athamanis aquis accendere lignum narratur; minimos
cum luna recessit in orbes." This idea we know is groundless;
for it is impossible, that wood, sprinkled with water,
whether the waters of Athamanis, or any other, should be
kindled when the moon is in the decrease, or at any time of
the moon's age.
To prevent the action of fire on wood, marine salt, vitriol,
and alum have all been used. Various ways of employing
them have been adopted; but they do not absolutely prevent
wood taking fire in an active heat. For the same purpose,
(Coll. Academ. tome xi, p. 487,) a mixture of green vitriol,
and quicklime is recommended, by which we form sulphate
of lime and oxide of iron. The Journal de Paris of 1781 contains
various processes. At Vienna, saline substances are
employed.
The combustion of wood is the same, in all cases, in
which oxygen is concerned; but the products in some particulars
may vary. Hence saw-dust, when mixed with nitrate
of potassa, and inflamed, will burn, and produce little
or no smoke, because the combustion is rapid and perfect;
but when employed with sulphur and nitre, it produces much
smoke. Here the oxygen is furnished by the nitre, and
carbonic acid gas is formed. The same thing takes place,
when a mixture of saw-dust and nitre is used in artificial
fire; and, according as the decomposition is more or less
rapid, the combustion will be so likewise. The particular
applications of saw-dust will be noticed hereafter.
With respect to lycopodium or puff ball and various species
of agaric, or the medullary excrescences of trees, which
are used in some preparations of artificial fire, we may observe,
that the first is confined principally to theatrical
fire-works, and the second to the preparation of spunk, or
tinder, called also pyrotechnical sponge. See Pyrotechnical
Sponge.
As to the substance usually called lightning wood, found
in the hollow of the stumps of trees, and sometimes on the
surface, which, from having lost its compactness and other
characters of ligneous fibre, is called rotten wood, it is in
fact the solid part of the wood in a state of decomposition,
in consequence of which, it becomes a solar phosphorus. It
appears to owe its phosphorescent property, i. e. its power
of shining in the dark, to the previous absorption of light,
and not, as some have suggested, to the presence of phosphorus,
or the emission of any gaseous compound, which
contains it. The process of animal putrefaction will produce
such appearances, but, in this case, the cause is different.
Turf or peat, a substance found, and employed as fuel, in
some countries, and found in boggy situations, is partially
decomposed vegetable matter, consisting of a congeries of
fibres or roots. But black mould is the result of a decomposition
of vegetable substances, in which the ligneous
fibre is carbonized, and mixed with earth. The formation
of mould, however, is owing more to the decay of leaves
&c. (See Coal.)
Dr. Shaw (Travels to the Holy Land) observes, that when
they were either to boil or bake, camel's dung was their common
fuel; which, after being exposed a day or two in the
sun, catches fire like touch-wood; and burns as light as
charcoal.
Sec. L. Of Linseed Oil.
Linseed, or flaxseed, oil is obtained by expression from
flaxseed. It is a thick mucilaginous oil, when first extracted,
called raw oil, and in this state, is seldom used. The preparation,
it undergoes before it is used as drying oil for mixing
with paints, is nothing more than boiling it with litharge, or
some oxide of lead, which separates the mucilage, and unites
with the oil. By this treatment, it acquires the property of
drying with facility, when exposed to the atmosphere.
Linseed oil unites with great ease with oils, tallow, fat,
wax, &c. Some of these compositions are used in fire-works.
A preparation of pitch, mutton suet, and linseed oil is used,
for instance, in preventing the access of moisture to fuses;
and in military fire-works, it is employed in combination
with pitch, rosin, mutton suet and turpentine for incendiary
works. Wax, and tallow, we may here add, are also used
in the preparations of similar works.
Sec. LI. Of Gum arabic, and Gum Tragacanth.
Gum arabic, which exudes from a tree that grows in
Egypt and Arabia (Mimosa nilotica) when pure is transparent,
and nearly colourless. There are several varieties of this
gum; the gum senegal, for instance, which is of a reddish
colour, and occurs in larger pieces. Other mucilaginous
substances, the peach tree gum, the cherry tree gum, &c.
which exist only in small quantities, are analogous to the
gum of the Mimosa.
Gum arabic is brittle, and for that reason may be easily
reduced to powder. It is readily dissolved in water, with
which it forms mucilage. In this state, it is employed in
fire-works, chiefly as a vehicle for the mixing of pastes,
matches, &c.
