Bromine and its Compounds—Iodine and its Compounds—Chlorine and its
compounds—Cyanide of Potassium—Hyposulphite of Soda—Hyposulphite of
Gold—Nitric Acid—Nitro-Muriatic Acid—Hydrochloric Acid—Hydrofluoric
Acid—Sulphuric Acid—Accelerating Substances—Liquid Sensitives—Dry
Sensitives, etc., etc.
An article so extensively used in the practice of the Daguerreotypic art
as Bromine, is deserving of especial attention, and accordingly every
person should endeavor to make himself familiar with its properties and
applications.
History.—This element was discovered in 1826 by M. Balard, in the
mother-liquor, or residue of the evaporation of sea-water. It is named
from its offensive odor (bromos, bad odor). In nature it is found in
sea-water combined with alkaline bases, and in the waters of many saline
springs and inland seas. The salt springs of Ohio abound in the compounds
of bromine, and it is found in the waters of the Dead Sea. The only use
which has been made of bromine in the arts is in the practice of
photography. It is also used in medicine In a chemical point of view it is
very interesting, from its similarity in properties, and the parallelism
of its compounds to chlorine and iodine.
Dr. D. Alter, of Freeport, Pa., is the only American manufacturer, and
furnishes all of the “American Bromine.” Yet we understand much purporting
to be of German manufacture is prepared from that made in Freeport. This
is done by individuals in this city, who get well paid for the deception.
For the successful application of bromine as an accelerating agent, we are
indebted to Mr. John Goddard of London, who at the time was associated
with Mr. John Johnson, now a resident of this city.
Preparation.—The mother-liquor containing bromides is treated with a
current of chlorine gas, which decomposes these salts, setting the bromine
free, which at once colors the liquid to a reddish brown color. Ether is
added and shaken with the liquid, until all the bromine is taken up by the
ether, which acquires a fine red color and separates from the saline
liquid.
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Solution of caustic potash is then added to the ethereal solution, forming
bromide of potassium and bromate of potash. This solution is evaporated to
dryness, and the salts being collected are heated in a glass retort with
sulphuric acid and a little oxide of manganese. The bromine is distilled,
and is condensed in a cooled receiver, into a red liquid.
Properties.—Bromine somewhat resembles chlorine in its odor, but is more
offensive. At common temperatures it is a very volatile liquid, of a deep
red color, and with a specific gravity of 3, being one of the heaviest
fluids known. Sulphuric acid floats on its surface, and is used to prevent
its escape. At zero it freezes into a brittle solid. A few drops in a
large flask will fill the whole vessel when slightly warmed, with blood
red vapors, which have a density of nearly 6.00, air being one. It is a
non-conductor of electricity, and suffers no change of properties from
heat, or any other of the imponderable agents. It dissolves slightly in
water, forming a bleaching solution.
Chloride of Bromine.—This as an accelerating agent is by many considered
superior {75} to the other Bromide combinations. It can be readily
prepared by passing a current of chlorine through a vessel containing
bromine. A mixture of two parts muriatic acid and one of black oxide of
manganese, should be put into a flask having a bent tube to conduct the
chlorine vapor into the bromine in another vessel. This last vessel should
also be supplied with a bent tube for conducting the combined vapors with
a third vessel or receiver. On the application of the heat from a spirit
lamp to the bottom of the flask, a current of chlorine gas will be
disengaged, and pass into the bromine, when it readily combines, and gives
off a vapor, which, when condensed in the third vessel, forms a volatile
yellowish-red liquid. It is best, even at ordinary temperature, to place
the receiver in an ice bath. For manner of using, see farther on, under
head of Accelerators.
Bromides.—A bromide treated with oil of vitriol, disengages chlorohyadic
acid; but vapors of bromine are constantly disengaged, at the same time
imparting a brown color to the gas. If the bromide be treated with a
mixture of sulphuric acid, and peroxide of manganese, bromide is only
disengaged. A solution of a bromide gives, with of nitrate {76} silver, a
light yellowish white precipitate of bromide of silver, which is insoluble
in an excess of acid, and readily dissolves in ammonia. The precipitated
bromide is colored by light like the chloride, but is immediately tinged
brown, while the chloride assumes at first a violet hue. The bromides, in
solution, are readily decomposed and chloride being set free, colors the
liquid brown.
In the whole range of heliographic chemicals there is probably not another
collection less understood and being so productive of interesting
investigation as the bromides.
Bromide of Iodine.—M. de Valicours furnishes us with the best method for
preparing this mixture:
“Into a bottle of the capacity of about two ounces, pour thirty or forty
drops of bromine, the precise quantity not being of importance. Then add,
grain by grain, as much iodine as the bromine will dissolve till quite
saturated. This point is ascertained when some grains of the iodine remain
undissolved. They may remain in the bottle, as they will not interfere
with the success of the preparation.
“The bromide of iodine thus prepared, from its occupying so small a space,
can very easily be carried, but in this state it is much too concentrated
to be used. When it is to be employed, pour a small quantity, say fifteen
drops, by means of a dropping-tube, into a bottle containing about half an
ounce of filtered river water. It will easily be understood that the
bromide of iodine can be used with a greater or less quantity of water
without altering the proportion which exists between the bromine and
iodine.”
This article forms a very good dry accelerator, and is by some persons
thought superior to all others, as it works with great uniformity, and is
less liable to scum the plate in coating at high temperatures, or when the
thermometer indicates a heat above 60 deg.
Bromide of Potassium—Is prepared by mixing bromine and a solution of pure
potass together, and evaporating to dryness; it crystallizes in small
cubes, and dissolves readily in water. This agent is extensively employed
in the paper and glass processes.
Bromide of Lime. This the principal accelerator used in the American
practice, and is the best of all dry combinations at present employed.
There are many reasons why the dry is advantageous; these are too familiar
to repeat.
“The bromide of lime may be produced by allowing bromine vapor to act upon
hydrate of lime for some hours. The most convenient method of doing this
is to place some of the hydrate at the bottom of the flask, and then put
some bromine into a glass capsule supported a little above the lime. As
heat is developed during the combination, it is better to place the lower
part of the flask in water at the temperature of about 50 deg. Fah.; the
lime gradually assumes a beautiful scarlet color, and acquires an
appearance very similar to that of the red iodide of mercury. The
chloro-iodide of lime may be formed in the same manner; it has a deep
brown color. Both these compounds, when the vapor arising from them is not
too intense, have an odor analogous to that of bleaching powder, and quite
distinguishable from chlorine, bromine, or iodine alone.”
Farther on, I have given, in connection with accelerators, a process I
adopt, which is far less tedious and equally reliable.
Bromide of Silver—May be formed by pouring an alkaline bromide into a
solution of nitrate of silver, in the shape of a white, slightly yellowish
precipitate, which is insoluble in water and nitric acid, but readily
dissolves in ammonia and the alkaline hyposulphites. Chlorine easily
decomposes bromide of silver, and transforms it into chloride.
M. Biot has expressed his opinion, that it is not possible to find any
substance more sensitive to light than the bromide of silver. This is true
to a certain extent, but in combination with deoxidizing agents, other
preparations have a decided superiority over the pure bromide of silver.
Bromide of Gold—Is readily prepared by adding a little bromide to the
brown gold of the assayers, and allowing it to remain some time under
water, or assisting its action by a gentle heat. It forms a salt of a
bright crimson color, but in its general properties is precisely similar
to the chloride used in gilding.
