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37. Chlorine


This section is from the American Hand Book of the Daguerreotype, by Samuel D. Humphrey. Published S. D. Humphrey, 37 Lispenard Street 1858.

37. Chlorine

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


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