Gum is a vegetable oxide, composed of carbon, hydrogen,
and oxygen. It does not crystallize. It is precipitated by some
metallic salts, as acetate of lead. It is insoluble in alcohol,
which distinguishes it from resins. Nitric acid decomposes
it, and changes it into the saclactic or mucous acid. With
sugar, the same acid produces oxalic acid.
Gum tragacanth, or gum dragon, is the produce of a thorny
shrub, which grows in Candia, and other islands of the
Levant, called astragalus tragacantha. The gum obtained
from this shrub has many properties in common with gum
arabic, and is, therefore, used as a paste. It dissolves readily
in boiling water; but is insoluble in alcohol, or ether.
It consists, almost entirely, of a peculiar vegetable principle,
which is called cerasin by Dr. John. Cerasin has the adhesive
qualities of gum arabic, but in a greater degree. It is
said to constitute a part of the gummy matter, that exudes
from the prunus cerasus, prunus avies, prunus domestica, &c.
Sec. LII. Of Cotton.
The soft down, which envelopes the seeds of different species
of gossypium, or cotton plant, is the cotton of commerce.
These plants are natives of warm climates. Cotton when
bleached is perfectly white. It is extremely combustible, and
burns with a clear lively flame. The ashes left behind contain
potash.
Cotton is the substance, usually employed in making match
rope, for the communication of fire. It has also other uses
in pyrotechny. Cotton match is much used in fire-works for
exhibition, not only for single cases, but also for a series of
cases of artificial fire, either for fixed or moveable pieces; and
serves to communicate fire, either singly, or from one case to
another, or to the whole piece at one time. Matches, so
used, are called leaders, and are generally confined in paper
tubes.
Cotton is one of the best applications to recent burns. Applied
to the part, it will, in a surprising manner, abate the
violence of the pain, and remove the inflammation.
Cotton is soluble in alkaline ley. For some of the earths,
it has a strong affinity, particularly alumina; as also for several
metallic oxides, and tannin. The action of mordants, in
dying of cotton-goods, depends on these affinities. Nitric
acid converts it into oxalic acid.
Cotton wick for lamps, candles, &c. is rendered very inflammable
by spirit of turpentine. By dipping the end of the
wick in turpentine, the candle will inflame at once, the moment
flame is applied. For candle-making, the wick is
sometimes dipped in a solution of camphor in spirits, or in a
melted mixture of camphor and wax. See Candle.
Sec. LIII. Of Bone and Ivory.
Bone, which is considered to be a combination of phosphate
of lime, gelatinous matter, animal oil, &c. is used occasionally
in fire-works. By destructive distillation, bones,
or osseous matter, afford ammonia, Dippel's animal oil, &c.;
and, when consumed by fire, leave a white ash, which is composed
principally of phosphate of lime. Bone-ash is the result
of the combustion of bone; for, while all the gelatinous
substance, oil, &c. are burnt off, that, which composes
the basis of bone, and which distinguishes it from gristle,
remains in the form of ash. Bone-ash furnishes phosphorus
by a certain process. See Phosphorus. Diluted muriatic
acid will take up the phosphate of lime of bone and leave
the gelatin. This mode is recommended for the separation
of gelatin from bone.
Bones, when carbonized in the same manner as wood,
furnish what is called bone-black, but commonly known by
the name of ivory-black. It is nothing more than animal
charcoal.
In Pyrotechny, bone, in the form of raspings, is employed
to communicate a lustre to the flame of gunpowder; but, for
this purpose, the most compact, and that, which contains the
least gelatin, is usually employed. Hence ivory is preferred.
Ivory, in the form of raspings, communicates to flame a
bright silver colour; and, on that account, is preferred to all
other kinds of bone. The compositions, into which it enters,
will be mentioned in a subsequent part of the work.
Ivory is the tusk, or tooth of defence, of the male elephant,
and is an intermediate substance between bone and
horn, not capable of being softened by fire. The finest and
whitest ivory comes from the island of Ceylon. The
tooth of the sea-horse is said to approach to ivory, properly
so called. It is, however, harder, and, for that reason, preferred
by dentists for making artificial teeth. The coal of
ivory is remarkably black; but the so called ivory-black, sold
in the shops, is nothing else than bone-black.