Bromide of Magnesia—Is prepared in the same manner as bromide of lime.
This mixture is particularly adapted for hot climates, and is used in this
country by some few who regard its use as a valuable secret.
Bromide of Starch.—This preparation is much used, but not alone. It is
combined with lime by putting about one part in measure of starch to four
of lime. It is prepared by adding bromine to finely pulverized starch, in
the same manner as bromide of lime. (See Accelerators.)
Experiments with Bromine.—Place in a very flaring wine glass a few drops
(say ten) of bromine, then place a small piece of phosphorus about
one-twentieth of an inch in diameter. Place the latter on the end of a
stick from five to ten feet in length. So place it that the phosphorus can
be dropped into the glass, and in an instant combustion giving a loud
report will be the result.
b. Expose a daguerreotype plate to the vapor of bromine, it assumes a
leaden-grey color, which, blackens by light very readily. Exposing this to
mercury will not produce any decided action upon the lights. Immerse it in
the solution of the muriate of soda, and the parts unacted upon by light
becomes a jet black, while the parts on which the light has acted will be
dissolved off, leaving a clean coating of silver. This will be a most
decided black picture on a white ground.
c. Expose an impressioned plate, that has been sufficient time in the
camera to become solarized, to the vapors of bromine, and the impression
will be fully developed and exhibit no signs of solarization. The exposure
over the bromine most be very brief. Chlorine or iodine will produce the
same result. The latter is preferable.
Again, should the impressioned plate be exposed too long over the vapor of
bromine, the impression would be rendered wholly insensitive to the
mercurial vapor. Hence this method is resorted to for restoring the
sensibility of the plate when there is reason to believe that the
impression would not be a desirable one; as, for example, if a likeness of
a child be wanted, and it had moved before the plate had been sufficiently
long exposed in the camera, the plate may be restored to its original
sensitiveness by re-coating over bromine, as above, thus saving the time
and labor of re-preparing the plate for the chemicals.
d. If by accident (we would not advise a trial to any extent of this), you
should inhale a quantity of the vapor of bromine, immediately inhale the
vapor of aqua ammonia, as this neutralizes the dangerous effect of the
bromine vapor. Every operator should be provided with a bottle of ammonia,
as a little sprinkled about the chemical room soon disinfects it of all
iodine or bromine vapor, and also tends to facilitate the operation in the
camera.
History of Iodine.—This is one of the simple chemical bodies which was
discovered in 1812 by M. Courtois, of Paris, a manufacturer of saltpetre,
who found it in the mother-water of that salt. Its properties were first
studied into by M. Gay Lussac. It partakes much of the nature of chlorine
and bromine. Its affinity for other substances is so powerful as to
prevent it from existing in an isolated state. It occurs combined with
potassium and sodium in many mineral waters, such as the brine spring of
Ashby-de-la-Zouche, and other strongly saline springs. This combination
exists sparingly in sea-water, abundantly in many species of fucus or
sea-weed, and in the kelp made from them. It is an ingredient in the Salt
Licks, saline, and brine springs of this country, especially of those in
the valley of the Mississippi. It is sparingly found in fresh-water
plants, as well also in coal, and in combination with numerous other
bodies.
Fermented liquors contain iodine; wine, cider, and perry are more
iodureted than the average of fresh waters. Milk is richer in iodine than
wine; independently of the soil, with which it varies, the proportion of
iodine in milk is in the inverse ratio of the abundance of that secretion.
Eggs (not the shell) contain much iodine. A fowl’s egg weighing 50 gr.
contains more iodine than a quart of cow’s milk. Iodine exists in arable
land. It is abundant in sulphur, iron, and manganese ores, and sulphuret
of mercury: but rare in gypsum, chalk, calcareous and silicious earths.
Any attempt to extract iodine economically should be made with the plants
of the ferro-iodureted fresh waters. Most of the bodies regarded by the
therapeutists as pectoral and anti-scrofulous are rich in iodine.
It is probably to the application of this body that we owe the discovery
of the daguerreotype. There is no record of the precise date when Daguerre
commenced experimenting with iodine, but by the published correspondence
between him and M. Neipce, his partner, it was previous to 1833. There is
no doubt, however, that the first successful application was made in 1838,
as the discovery was reported to the world early in January, 1839.
Preparation.—Iodine is mostly prepared from kelp, or the half vitrified
ashes of seaweed, prepared by the inhabitants of the western islands, and
the northern shores of Scotland and Ireland. It is treated with water,
which washes out all the soluble salts, and the filtered solution is
evaporated until nearly all the carbonate of soda and other saline matters
have crystallized out. The remaining liquor, which contains the iodine, is
mixed with successive portions of sulphuric acid in a leaden retort, and
after standing some days to allow the sulphureted hydrogen, etc., to
escape, peroxide of manganese is added, and the whole gently heated.
Iodine distills over in a purple vapor, and is condensed in a receiver, or
in a series of two-necked globes.
Properties.—Iodine is solid at the ordinary temperature, presenting the
appearance of dark-grey or purple spangles, possessing a high degree of
metallic lustre. It somewhat resembles plumbago, with which it is
sometimes diluted, particularly when it is fine. Operators should endeavor
to secure the larger crystals. It melts at 224.6 deg., forming a brown or
nearly black liquid. It boils at about 356 deg., and emits a very deep
violet colored vapor. It gives off a very appreciable vapor, sufficient
for all purposes of forming the iodide of silver on the daguerreotype
plate, at a temperature of 45 deg. or even lower. Iodine crystallizes
readily. Every operator has found upon the side of the jar in his
coating-box, perfectly regular crystals, deposited there by sublimation.
Water dissolves but a small proportion of iodine, requiring 7000 parts of
water to dissolve one of iodine, {85} or one grain to the gallon of water.
Alcohol and ether dissolve it freely, as does a solution of nitrate or
hydrochlorate of ammonia and of iodides.
The density of solid iodine is 4.95; that of its vapor 8.716. It greatly
resembles chlorine and bromine in its combinations, but its affinities are
weaker. It does not destroy the majority of organic substances, and
vegetable colors generally resist its action. It combines with several
organic substances, imparting to them peculiar colors. It colors the skin
brown, but the stain soon disappears.
Chloride of Iodine—Is formed by passing chlorine into a bottle containing
some iodine. This can be readily done by pouring one ounce and a half of
muriatic acid upon a quarter of an ounce of powdered black oxide of
manganese, and heat it gradually in a flask, to which is adapted a bent
glass tube. This tube must connect with the bottle containing the iodine,
and the yellowish-green gas disengaged will readily combine with the
iodine, forming a deep red liquid, and the operation is complete. The use
of chloride of iodine will be referred to in connection with the
Accelerators.
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Iodides.—The iodide treated with the oil of vitriol, instantly produces a
considerable deposit of iodine; and if the mixture be heated, intense
violent vapors are disengaged. The reaction is due to the decomposition of
oil of vitriol by iodohydric acid, water and sulphurous acid being formed,
and iodine set free. The iodides in solution are decomposed by chlorine,
iodine being precipitated, the smallest quantity of which in solution is
instantly detected by its imparting to starch an intensely blue color.
Iodide of Potassium.[4]—This
compound is easily made in the following manner: Subject to a moderate heat a
mixture of 100 parts of iodine, 75 of carbonate of potash, 30 of iron filings,
and 120 parts of water. This mass must be thoroughly dried and then heated to
redness; the resulting reddish powder is to be washed with water, and the
solution obtained filtered, and evaporated to dryness. It is found that 100
parts of iodine yield 135 parts of very white, but slightly alkaline, iodide of
potassium.