Bone and ivory may be stained of various colours. One
hundred parts of ivory contain,
| Gelatin, | 24 |
| Phosphate of lime, | 64 |
| Carbonate of lime, | 0.1 |
One hundred parts of ox-bone gave
| Gelatin, | 51 |
| Phosphate of lime, | 37.7 |
| Carbonate of lime, | 10 |
| Phosphate of magnesia, | 1.3 |
Berzelius, however, detected in bone-fluate of lime, muriate
of soda, and uncombined soda. Albumen is most generally
present. One hundred parts of bone are reduced by
calcination to sixty-three. One hundred parts of human
bone afforded Berzelius 81.9 phosphate of lime, 3 fluate of
lime, 10 lime, 1.1 phosphate of magnesia, 2 soda, and 2 carbonic
acid.
Sec. LIV. Of Galbanum.
Galbanum is a gum-resin, obtained from the bubon galbanum,
a plant peculiar to Africa. It is at first a juicy fluid,
which exudes when the plant is cut above the root, and hardens
by exposure to the air. Alcohol dissolves about three-fifths
of it. It contains some volatile oil.
The only instance we know of, in which galbanum has been
used in fire-works, is in the composition of rain-fire, employed
as an incendiary, before the present fire-stones were invented.
The rain-fire, which may be found in the fourth part
of this work, it is said, gave rise to the composition of fire-stone.
There is no advantage, however, in using galbanum for
this purpose; since pitch, tar, turpentine, and many other substances
are more inflammable, and, therefore, better adapted
for such compositions. We mention it merely because it
was one of the ingredients in that once celebrated incendiary
preparation, the fire-rain of Siemienowicz.
Sec. LV. Of Tow and Hemp.
In military fire-works, tow and hemp are much used, and
principally for the preparation of incendiary works. Both
tow and hemp are employed in forming match. Although
old rope, &c. are used for immersion in the tourteaux, carcass,
or fire-stone composition, which is readily imbibed, if
the rope is untwisted and beaten; yet tow or hemp is a better
material, and receives more of the composition. The manner
of using it may be seen by referring to the composition
for fire-stone. For very nice purposes, the tow or hemp
should be well dressed. Flax is, therefore, to be preferred
in such cases.
Sec. LVI. Of Blue Vitriol.
Different preparations of copper are used in fire-works, to
communicate colour to the flame; and besides copper filings,
brass filings, verdigris, and the oxides of copper, the sulphate
of copper, or blue vitriol, has been employed. We may
observe here, that there are three sub-species of this salt;
the bisulphate, sulphate, and sub-sulphate, the first properly
speaking being the blue vitriol of commerce.
The sulphate, although recommended in some of the old
formulæ for coloured fire, is not, however, preferable to some
other preparations of copper. The use and application of
copper, and its preparations, will be seen in the article on
coloured fire.
When sulphate of copper is heated, it is converted into a
bluish-white powder. If the heat be increased, the acid is
expelled, and the black oxide of copper remains. Before it
is used, it is exposed to heat to expel the water of crystallization.
It ought to be in the state of impalpable powder. It
is composed of 33 acid, 32 oxide, and 35 water. It is decomposed
by the alkalies and earths, the alkaline carbonates,
borates, and phosphates, and several metallic salts.
The oxide may be obtained very readily from this salt,
for the purpose of fire-works, by dissolving it in water, and
adding a solution of caustic potassa; collecting the precipitate,
and drying it in a moderate heat. This will expel the
water that may be contained in it; as metallic precipitates,
made in this way, are more or less in the state of hydrates.
When metallic copper is required, it may be obtained in
fine powder, and very expeditiously, by immersing a plate of
iron in a solution of any of the salts of copper, as the sulphate.
It will precipitate on the iron, and gradually fall to
the bottom of the vessel. This metallic copper will be found
to be much more impalpable than the filings, however fine,
and, for that reason, may be mixed more accurately with different
substances.
Copper burns with a beautiful green flame, and deposites
a loose greenish-gray oxide. The ammonia-oxalate of copper,
of which there are three sub-species, burns with flame.
Sec. LVII. Of Nitrate of Copper.