Experiment.—On projecting dry pulverized iodide of potassium into fused
anhydrous phosphoric acid, a violent disengagement of iodine takes place,
attended by a transient ignition; fused hydrate of phosphoric acid
liberates iodine abundantly from iodide of potassium; this reaction is
accompanied by the phenomenon of flame and formation of a considerable
quantity of hydriodic acid.
Iodide of Mercury.—For the preparation of iodide of mercury, Dublanc
recommends to cover 100 grms. of mercury with 1 kilogrm. of alcohol, to
add 124 grms. of iodine gradually in portions of ten grms., and agitating
between each fresh addition, until the alcohol becomes colorless again.
After the addition of the last 4 grms. the alcohol remains colored, the
whole of the mercury having become converted into iodide. The resulting
preparation is washed with alcohol; it is crystalline and of a hyacinth
color.
Iodide of Silver.—This compound is formed upon every plate upon which a
Daguerreotype is produced. The vapor of iodine coming in contact with the
silver surface, forms an iodide which is peculiarly sensitive to light.
The various colors produced are owing to the thickness of the coating, and
the maximum sensibility of the coating, as generally adopted, is when it
assumes a deep yellow, or slightly tinged with rose color.
This compound is largely employed in most photographic processes on paper,
and may be easily prepared by the following formula: By adding iodide of
potassium to a solution of nitrate of silver, a yellowish-white
precipitate of iodide of silver is obtained, which is insoluble in water,
slightly soluble in nitric acid, and soluble in a small degree in ammonia,
which properties seem easily to distinguish it from the chloride and
bromide of silver. Chlorine decomposes it and sets the iodine free, and
chlorohydric acid converts it into a chloride. It fuses below a red heat.
Although the effect of light on the iodide is less rapid than on the
chloride, the former sooner turning black, assuming a brown tinge; but
when in connection with gallic acid and the ferrocyanate of potash, it
forms two of the most sensitive processes on paper.
Iodide of silver dissolves easily in a solution of iodide of potassium,
and the liquid deposits in evaporation crystals of a double iodide.
Iodide of Gold.—If a solution of potassium be added to a solution of
chloride of gold, a precipitate of iodide of gold takes place, soluble in
an excess of the precipitate. A little free potash should be added to
combine with any iodide that may chance to be set free by the chloride of
gold.
Iodide of Lime is prepared by adding iodine to hydrate of lime (which will
be referred to farther on) until the mixture assumes a light yellow shade,
when wanted for combinations with accelerators, or to a dark brown when
employed for the first coating. This latter mixture has been sold in our
market under the name of “Iodide of Brome.”
Iodide of Bromine.—(See page 76.)
Experiments with Iodine.—Place a plate which has been exposed in the
camera over the vapor of iodine for a very brief period, and it will
present the appearance of the impression having been solarized.
b. Upon a Daguerreotype plate, from which an impression has been effaced
by rubbing or otherwise, the picture may be made to reappear by merely
coating it over with iodine.
c. Place in a vessel a little water, into which put the smallest possible
quantity of free iodine and add a little starch, and the liquid will
instantly assume a blue color. Advantage is taken of this fact in the
laboratory to detect the presence of iodine in liquids. The starch should
be dissolved in boiling water and allowed to cool. There are numerous
other interesting experiments that can be performed by the aid of iodine,
but it is unnecessary here to consume more space.
History.—The Swedish chemist, Scheele, in 1774, while examining the
action of hydrochloric acid on peroxide of manganese, first noticed this
element. He called it dephlogisticated muriatic acid. It was afterwards,
by the French nomenclaturists, termed oxygenated muriatic acid, conceiving
it to be a compound of oxygen and muriatic acid. This view of its notice
was corrected by Sir H. Davy (in 1809), who gave it the present name. In
1840-41, this gas vas employed for accelerating the operation of light
upon the iodized Daguerreotype plate. John Goddard, Wolcott & Johnson,
Claudet, Draper, Morse and others, were among the first made acquainted
with its use. Count Rumford, Ritter, Scheele, Seebert and others,
experimented with chlorine in regard to its effect when exposed to the
action of light in combination with silver. In 1845, M. Edward Becquerel
announced that he had “been successful in obtaining, by the agency of
solar radiations, distinct impressions, of the colors of nature.”
On the 4th of March, 1851, Neipce, St. Victor, a former partner of
DAGUERRE, announced that he had produced “all the colors by using a bath
of bichloride of copper, and that a similar phenomenon occurs with all
salts of copper, mixed with chlorine.”
Preparation.—This is easily accomplished by putting about two parts of
hydrochloric (muriatic) acid on one of powdered black oxide of manganese,
and heating it gradually in a flask or retort, to which may be adapted a
bent glass tube. A yellowish-green gas is disengaged, which being
conducted through the glass tube to the bottom of a bottle, can readily be
collected, being much heavier than the air, displaces it completely and
the bottle is filled (which can be seen by the green color); a greased
stopper is tightly fitted to it, and another bottle may be substituted.
In all experiments with chlorine, care should be taken not to inhale the
gas!
Properties.—Chlorine is a greenish-yellow gas (whence its name, from
chloros, green), with a powerful and suffocating odor, and is wholly
irrespirable. Even when much diluted with air, it produces the most
annoying irritation of the throat, with stricture of the chest and a
severe cough, which continues for hours, with the discharge of much thick
mucus. The attempt to breathe the undiluted gas would be fatal; yet, in a
very small quantity, and dissolved in water, it is used with benefit by
patients suffering under pulmonary consumption.
Under a pressure of about four atmospheres, it becomes a limpid fluid of a
fine yellow color, which does not freeze at zero, and is not a conductor
of electricity. It immediately returns to the gaseous state with
effervescence on removing the pressure.
Water recently boiled will absorb, if cold, about twice its bulk of
chlorine gas, acquiring its color and characteristic properties. The moist
gas, exposed to a cold of 32 deg., yields beautiful yellow crystals, which
are a definite compound of one equivalent of chlorine and ten of water. If
these crystals are hermetically sealed up in a glass tube, they will, on
melting, exert such a pressure as to liquefy a portion of the gas, which
is distinctly seen as a yellow fluid, not miscible with the water which is
present. Chlorine is one of the heaviest of the gases, its density being
2.47, and 100 cubic inches weighing 76.5 grains.
Chlorine Water.—This combination, which is used in conducting M. Neipce’s
process, can be readily prepared by conducting the gas into a bottle
containing distilled water. One part water dissolves two parts of
chlorine.
Chlorides.—The metallic chlorides are nearly all soluble in water; that
of silver and protochloride of mercury being the only exceptions. A
metallic chloride, treated with oil of vitriol, disengages chlorohydric
acid. Heated with a mixture of peroxide of manganese and sulphuric acid,
chlorine is given off, which is easily recognized by its odor and other
physical properties.
The chlorides dissolve in water; give with nitrate of silver, a white
precipitate, even in highly diluted solutions, becoming violet colored and
finally black when exposed to the light. The rapidity of the change of
color is proportioned to the intensity of the light. It is insoluble in
nitric acid, but readily soluble in ammonia; it fuses without
decomposition, forming, when cold, a tough, horny mass, and is reduced by
hydrogen and by fusion with carbonate of soda, or with resin.
Chloride of Bromine. (See page 74.)
Chloride of Iodine. (See page 85.)
Chloride of potassium.—or (Muriate of Potassa).—Dissolve half an ounce
of carbonate of potassa in water, and neutralize with muriatic acid. Upon
concentrating the solutions, cubic crystals will be obtained, having a
taste similar to common salt. They consist of potassium and chloride, and
when dissolved in water they may be regarded as muriate of potassa.
Chloride of Lime.—Mix half an ounce of slacked lime (hydrate of lime)
with six ounces of water, and conduct into this milk of lime, with
frequent agitation, as much chlorine gas as will evolve from two ounces of
muriatic acid and half an ounce of black oxide of manganese. The liquid
clarifies by standing; may be regarded as a solution of chloride of lime,
and must be protected from the air and light. It may also be made without
putting in the water with the hydrate of lime, by merely passing the
chlorine into the hydrate of lime. This last is by some used in
preparations for accelerating the operation of taking Daguerreotypes, but
when used for this purpose it is in small quantities.
Chloride of Calcium.—To one part of water add two parts of muriatic acid,
and add pieces of common chalk until effervescence ceases; then filter
through cotton cloth and evaporate it by placing it in all earthen or
porcelain dish, over a slow fire, to the consistency of a syrup. When
cooling, large prismatic crystals of chloride of calcium are formed. These
must be quickly dried by pressing between folds of blotting paper and kept
carefully excluded from the air, as it readily attracts hydrogen. For most
daguerreotype purposes, the syrup may be at once evaporated to dryness.
This is frequently placed in the iodine coating box for the purpose of
keeping the atmosphere dry. It is so easily made that every operator can
provide himself with it in a short time, and at little expense.
Chloride of Gold.—Is prepared by dissolving gold in aqua regia, a
composition of one part of nitric to two parts of muriatic acid. Gold foil
is the best for our purposes; coin, however, answers, in most cases, for
the daguerreotype operator, as the alloy, being so slight is not noticed
in the gilding process. When the latter is used, it will facilitate the
operation to beat it out, forming a thin sheet, and then cutting in small
strips. Where purity is required, foil is better. The gold is placed in
three or four times its own weight of the above acids. For this purpose,
an evaporating dish is best (a common saucer will do); a moderate heat may
be applied to favor the action. The mixture should be stirred often with a
glass rod; care should be observed not to apply too much heat, for at a
temperature of about 300 deg. the chlorine would be expelled and leave a
metallic precipitate, which would require re-dissolving. Acid may at any
time be added if necessary to dissolve the gold, but it is advisable to
add as little excess as possible, as it would require more time to
evaporate. After all the gold has dissolved, and the liquid assumes a deep
red color, the solution should be allowed to cool, being stirred nearly
all the time. This salt is of a reddish-brown color. It is rarely we find
in our market good chloride of gold, as common, salt is used for the bulk;
and when the bottles are labelled “15 grains,” “20 grains,” nine-tenths do
not in reality contain exceeding five grains of chloride of gold. The salt
is mixed with the above solution when it is cooling, and gives bright
yellow crystals, which some of our uninformed operators conceive to be the
best quality.
Chloride of Silver.—(Oxide of Silver.)—Take any quantity of silver coin
or other silver, roll or hammer it thin; cut in small pieces. This in
order to save time. Put the silver in a glass or earthen vessel (Florence
flask is best); pour in nitric acid and water, about three parts of the
former to one of the latter. The operation of cutting up the silver may be
facilitated by applying a gentle heat. This blue solution consists of
oxide of silver and oxide of copper, both combined with nitric acid.
Should the operator wish a pure solution of silver, which, however, is not
always used, he may obtain it in the following manner:
To separate the two metals contained in the above solution from each
other, put some bright copper coins into the solution and set it aside in
a warm place for three or four days, occasionally giving it a circular
motion. The separated laminae are pure silver, which is to be digested
with ammonia until it ceases to be colored blue. The silver, after being
washed and dried, is again dissolved in nitric acid, and the liquid,
diluted with water, is kept as solution, of silver.
Either of the above solutions (the one of oxide of silver and copper, and
the pure silver solution) may be prepared for use by putting them in a
bottle, with a quantity of water, and adding common fine salt, you obtain
a white curdy precipitate of chloride of silver. No matter how much salt
is used, provided enough be added to throw down all the chloride of
silver. This solution should be well agitated and then allowed to stand
for a few minutes; thus the white precipitate is in the bottom of the
bottle. When the water has become clear, pour it off with care, leaving
the sediment behind, then add a fresh quantity of clean water, shake, let
settle, and pour off as before. Repeat the same for several times, and the
excess of salt will disappear, leaving the white precipitate, which may be
drained of the water and dried in the dark, and kept free from light and
air.
Cyanide of Potassium.—This important article is worthy the undivided
attention of every Daguerreotypist. I here give Mr. Smee’s process for its
preparation. This is from that author’s work entitled, “Electro
Metallurgy,” American edition:
“The cyanide of potassium, so often alluded to while treating of the
metallo-cyanides, may be formed in several ways. It may be obtained by
heating to a dull redness the yellow ferrocyanate of potash, in a covered
vessel, filtering and rapidly evaporating it. The objection to this
method, however, is that without great care the whole of the ferrocyanate
is not decomposed, a circumstance which much reduces its value for
electro-metallurgy. By boiling, however, the ignited residue with spirits
of wine this difficulty is said to be overcome, as the ferrocyanate is
absolutely insoluble in that menstruum, while the cyanuret, at that heat,
freely dissolves, and is as easily re-deposited on cooling.
“There is, however, a much better process by which this salt may be
formed, viz. by simply transmitting hydrocyanic acid through potassium.
Although the modes of making this acid are very numerous, there is but one
which is likely to be employed on a very large scale, and that is its
formation from the yellow ferrocyanate by means of sulphuric acid. This
process is performed as follows: any given weight of the yellow salt is
taken and dissolved in about five times its weight of water; this is
placed in a retort, or some such analogous vessel, to which is then added
a quantity of strong sulphuric acid, twice the weight of the salt, and
diluted with three or four times its quantity of water. A pipe is carried
from the neck of the retort to the receiving bottle, which should be kept
as cool as possible.
“For small operations, those invaluable vessels, Florence flasks, answer
well: a bent tube being connected at one end to its month, the other
passing into the second vessel; heat should be cautiously applied by means
of an Argand lamp, a little vessel of sand being placed under the flask,
which helps the acid to decompose the salt. Prussic acid is then generated
and passes through the tube to the recipient vessel, which is to be
charged with liquor potassae.
“When the potash is saturated, the operation is completed. The Germans
recommend a strong, alcoholic solution of potassa to be used in the second
vessel, for in this case, the hydrocyanic or prussic acid combines with
the potassa, forming a hydrocyanate of potassa, or, the water being
abstracted, the cyanuret of potassium, which spontaneously precipitates,
on the saturation of the fluid, the cyanuret, being insoluble in strong
alcohol. The ferrocyanate of potash may be considered as containing three
equivalents of hydrocyanic acid, two of potash and one of iron; but,
unfortunately, we can only obtain half the acid from the salt, owing to
the formation of a compound during its decomposition which resists the
action of the acid. The decomposition of this salt taking 2 equivalents or
426 grains (to avoid fractions) would afford 3 equivalents or 81 grains of
hydrocyanic, or prussic acid, capable of forming 198 grains of cyanuret of
potassium, while in the retort there would remain 384 grains or 3
equivalents of bisulphate of potash, and 1 equivalent or 174 grains of a
peculiar compound, said to contain 3 equivalents of cyanogen, 1 of
potassium, and one of iron (Pereira). It is manifest that, but for this
later compound, we might double the quantity of hydrocyanic acid from the
yellow salt.”