This preparation of copper is used in some fire-works. It
communicates a green colour to flame. When combined with
carbonaceous substances, the combustion is vivid. This is owing
to the decomposition of the nitric acid, (in the same manner
as the acid of nitrate of potassa and other nitrates is decomposed),
during which carbonic acid and deutoxide of azote
are produced. Nitrate of copper has been more particularly
recommended for the preparation of match stick, similar to
that of M. Cadet, and of match rope. It is used in the
same manner as the nitrate of lead. M. Proust used it in
lieu of nitrate of lead when repeating some experiments of
M. Born. It is more expensive than the acetate, or even the
nitrate of lead. Its effect, however, is the same.
Nitrate of copper attracts the moisture of the atmosphere,
and deliquesces. Acetate of lead, on the contrary, by exposure
to the air gradually effloresces, and in time is decomposed.
The preparations of lead, for that reason, are preferable
to the nitrate of copper.
Nitrate of copper is formed by dissolving copper in nitric
acid; and, when the acid is saturated, the requisite quantity
of water may be added. The salt may be obtained in a dry
state by evaporation; and, after being dissolved in water, the
wood or rope may be soaked in it.
Dry nitrate of copper, wrapped up in tin-foil, will produce
no action; but, if water be added, sufficient to moisten it, and
then the foil closed tightly, combustion will take place. The
water promotes chemical action by dissolving the nitrate of
copper, which is then decomposed by the tin, and the quantity
of caloric, put in a distributable state, is sufficient to inflame
the tin. The details of the rationale will be given
hereafter.
The ammonia-nitrate of copper is fulminating copper.
The chlorate of copper is a deflagrating salt. Ammonia
added to nitrate of copper, first separates an oxide, and then
dissolves it. It is more than probable, that nitrate of ammonia
causes the ammonia-nitrate to explode.
Sec. LVIII. Of Strontia.
The earth called strontia or strontian, is found abundantly
in different parts of the world, in combination with carbonic
and sulphuric acids. The carbonate of strontia or strontianite,
effervesces with acids, and burns with a purple flame.
It contains about 60 or 70 per cent. of earth. The sulphate
of strontia, or celestine, contains about 57 of strontia.
When carbonate of strontia is mixed with charcoal powder,
and exposed to a heat of 140° of Wedgwood's pyrometer,
the carbonic acid will be expelled, and pure strontia
remain. The earth may be obtained in a pure state, by dissolving
the carbonate in nitric acid, and evaporating the solution
until it crystallizes, and exposing the crystals, in a
crucible, to a red heat, until the nitric acid is driven off. If
the carbonate cannot be had, the sulphate may be employed.
For this purpose, it is to be pulverized and mixed with an
equal weight of carbonate of potassa, and boiled in water.
The carbonate of strontia, thus obtained, which exists in the
form of a powder, is to be treated with nitric acid as already
described.
Strontia, like the other earths, is a compound body, having
a metallic basis, called strontium, which, united with
oxygen, forms the earth.
The specific gravity of strontia approaches that of barytes.
Like pure barytes, it is soluble in water, forming strontia
water. It requires rather more than 160 parts of water at
60° to dissolve it; but much less of boiling water.
The solution of strontia in water, when evaporated, will
crystallize in thin, transparent, quadrangular plates, generally
parallelograms, seldom exceeding a quarter of an inch
in length. These crystals contain about 68 per cent. of water;
and are soluble in little more than twice their weight of
boiling water, and in 54.4 times their weight of water at 60°.
When dissolved in alcohol, they give a blood-red colour
to its flame. The solution of strontia changes vegetable
blues to green. Strontia differs from barytes in being infusible,
much less soluble, of a different form, weaker in its
affinities, and not poisonous.
The metallic base of strontia, which was discovered by Sir
H. Davy, in 1808, when exposed to the air, or when thrown
into water, rapidly absorbs oxygen, and is converted into
strontia.
As strontia communicates a red colour to flame, it has
been used in certain compositions of artificial fire. The brilliant
red fire, sometimes used in theatres, owes its colour to
this earth. See Theatrical fire-works. Muriate and nitrate
of strontia will give a red or purple colour to the flame of
alcohol. See coloured flame of alcohol.
If a piece of cloth be dipped in a solution of muriate, nitrate,
or acetate of strontia, or in strontia water, and then
immersed in alcohol, it will burn with a red flame.
M. Fourcroy, (Système des Connaissances Chimiques, &c.
tome iii,) mentions the use of nitrate and muriate of strontia,
in artificial fire-works, for the purpose of communicating a
red colour to the flame of combustible bodies. Since that
time, the nitrate, in particular, has been recommended and
used.