The decomposition just described is the one usually received; but too much
reliance must not be placed on its accuracy, for the analysis of the
several compounds is too difficult for the results to be fully admitted.
The residue left in the retort speedily turns to one of the blues,
identical with, or allied to, Prussian blue. This is at best a
disagreeable process to conduct, for the hydrocyanic acid formed adheres
so strongly to the glass, that, instead of being freely given off, bubbles
are evolved suddenly with such explosive violence as occasionally to crack
the vessel. This may be remedied as far as possible by the insertion of
plenty of waste pieces of platinum—if platinized, so much the better, as
that facilitates the escape of the gas. The heat should be applied to
every part of the vessel, and the flame should not be allowed to play upon
one single part alone. Large commercial operations are performed in green
glass or stone-ware retorts.
“Now for one word of advice to the tyro: Remember that you are working
with prussic acid; therefore, never conduct the process in a room, the
fumes being quite as poisonous as the solution of the acid itself;
moreover, have always a bottle of ammonia or chlorine by your side, that
should you have chanced to inhale more than is pleasant, it will be
instantly at hand to counteract any bad effects. It is stated by Pereira,
that a little sulphuric acid or hydroferrocyanic acid passes to the outer
vessel, but probably the amount would be of no consequence for
electro-metallurgy, otherwise, it might be as well to use a Woulfe’s
apparatus, and discard the salt formed in the first vessel. To the large
manufacturer it may be worth considering whether some other
metallo-cyanuret, formed in a similar manner to the ferrocyanuret, might
not be more advantageously employed, because the residue of the process
last described contains a large quantity of cyanogen which the acid is
unable to set free.
“There are other modes of procuring prussic acid, besides the one which
has been so tediously described; but these are found to be more expensive.
The only one which I shall now notice is the process by which it is
obtained from bicyanide of mercury. The bicyanide of mercury itself is
formed when peroxide of mercury is digested with Prussian blue, the
peroxide of mercury abstracting the whole of the cyanogen from the blue,
and leaving the oxides of iron at the bottom of the vessel. The solution
may be evaporated to dryness, and one part of the salt dissolved in six of
water; one part of muriatic acid, sp. gr. 1.15, is then added, and the
solution distilled, when the whole of the hydrocyanic acid passes over,
and by being conducted into a solution of potassa, as in the former
process, forms cyanuret of potassium. This process, though easier than the
first described, is rather given as a resource under peculiar
circumstances than as one to be adopted by the large manufacturer. The
expense is the only objection, but in a small quantity this cannot be a
consideration.
“In giving this very rough outline of the general mode of forming salts,
the minutiae necessary for chemical work have altogether been avoided, and
those parts alone are entered upon which are more immediately necessary
for the electro metallurgist to know and practice for himself. This will
account for the long description of the cyanuret of potassium, while the
preparation of the equally important and even more used acids, the
sulphuric, muriatic, etc., commonly found in commerce, are altogether
neglected.
“In using solutions of cyanide of potassium, the workman should not
immerse his arms into them, otherwise it occasionally happens that the
solution produces very troublesome eruptions over the skin.”
Hyposulphite of Soda.—This salt forms one of the important chemicals for
the Daguerreotype operator. Its application to this art is of an
interesting nature. It is used to dissolve the sensitive salt of silver
which remains unchanged during the exposure in the camera. It has the
property of readily dissolving the chloride, bromide and iodide of silver.
It should be pure and free from sulphuret of sodium; should this last be
present, it will cause brown spots of sulphurated silver upon the
Daguerreotype impression. This annoyance is a great source of complaint
from many operators, and ever will be, so long as it is prepared by men
who have no reputation to lose, and whose eyes are blinded by the
“Almighty Dollar.”
A good article may be prepared as follows:
“Mix one pound of finely pulverized carbonate of soda with ten ounces of
flowers of sulphur, and heat the mixture slowly in a porcelain dish till
the sulphur melts. Stir the fused mass, so as to expose all its parts
freely to the atmosphere, whereby it passes from the state of a sulphuret,
by the absorption of atmospheric oxygen, into that of a sulphite, with the
phenomenon of very slight incandescence. Dissolve in water, filter the
solution, and boil it immediately along with flowers of sulphur. The
filtered concentrated saline liquid will afford, on cooling, a large
quantity of pure and beautiful crystals of hyposulphite of soda.”
Hyposulphite of Gold.—This compound salt is by a few considered
preferable to the chloride of gold, but our experience has induced us to
use the latter, believing we are enabled to produce a more brilliant and
warm-toned impression with it. When the hyposulphite of gold is used in
gilding, it requires less heat and a longer application, as there is some
danger of producing a glossy scum over some parts of the surface of the
plate. I prepare this salt as follows:
Dissolve one part chloride of gold and four parts hyposulphite of soda in
equal quantities of distilled water: pour the gold into the hyposulphite
solution, in the same manner as in mixing the gilding solution; let it
stand until it becomes limpid; filter and evaporate to dryness.
Re-dissolve and add a few grains of burnt alum.
After standing a few hours, filter and evaporate again. If not
sufficiently pure, repeat the crystallization until it is so. For gilding,
dissolve in water and use in the same manner as the common gilding
solution.
N.B.—The four following mixtures were employed in Neipce’s process in his
earliest experiments:
Aqueous Solution of Bichloride of Mercury.—Eight grains of bichloride of
mercury in 10,000 grains of distilled water.
Solution of Cyanide of Mercury.—A flask of distilled water is saturated
with cyanide of mercury, and a certain quantity is decanted, which is
diluted with an equal quantity of distilled water.
Acidulated White Oil of Petroleum.—This oil is acidulated by mixing with
it one tenth of pure nitric acid, leaving it for at least 48 hours,
occasionally agitating the flask. The oil, which is acidulated, and which
then powerfully reddens litmus paper, is decanted. It is also a little
colored, but remains very limpid.
Solution of Chloride of Gold and Platinum.—In order not to multiply the
solutions, take the ordinary chloride of gold, used for fixing the
impressions, and which is composed of 1 gramme of chloride of gold and 50
grains of hyposulphate of soda, to a quart of distilled water.
With respect to chloride of platinum, 4 grains must be dissolved in 3
quarts of distilled water; these two solutions are mixed in equal
quantities.
Acids.—I shall not go into the preparations of the various acids employed
in the Daguerreotype. This would be useless to the operator, as there are
few, if any, that it would be advisable to prepare. It is only necessary
for the experimenter to be made acquainted with their properties, and this
in order to prevent any haphazard experiments, which are too common among
operators. Any person who may be desirous to try an experiment, should
first study the agents he wishes to employ. By so doing much time and
money will be saved; while the searcher after new discoveries would rarely
become vexed on account of his own ignorance, or be obliged to avail
himself of the experience of others in any department of science.
Nitric Acid—Exists in combination with the bases, potash, soda, lime,
magnesia, in both the mineral and vegetable kingdoms, and is never found
insoluble. It has the same constituents as common air, but in different
proportions. The strongest nitric acid contains in every pound, two and a
quarter ounces of water. Pure nitric acid is colorless, with a specific
gravity of 1.5, and boiling at 248 deg.. It is a most powerful oxidizing
agent, and is decomposed with more or less rapidity, by almost all the
metals, to which it yields a portion of its oxygen.
The nitric acid of commerce, is generally the article used by the
Daguerreotypist. This usually contains some chlorine and sulphuric acid.
It is obtained by the distillation of saltpetre with sulphuric acid. It is
employed in the Daguerreotype process for dissolving silver, preparing
chloride or oxide, nitrate of silver, [the former used in galvanizing,]
and in combination with muriatic acid for preparing chloride of gold, used
in gilding. It is also used by some for preparing the plate.
Acidulated Solution.—This solution is used for cleaning the surface of
the Daguerreotype plate. It has the property of softening the silver, and
bringing it to a state in which it is very susceptible of being either
oxidized or iodized, hence it contributes to increase the sensibility of
the plate. The proportions are to one drop of acid add from 15 to 20 drops
of water, or make the solution about like sharp vinegar to the taste.
Nitro-Muriatic Acid.—Aqua Regia is a compound menstruum invented by the
alchemists for dissolving gold. It is composed of colorless nitric acid
(aqua-fortis) and ordinary muriatic acid; the mixture is yellow, and
acquires the power of dissolving gold and platinum. These materials are
not properly oxidized; it nearly causes their combination with chlorine,
which is in the Muriatic acid.
Hydrochloric Acid (Muriatic Acid).—This acid forms a valuable addition to
the chemicals employed by the practical Daguerreotypist. This acid is
formed by acting upon common salt (which is chloride of sodium) by
concentrated sulphuric acid. The water of the acid is decomposed, and its
hydrogen combines with the chloride of the salt to form muriatic acid, and
this unites with the sulphuric acid to form sulphate of soda; 60 parts of
common salt and 49 parts of concentrated sulphuric acid, afford, by this
mutual action, 37 parts of muriatic acid and 72 parts of sulphate of soda.
The muriatic acid of commerce has usually a yellowish tinge, but when
chemically pure it is colorless. The former is commonly contaminated with
sulphurous acid, sulphuric acid, chlorine, iron, and sometimes with
arsenic.
Muriatic acid, from the fact of the presence of the chlorine, is used in
the Daguerreotype process for dissolving gold, and in combination with
various accelerators. Its presence can be detected by ammonia. A strip of
paper dipped in this and waved to and fro will emit a thick white smoke if
the acid vapor be in the atmosphere. The ammonia neutralizes the acid
fumes. By reversing the experiment we can determine whether vapor of
ammonia be in the air, and also deprive these suffocating and dangerous
gases of their injurious properties, and remove them from the air. Every
Daguerreotype operator should be furnished with, at least, a six ounce
bottle of aqua ammonia. Its operation is very nearly the same on bromine
and iodine vapor.
Hydrofluoric Acid (Fluorohydric Acid).—This acid is used to form some of
the most volatile and sensitive compounds employed in the Daguerreotype.
It is one of the most dangerous bodies to experiment with: it is volatile
and corrosive, giving off dense white fumes in the air. It combines with
water with great heat. At 32 deg. it condenses into a colorless fluid,
with a density 1.069. It is obtained from decomposition of fluorspar by
strong sulphuric acid. It readily dissolves the silica in glass, and
consequently cannot be kept in a vessel of that material. It is prepared
and kept in lead. It is employed in accelerators on account of its
fluorine.
One small drop on the tongue of a dog causes death. The operator who
wishes to use it should pour some of the liquid for which he intends it
into a graduate, or other vessel, and then add the desired quantity of
acid. If by accident any of the spray should fall upon the skin, it should
at once be copiously drenched with water.
Sulphuric Acid.—There are two sorts of this acid: one is an oily, fuming
liquid; this is made in Nordhausen, in Saxony, and is commonly called
“Nordhausen sulphuric acid,” or oil of vitriol. The other which is the
kind used in connection with the Daguerreotype, is common sulphuric acid.
It is somewhat thinner, and when undiluted is not fuming. This acid may be
obtained in a solid and dry state, called anhydrous sulphuric acid.
The common sulphuric acid is made by burning sulphur, which forms
sulphurous acid. To convert this into sulphuric acid and gain more oxygen,
nitric acid, which is rich in that body, is added. It forms a limpid,
colorless fluid, of a specific gravity of 1.8. It boils at 620 deg.; it
freezes at 15 deg. It is acrid and caustic, and intensely acid in all its
characters, even when largely diluted.
Its attraction for basis is such that it separates or expels all other
acids, more or less perfectly, from their combinations. Its affinity for
water is such that it rapidly absorbs it from the atmosphere, and when
mixed with water much heat is evolved. It acts energetically upon animal
and vegetable substances, and is a poisonous, dangerous substance to get
on the skin. It is a powerful oxidizing agent; hence its use in the
galvanic battery, for which purpose it is mostly used by the
Daguerreotypist. The fumes of this being so much more offensive than
nitric acid, the latter is sometimes used. It is also employed in some of
the more sensitive accelerators.
Remarks on the Accelerating substances Used in the Daguerreotype.—I have
now arrived at a point in this work, where the eye of the Daguerreotype
public will intently search for something new. This search will prove in
vain, at least so far as regards those who have enjoyed and embraced the
opportunities for studying the principles of our art. Every experienced
operator has in a degree become familiar with the mechanical uses of all
the agents employed, while I fear but few understand the properties, and
laws governing those properties, which are so indispensable to produce an
image impressed upon the silver surface.
There are three substances which form the bases for producing a
Daguerreotype; silver, iodine and bromine. Each forms a separate body
which is indispensable to the operators success as the art is now
practiced in America. With these three, compounds of great variety are
formed.
The silver surface is first thoroughly cleaned and freed from all organic
matter, then exposed to vapor of iodine, producing an iodide of silver.
The plate upon which is this salt, is again exposed to the vapor of
bromine, forming a bromo-iodide of silver, a salt also.
As most of the various accelerators are compounds of bromine, with either
chlorine or fluorine combination, they partake somewhat of the nature of
these latter, giving results which can be detected by the experienced
operator. Thus muriatic acid is added for its chlorine, which can
generally be detected by the impression produced, being of a light, soft,
mellow tone, and in most cases presenting a brilliant black to that
colored drapery. Those who wish to experiment with agents for accelerating
substances, should first study to well understand their peculiar nature
and properties; as well, also, to endeavor to find out what will be the
probable changes they undergo in combination as an accelerator. This
should be done before making the experiments. From the foregoing it will
be seen that numerous compounds are formed from the same basis, and,
consequently, it would be a waste of time and a useless appropriation to
devote more of our space than is necessary to give the principal and most
reliable combination.
In America, the words “Quick” and “Quick Stuff,” are more generally used
for and instead of the more proper names, “Sensitives,” or “Accelerators,”
etc. As it has by use become common, I frequently use it in this work.