One of the characters of the salts of strontia, is, that they
give a red flame to burning bodies; whereas the salts of
barytes or of lime, used in the same manner, communicate
a yellow flame.
The saline combinations of strontia were examined with
particular attention by Dr. Hope. See Edinburg Philosoph.
Transactions for 1790.
Nitrate of strontia may be formed by dissolving carbonate
of strontia, or the sulphuret obtained by decomposing the
sulphate by charcoal, in nitric acid, filtering the solution,
evaporating it, and suffering it to crystallize.
Nitrate of strontia deflagrates on ignited coals. Dr. Hope
pointed out, that if nitrate of strontia be exposed to a red heat,
and a combustible substance be, at this time, brought in contact
with it, a deflagration, with a very vivid red flame, will
be produced. When a crystal of this salt is put into the wick
of a candle, it communicates a beautiful purple flame. It does
not deliquesce in the air, and, therefore, the compositions,
into which it enters, cannot spoil on that account. Nicholson
(Chemical Dictionary,) observes, that nitrate of strontia may
be used in the art of pyrotechny. For this purpose, however,
it is mixed with sulphur, chlorate of potassa, and sulphuret of
antimony; and sometimes with the addition of sulphuret of
arsenic and charcoal, as in the red fire for theatrical uses.
The muriate of strontia has similar properties. Davy first
observed, that when strontia was heated in chlorine gas, it
gave out oxygen gas, and a chloride of strontium was
formed.
Muriate of strontia is formed very readily, by dissolving
the carbonate or sulphuret of strontia in muriatic acid,
and evaporating the solution in order to obtain crystals.
These crystals are very soluble in water. They are soluble,
also, in twenty-four times their weight of pure alcohol, at the
temperature of 60°. This alcoholic solution, we remarked,
burns with a fine purple colour. These crystals suffer no
change when exposed to the air, except they be very moist;
in which case, they deliquesce. When heated, they first undergo
the watery fusion, and are then reduced to a white
powder. Fourcroy recommends the muriate of strontia for
fire-works.
Carbonate of strontia, when thrown in powder on burning
coals, produces red sparks.
Acetate of strontia, another salt used in fire-works, is
formed by dissolving strontia, or its carbonate, in acetic
acid. It will crystallize. The crystals are not affected by
exposure to the air. When heated, its acid is decomposed,
as happens to all the other acetates.
Sec. LIX. Of Boracic Acid.
Borate of soda, or borax, is a salt, which has long been
known, and is used chiefly in the arts as a flux for the fusion
of bodies, and for soldering. Boracic acid is a compound
body, consisting of a newly discovered substance, called boron,
and oxygen. Homberg obtained the acid from borax in
1702, by distilling a mixture of borax, and sulphate of iron.
He supposed that it was a product of the latter; and hence it
was called the volatile narcotic salt of vitriol, or sedative
salt.
Boracic acid forms two salts with soda; the borate, properly
so called, and borax. It is supposed to be our borax,
that Pliny mentions under the name crysocolla, so called by
the ancients. Others, however, assert, that their crysocolla
was nothing more than the rust of copper, triturated with
urine. The impure borax in the East Indies, is called tincal.
When borax is melted, and exposed for some time to
heat, it loses its water, and is changed into what is known by
the name of calcined borax.
The easiest process for obtaining boracic acid is to make
a concentrated solution of borax in hot water, and add by degrees,
sulphuric acid, which will unite with the soda; and, as
the fluid cools, the boracic acid will separate in shining laminated
crystals. No more acid should be added than is
sufficient to make the solution slightly sour. The crystals
are to be washed with cold water, and drained upon brown
paper.
One of the principal characters of boracic acid is, that it
is very soluble in alcohol, to the flame of which it communicates
a green colour. Paper dipped in this solution, burns
in the same manner.
In consequence of this property of imparting a green colour
to flame, I made some experiments with it, for the purpose
of preparing green fire; and found, that, by employing
it in the proportion of one-eighth, the flame was always
green, provided that the flame of the combustible used, was
not tinged of any other colour. Nitre, charcoal, and boracic
acid will give a green; also nitre, lamp oil, and boracic
acid; nitre, alcohol, and boracic acid, along with charcoal;
and chlorate of potassa, charcoal, and boracic acid, with or
without the addition of alcohol. But, although boracic acid
communicates a lively green, its expense will prevent its use
in that way, especially as many other preparations, as those
of copper, will have the same effect, and are more economical
on account of their price. See the Coloured Flame of Alcohol,
and Coloured Fire.