Liquid Accelerator, No. 1.—This mixture was used by me in 1849, and is
given as it appeared in my “System of Photography,” published at the above
date:
Take pure rain or distilled water, one quart, filter through paper into a
ground stopper bottle, and add, for warm weather, one and a half ounce
chloride of iodine; or for cold, one ounce; then add one ounce bromine,
and shake well. Now with care not to allow the vapor to escape, add drop
by drop, thirty drops of aqua ammonia, shaking well at each drop. Care
must be taken not to add more at a time, as it evokes too much heat. This
mixed, in equal proportions with John Roach’s quick, forms an excellent
chemical combination. For this purpose, take one and a half ounce of each,
to which add ten ounces water, for warm weather, or from six to seven for
cold. Pour the whole into a large box, and it will work from two to four
months. I am now using (1849) one charged as above which has been in
constant use for three months, and works uniformly well. The above is
right for half or full size boxes, but half of it would be sufficient for
a quarter size box.
Coat to the first shade of rose over iodine, change to a deep rosy red
over quick, and black about one tenth the first.
I would not now recommend the addition of “John Roach’s quick,” as I
believe equally good results can be produced without it. This liquid is
now used by many, and is very good for taking views.
Lime Water Quick.—This mixture is more used at present than all the other
liquids ever introduced. It produced the most uniform results, giving the
fine soft tone so characteristic in pictures produces from accelerators
containing chlorine. To one quart of lime water (this can be had of any
druggist) add one and a half ounce of pulverized alum. This should be
shook at intervals for twenty—four hours; then add one ounce of chloride
of iodine and three fourths ounce of bromine.
Lime Water.—This is easily prepared by putting lime into water, say a
piece of quick-lime about the size of an egg into one quart of water. This
should be shook occasionally for two or three days and allowed to settle,
when the water can be poured off and used.
Use.—To one part of quick add six parts of water; coat to a light yellow
over the iodine, to a rose color over the quick, and recoat about one
tenth. The above coating may be increased or diminished, it matters not,
so that there is not too much, and the proper proportions are preserved.
Some add to the above a small quantity of magnesia, say about a
teaspoonful to the quart of liquid.
Liquid Accelerator, No. 2.—The following was for a long time used by one
of the first houses in the United States, and probably was one of the
first liquids ever used. It produces a fine-toned picture, but is not
considered as sure as the lime water quick:
Take rain water one quart, add pulverized alum until it is a little sour
to the taste, and a small piece, say one half inch square, of magnesia.
Filter through paper, and add chloride of iodine one half ounce, bromine
sufficient to take it up, which is a little less than half an ounce.
Charge with one of quick to six of water; coat over iodine to a soft
yellow, nearly, but not quite, bordering on a rose; over quick to a dark
purple, or steel, and back one sixth to one tenth.
Wolcott’s American Mixture.—Van Loan Quick.—This mixture was first
formed and used by T. Wolcott & Johnson and gained great celebrity for
its productions. I have now a bottle hermetically sealed that contains
about a half ounce of this mixture prepared in 1841 by John Johnson, now a
resident of this city, and the former partner of Mr. Wolcott. The
preparation of this mixture, as furnished by Mr. Johnson himself, is given
as follows:
“One part of bromine, eight parts of nitric acid, sixteen parts of
muriatic acid, water one hundred parts. This mixture should be allowed to
stand for several days; it improves by age.
“Use.—A few drops say, 6 to 12, of this mixture, should be put into about
6 or 8 ounces of water; it will require frequent replenishing by the
addition of a few more drops. The plate should be coated over the dry
iodine to a red just bordering on a slate, and then exposed to the mixture
only sufficiently long to change the color. If this is not done in less
than six seconds it is not strong enough. Re-coat over the iodine full one
fourth as long as first coating.”
This exceedingly volatile compound is difficult to control from its
instability; it is but little used. The impressions successfully produced
by this mixture are very brilliant, and possess a pleasing peculiarity.
Hydrate of Lime.—The operation by which water is combined with lime is
called slaking. Take a piece of quick lime, common lime used in mortar,
and immerse it in warm water for about fifteen seconds; then place it in
an iron or tin vessel. It will soon begin to swell, evolving a great deal
of heat and emitting steam, and soon falls into a fine powder, hydrate of
lime. This should be well stirred and allowed to cool, and then bottled in
order to prevent it from giving off the hydrate and recovering the
carbonic acid from the atmosphere. The last is detrimental to its use with
bromine, and is one cause of the complaint that “it will not take
bromine.” The hydrate of lime should, not be dried over a heat, as has
been supposed by many, for in that case the hydrogen is expelled and it
returns to a carbonate. It is advisable to cool it in a damp place like a
ground cellar. Much of the lime in our market will not, except it be quite
damp, combine with the bromine. This is owing to impurities. Nothing is
equal to oyster-shell lime, which I use altogether.
Bromide of Lime.—In preparing large quantities of this, we adopt the
following method: Fill a four-quart bottle about two-thirds full of
hydrate of lime; pour into this about one or two ounces of bromine; then
shake well, add more of the bromine, shake well and let it stand for a few
hours, adding sufficient bromine to give it a fine red color. It is better
when kept in the large bottles, as it forms a more perfect combination: in
other words it improves by age.
Use.—Coat over the iodine to a rose red and then over this mixture to a
purple or slate; recoat over the first about one fourth as long as first
coating.
Gurneys American Compound.—Of this compound there are two combinations,
one for use, when the temperature of the atmosphere is above 65 or 70
deg., and the other at a lower temperature. The first is called No. 1, the
second No. 2.
No. 1 is prepared by placing hydrate of lime in a bottle, say to three
quarts of the hydrate of lime, add one ounce of pulverized burnt alum, and
as much chloride of lime as can be put on a quarter of a dollar, and from
15 to 30 grains of dry pulverized iodine, or enough to change the color of
the hydrate of lime, to the slightest possible tinge of yellow. There had
better be less than carry the color to a deeper shade. The object of using
the iodine is to form a compound with bromine that is not so volatile as
the bromine itself. No matter how little iodine is combined with the
bromine, the vapors possess their relative proportion; hence, only enough
iodine to prevent “flaring,” or as it is often termed a “scum-coating,” is
used. The iodine should be thoroughly combined with the lime, which will
take about one or two days. Should add bromine the same as in bromide of
lime, until the compound assumes a light red color.
No. 2 is prepared in the same manner as No. 1, except the addition of the
iodine, which is omitted.
Use.—No. 1. Coat over the iodine to a bright yellow color, then over the
compound, No. 1, to red color, recoat over iodine, about one sixth as
long, as the time occupied in first coating.
No. 2. Coat over iodine same as above, except recoat over the iodine about
one fourth to one half as long as first coating.
Dry Quick, No. 1.—Bromide of Lime and Starch.—The following compound
forms an excellent accelerator, and is used by many. It is claimed for
this preparation, that it will hold the bromine longer than others where
starch is not employed. As regards this claim we do not think it can be
substantiated. Our experience in practice has led us to the conclusion
that there is no great difference as respects durability, but there is
some little difference as regards the tone of the impressions produced by
its use.
To one quart of hydrate of lime add one quart of finely pulverized starch.
To this mixture add bromine, until it assumes a deep yellow or pink color.
Starch may be added to any of the dry mixtures.
Use.—Coat over the iodine to a deep yellow, then over this quick to a red
color, recoat about one sixth of the time of first coating.
I will here again remark, that the exact color of the coating is not
essentially provided a proper proportion is preserved.
I have never seen it stated, though it be a fact worthy of note, that a
proportionate time for coating over the iodine and accelerator, will not
answer. For example: if a plate exposed to the vapor of iodine be
perfectly coated in sixteen seconds, and then exposed to an accelerator,
(not having iodine in its combination) receives its coating in four
seconds, it will be found that a proper proportionate coating cannot be
preserved by adopting, a proportion of time, but on the contrary, the time
will diminish; for exposure over the accelerator, as in the above example,
if it be desired to coat the plate with twice as much iodine as in the
above example, the time would be, over iodine thirty-two seconds, and over
the accelerator (to possess a proper proportion) from six to seven
seconds. Hence it is that many inexperienced operators, when wishing to
vary their usual manner of coating, fail in producing a favorable result.
They coat calculating a proportion of time when they should not.
Dry Quick, No. 2.—Bromide of Lime and Magnesia.—To one quart of hydrate
of lime add one quart of magnesia, and mix them well together; add bromine
same as in preparing bromide of lime; coat the same as over dry quick No.
1. This combination produces very uniform results, and is worked with much
success by beginners.
Chloro-Bromide of Lime.—To the bromide of lime add chloride of bromine
until the mixture becomes a pale yellow color, resembling sulphur. It
should be shook well, and enough of the chloride of bromine added to bring
the compound to a deep blood red color.
Use.—Coat over the iodine to a pink color, and then over the above to a
red, or just changing the color. It should be remembered that accelerators
containing chlorine do not admit of a great change of color of coating on
the plate.
Iodide of Starch.—This mixture can be employed for coating over in warm
weather, and prevent the flashing resulting at high temperatures. It may
be used the same as the iodide alone.
To six ounces of finely pulverized starch, add one fourth ounce of dry
iodine.
Use.—Same as the dry iodine alone.
The same combination may be made with lime, magnesia and other substances.
Concentrated Solution of Iodine for First Coating.—It may appear strange
to some of our old operators that an aqueous solution of iodine can be
used for coating the plate and forming the iodide of silver. It has long
been a cry among most operators that it is impossible to succeed when the
iodine box contains dampness. Now this is a great mistake, and we will
here state that in all cases where dampness appears upon a properly
prepared Daguerreotype plate, it is the result of a different temperature
of the metal from the air which surrounds it. Mr. Senter, of Auburn, was
the first of our operators who used a solution of iodine for coating the
plate, and we several years since saw his results, which would rival the
production of any other operator. A concentrated solution of iodine is
prepared by putting into a common bottle two thimblesful of hyposulphite
of soda and a rather larger quantity of iodine, so that there may be more
than sufficient. Add to it about 40 ounces of common water (heated to 60
or 70 degrees), by little and little, moving, the bottle to warm it, for
fear of breaking. After shaking it a short time, the water is rapidly and
strongly colored. The solution should be poured into a bottle with a
ground stopper, and when cool used for iodizing.
A solution of sufficient strength can be made by moistening or just
covering the iodine with water.
Chloride of Iodine as an Accelerator.—This is probably one of the best
accelerators that can be used for coating the plate for taking views; it
works too slow, however, to meet the wants of the operating room, yet its
use was formerly, for a long time, adhered to by some of our best
professors. In producing views with this, we are successful in obtaining
well-developed impressions, with a depth of tone and richness of
appearance not to be met with in the productions of any other substances.
I give its use as furnished me by an old and experienced operator, and
published in Humphrey’s Journal, vol. i. p. 180:
“As the process of using chloride of iodine may be of interest to some of
our subscribers, I take pleasure in giving the following manipulation. To
one ounce of chloride of iodine add two ounces of water; place this
mixture in a coating-box, the same as quick stuff; coat the plate with dry
iodine to a light yellow, or lemon color; then bring the coating to a deep
pink over the chloride. The plate must be recoated over the dry iodine.”
This combination has been very successfully used in one of our most
extensive establishments in this city, and the superiority of the pictures
produced by it was considered as an equivalent for the additional time
required to bring out the impressions.
Chlorine as an Accelerator.—I shall here refer to but a single experiment
in which I employed chlorine gas for coating the plate. I was provided
with a retort, the neck of which was fitted to the jar of my coating-box,
through a hole drilled for its reception. This was fitted perfectly tight
in my coating-box. I placed some pure undiluted bromine water and the
agents necessary for producing chlorine gas (in small quantity) in the
retort. The result was that my first experiment produced an impression
completely solarized in all its parts by an exposure of four seconds of
time, which would have required an exposure of twenty seconds to produce a
perfectly developed impression by the usual process.
Another trial immediately produced one of the finest toned impressions I
ever saw, perfectly developed in one second of time.
My next two or three experiments proved total failures. I was unable to
produce even a sign of an impression. By accident my retort was broken,
and not being in a locality convenient to obtain another, my experiments
were necessarily suspended.
My attention was not called to this subject again for several years, when
I noticed an account of some similar experiments by F. A. P. Barnard and
Dr. W. H. Harrington, the latter of whom is now of the firm of Dobyns
& Harrington, of New Orleans.
From reading this article, I found my own difficulties explained. Too much
of the chlorine gas was present in my coating jar. I would like to see
some of our enterprising operators investigate this combination.
It is a singular fact, that the vapors of bromine and chlorine combining
upon the iodide of silver, produce a more sensitive coating than when the
two are combined in solution, as in chloride of bromine solution. Those
having Humphrey’s Journal at hand, can refer to vol. i. p. 142.
To use Bromine Water or other Accelerators in Hot Weather.—An excellent
plan for using bromine water is as follows:
Fill a two-ounce bottle quarter full of it, and then fill the bottle with
fine sand, which serves to preserve a low temperature; then place the
bottle in a porous cup, same as used in the battery; fill this also with
sand, and close the end with plaster of Paris. Place this in a
coating-box, and it will be found to act with great uniformity and be
quite permanent.
Bromide of Lime, another accelerator, can be used in the same manner,
except it is, only necessary, when a solid sensitive is used, to mix it
with the sand without placing it in a bottle. This method is employed with
great success by a few, who have regarded it as a secret worth keeping.
A Combination, requiring the Use of only One Coating-box.—It is often
wondered by beginners, why some solution requiring only one coating cannot
be employed. This can be done, but the results are not so satisfactory as
when two or more are employed. Such an accelerator may be produced by
adding alcoholic solution of iodine to a solution of chlorate of potash,
until the latter will take up no more of the former, and to each ounce, by
measure of this solution, ten drops of a saturated solution of bromide in
water are added. The solution of chlorate of potash is made by diluting,
one part of a saturated solution of the salt with ten parts of water. The
use of the chlorate is simply as a solvent of iodine.
Fats as Accelerators.—The use of fats, oils, or greasy substances, has
been one of the most emphatic prohibitions about the Daguerreotype plate.
Yet it has been proved that its presence in a small quantity upon the
silver surface has the effect of reducing the time of exposure in the
camera from two-thirds to three-fourths. An application may be made as
follows: Pour sweet oil, or rub beef or mutton fat, on a common buff,
which is free from all polishing powders. With this, buff a well-cleaned
plate, and it will leave a scum, which should be mostly removed by using
another buff, which should be clean. Coat the plate in the usual manner,
and the result will be a great reduction in the time of exposure in the
camera. The impression produced upon a plate so prepared presents, when
coming from the vapor of mercury, a grey, scummy appearance, which, on the
application of heat in gilding, does not improve; hence its use is not
generally adopted.
We have instituted some investigations upon this subject, and in the
present volume, we shall not refer to it further. Those wishing to learn
more fully the effect of light upon organic substances will find Robert
Hunt’s “Researches on Light” an invaluable work.