Oils, when assisted by heat, will dissolve boracic acid. In
naphtha, it is very soluble. With oils, it yields fluid and solid
products, which give a green colour to the flame of alcohol.
It is not a combustible acid, but only imparts colour
to the flame of combustible bodies.
Boron will unite with fluorine, the radical of fluoric acid.
When one part of vitrified boracic acid, two of fluate of
lime or fluor spar, and twelve of sulphuric acid are distilled,
an acid gas will be obtained, called fluo-boric gas. For the
properties of boron, consult Thenard's Traité de Chimie.
INSTRUMENTS, TOOLS, AND UTENSILS.
OF THE LABORATORY.
The laboratory for pyrotechny may consist of a building,
furnished with furnaces, boilers, &c. for the preparation or
refining of saltpetre, and other substances for use; but according
to its present acceptation, it is a place where all
kinds of fire-works are prepared, both for actual service and
for exhibition; such as, besides the ordinary works for show,
quick matches, fuses, port-fire, grape-shot, case-shot, carcasses,
hand granades, cartridges, &c. It should have tables,
benches, and closets, where the tools, paper, thread, &c. may
be commodiously placed, and an adjoining room to contain a
supply of materials for two days' work.
The chief artificer takes the weight of the materials made
use of, attends to the weighing of the different substances, and
sees that the mixtures are made properly, &c. He also keeps
an account of the number and kinds of fire-works. The prepared
fire-works ought to be removed daily to the magazine.
If they are made up in the field, under a tent, (denominated
the Laboratory tent,) they should be packed in barrels or in
caissons.
Sec. I. Of Laboratory Tools and Utensils.
The following constitute the furniture and equipments of
a laboratory:
- Copper rods, to load port fires, and the fuses of shells, howitzers, &c.
- Wooden formers, on which to roll the paper cases of the port fires.
- Wooden formers, to roll the cases of rockets.
- Balances, large and small, with weights, &c.
- Buckets to carry water.
- Boxes for loading priming tubes.
- Barrels with leather tops, that draw, in order to keep grained and meal gunpowder.
- Rods, or rammers for charging rockets.
-
Brushes to wipe the tables and sweep the compositions together.
- Frames to dry priming tubes.
- Copper calibers to regulate the size of priming tubes.
- Penknives.
- Needles for piercing priming tubes in the direction of their length.
- Fuse drivers.
- Coopers' adzes.
- A copper kettle.
- Scissors for cloth and paper.
- Paper cutters.
- Priming wires.
- Skimmers for skimming the froth of boiling saltpetre.
- Funnels for charging port-fires, howitzers, shells, &c.
- Square ruler.
- Fuses for shells, &c. (or a lathe to make them.)
- Large and small wooden bowls.
- Small axes.
- Ladles for charging the fuses of shells, port-fires, &c.
- Mallets to hammer the fuses.
- Glue pots and brushes.
- Heavy mallets to beat the powder.
- Tin measures, of different sizes.
- Hand mortar.
- Foot rules.
- Rat-tail files to cleanse the interior of the reeds of priming tubes.
- Wooden rasps.
- Iron rulers, 1/2 foot long.
- Leather bags, in which gunpowder and charcoal are reduced to powder.
- Pocket saws.
- Pallet knives for saltpetre.
- Tables, small ones to mix the composition; large ones with a ledge to meal the powder on.
- Sieves, fine and common; of silk, and of hair.
- Fuse drawers.
- Tools for rolling cartridges.
- Gimblets of different sizes.
The materials required more particularly for military fire-works,
are:
- Gunpowder.
- Saltpetre.
- Sulphur.
- Charcoal.
-
Camphor.
- Beeswax.
- Glue, rosin.
- Cotton yarn for quick match.
- Brandy or other spirits.
- Gum arabic.
- Linseed oil.
- Spirits of turpentine.
- Pitch.
- Reeds or quills for priming fuses.
- Mutton tallow.
- Vinegar.
- Thread for tying quick match.
- Cartridge paper.
- Thread, tow and spun yarn, to make match rope.
- Cordage, to make tourteaux.
- Flour to make paste.
The characters used to express certain substances employed
in fire-works, are the following: (James's Mil. Dict. p.
101.)
M. means meal powder,
⊝. Saltpetre.
C. Z. Crude sulphur.
C. S. Sea coal.
S. x Steel or iron filings.
G. x Glass dust.
C. I. Cast iron.
X. Camphor.
B. L. Lampblack.
L. S. Lapis Calaminaris.
W. Spirits of wine.
P. O. Oil of spike.
∋. Corn powder.
Z. Brimstone.
C. + Charcoal.
B. R. Beech raspings.
B. x Brass dust.
T. x Tanners' dust.
C. A. Crude antimony.
A. Y. Yellow amber.
G. I. Isinglass.
⩀. Gum.
S. T. Spirits of turpentine.
Sec. II. Of Mandrils and Cylinders for forming Cartridges
and Cases.
The rollers or rods, on which cartridges are formed, ought
to be solid, and perfectly straight and round. Very dry,
sound wood should be selected, and when turned, the rod
should be perfectly cylindrical; one extremity being concave,
and the other convex.
Mandrils may be made of copper, which is preferable to
wood, as this is apt to warp and crack; and in both cases,
should be longer than the cartridge, so as to be drawn out
easily. They are of different lengths and diameters, according
to their respective uses.
Sec. III. Of Rammers, Chargers, and Mallets.
The rammers which are used for compression, are cylindrical
like the preceding. They have a head much larger
in dimensions than the part that enters the tube. (See A, B,
C, D, and E of Fig. 1. in the Plate). Besides being made
of wood, which should be of the hardest kind, as lignum vitæ,
they may be formed of copper or brass. In this case, they
are first cast of the requisite size and shape, and finished in
a lathe. Wooden heads are sometimes put to them, but
with little advantage; as they frequently split and require to
be renewed.
The wooden rammer may be struck with metal; but when
the rammer is of copper or brass, wooden mallets must be
always employed.
We may here remark, that in charging rockets, it has
been customary to employ several rammers. The first drift
must be six diameters from the handle, and this, as well as
all other rammers, ought to be a little thinner than the former,
to prevent the tearing of the paper, when the charge is
driven in. In the end of this rammer is a hole to fit over
the piercer. (See B. Fig. 1.) The line marked on this
rammer, as will be explained hereafter, when it appears at
the top of the case, indicates that a second rammer must be
used. This second rammer, from the handle, is four diameters,
having a hole for the piercer, 11/2 diameters long. (C.
Fig. 1.) When the case is filled as high as the top of the
piercer, a short and solid drift is used. (E. Fig. 1.).
Rammers must have a ferrule, or collar of brass at the
bottom, to keep the wood from spreading, or splitting. With
regard to the handles of the rammers, if their diameter be
equal to the bore of the mould, and two diameters long, the
proportion is a good one. The shorter they can be used, the
better. The longer the drift, the less of course, will be the
pressure on the composition, by the blow given by the mallet.
We may observe here, that rockets may either be driven
over a piercer, or driven solid, and afterwards bored.
As much of the effect of rockets depends upon the manner
they are driven, whether lightly or compactly, or uniformly
throughout, circumstances which affect their quality; it is
necessary, in using the rammer, to employ an equal force
for driving the composition. The mallet, therefore, should
be of a given weight; and a certain number of strokes with
the same force, on each new charge, must be accurately followed,
until the driving is completed; taking care, at the
same time, that the rocket stands firm on a solid body.
Dry beech is the best wood for mallets. A writer very
judiciously observes, in the Encyclopedia Britannica, (vol. xv,
695), that, if a person uses a mallet of a moderate size, in
proportion to the rocket, according to his judgment, and if
the rocket succeeds, he may depend on the rest, by using the
same mallet; yet it will be necessary, that cases of different
sorts, be driven with mallets of different sizes. In all cases,
under one ounce, the charge may be rammed with an ounce
mallet.
There is an advantage, also, by having the handle of the
mallet turned out of the same piece as the head, and made
in a cylindrical form. If their dimensions are regulated
by the diameters of the rockets; then, for example, if the
thickness of the head be three diameters, and its length four,
the length of the handle will be five diameters, whose thickness
must be in proportion to the hand.
Bigot (Artifice de Guerre, p. 118) speaking of the flying
fuses, or sky-rockets, observes, that the mallet used for driving
the composition, is proportionably large, according to
the rockets, and that it is five inches in length, and four in
breadth, when the diameter of the rocket is from 12 to 18
lines. The mallets for larger rockets are stronger and heavier,
and, in some instances, where a great force is required, as in
driving war-rockets, a machine similar to the pile-engine, is
used. See Congreve Rockets.
Sec. IV. Of Utensils necessary for constructing of Signal
Rockets.
A detailed account of the tools used in making signal
rockets, may be seen in Ruggeri, Pyrotechny, p. 143; but
M. Bigot has enumerated them as follows:
- One mandril for forming the cartridge, or case.
- One pair of curved compasses to determine the exterior diameter.
- Three conical mandrils. (See fig. 3, plate.)
- One solid, or massive cylinder.
- One mould for garnishing.
- Two moulds for the capitals, or heads, one of which is for the rockets with, and the other for the rockets without, the garnish, or furniture.
- One piercer and block (See plate, fig. 1, I & H.)
-
One scoop.
- One punch.
- One mallet.
- One press.
- One large knife.
- One pair of scissors.
All the wooden utensils ought to be made of hard and
sound wood, without knots. The rammers should be furnished
with rings or ferrules, and the first bored with a hole
of sufficient length to receive the piercer. The second should
be bored deep enough to receive two-thirds of the piercer,
and the third, to receive one-third, while the fourth should
be solid. These rammers are all furnished with heads. (See
section iii.)
Sec. V. Of the Rolling, or Plane Board.
This board is furnished with a handle, and is used for
rolling rocket cases, &c. and is of different dimensions, according
to its application. It is made of hard wood, such as
oak or walnut.
When the paper is wrapped round the mandril or former,
the rolling board is used to compress the paper, and make it
round and smooth.
Sec. VI. Of the Driver for charging large Rockets.
This contrivance is similar to a pile driver in construction;
and, by means of a weight falling upon the rammer,
the charge is sent home with great force. Its use is confined
to the largest kind of rockets.
Sec. VII. Of Mortars and Pestles.
Mortars are employed for the pulverization of substances,
and, according to their use, may be either of wood, marble,
brass, or cast-iron, which last costs less than the others.
Large mortars have covers, in order to confine the finer particles.
The pestles should be of very hard wood; because,
in that case, no danger would be apprehended of an explosion
of the materials, an occurrence which might take place, if
iron were used. This, however, depends on the substances
submitted to the pestle.
Sec. VIII. Of the Choaker or Strangler.
The choaker is nothing more than a contrivance, usually
made of rope, by which the closing of the end of the rocket
is effected, so as to form a kind of cup or mouth.
Sec. IX. Of the Table and Sack for mealing Gunpowder.
This table may be either square or an octagon, and made of
hard wood. There is a rim, a few inches high, raised round
it, and a gutter at one end to allow the powder to pass out,
when the operation is finished. See plate, fig. 7 and 8.
This mode of mealing powder is by no means to be preferred.
(See Gunpowder.)
A sack is also used for crushing powder. It should be
made of strong elastic leather, and sewed together in such a
manner as to prevent the impalpable powder from passing
through its seams. They are of an oblong shape, and contain
from 20 to 25 pounds. Fifteen pounds are generally
put in at a time. This method of crushing powder is preferred,
as it is less liable to accidents. It is hardly necessary
to add, that the bag is beaten with a cylindrical stick.
Sec. X. Of Sieves.
There are several kinds of sieve. The common sieve
has neither a cover nor a receiver, and may be either formed
of horse hair, or of brass or copper wire. It is necessary
to have some sieves of a finer kind. For this purpose, silk
and gauze are generally used. The cover is merely leather,
fixed in a frame, which fits on the top. The receiver is
formed nearly in the same manner, having a skin stretched
over a frame, which fits on the under part of the sieve.
Sec. XI. Of the Paper Press.
A press, for the purpose of pressing paper, is formed of
two pieces of wood, which are brought together by means
of one, or several screws. This press is sometimes, though
seldom, used. If pasteboard is made, when it cannot be
had ready prepared, then the press is actually necessary.
The intention is to unite the several sheets, which have been
pasted, by using the pressure of the screw, and to remove any
extraneous paste, so that the paper may have no inequalities
on its surface. In lieu of the screw-press, heavy weights
laid on the paper for several hours, will answer the same
purpose.