SECTION I.. _collodion._

Collodion.

Collodion (so named from the Greek word κολλἁω, to stick) is a glutinous, transparent fluid, procured, as generally said, by dissolving Gun-Cotton in Ether. It was originally used for surgical purposes only, being smeared over wounds and raw surfaces, to preserve them from contact with the air by the tough film which it leaves on evaporation. Photographers employ it to support a delicate film of Iodide of Silver upon the surface of a smooth glass plate.

Two elements enter into the composition of Collodion: first, the Gun-Cotton; second, the fluids used to dissolve it. Each of these will be treated in succession.

CHEMISTRY OF PYROXYLINE.

Gun-Cotton or Pyroxyline is Cotton or Paper which has been altered in composition and properties by treatment with strong acids.

Both Cotton and Paper are, chemically, the same. They consist of fibres which are found on analysis to have a constant composition, containing three elementary bodies, Carbon, Hydrogen, and Oxygen, united together in fixed proportions. To this combination the term Lignine or Cellulose has been applied.

Lignine and Cellulose are not precisely identical substances. The latter is the material composing the cell-wall; the former, the contained matter in the cell.

Cellulose is a definite chemical compound, in the same sense as Starch or Sugar, and consequently, when treated with various reagents, it exhibits properties peculiar to itself. It is insoluble in most liquids, such as Water, Alcohol, Ether, etc., and also in dilute acids; but when acted upon by Nitric Acid of a certain strength it liquefies and dissolves.

It has been already shown (p. 12) that when a body dissolves in Nitric Acid the solution is not usually of the same nature as an aqueous solution; and so in this case--the Nitric Acid imparts Oxygen first to the Cotton, and afterwards dissolves it.

Preparation of Pyroxyline.--If, instead of treating Cotton with Nitric Acid, a mixture of Nitric and Sulphuric Acids in certain proportions be used, the effect is peculiar. The fibres contract slightly, but undergo no other visible alteration. Hence we are at first disposed to think the mixed Acids ineffectual. This idea however is not correct, since on making the experiment the properties of the cotton are found to be changed. Its weight has increased by more than one-half; it has become soluble in various liquids, such as Acetic Ether, Ether and Alcohol, etc., and, what is more remarkable, it no longer burns in the air quietly, but explodes on the application of flame with greater or less violence.

This change of properties clearly shows, that although the fibrous structure of the material is unaffected, it is no longer the same substance, and consequently chemists have assigned it a different name, viz. Pyroxyline.

To produce the peculiar change by which Cotton is converted into Pyroxyline, both Nitric and Sulphuric Acids are, as a rule, required; but of the two the former is the most important. On analyzing Pyroxyline, Nitric Acid, or a body analogous to it, is detected in considerable quantity, but not Sulphuric Acid. The latter Acid, in fact, serves but a temporary purpose, viz. to prevent the Nitric Acid from dissolving the pyroxyline, which it would be liable to do if employed alone. The Sulphuric Acid prevents the solution by removing water from the Nitric Acid, and so producing a higher degree of concentration; Pyroxyline, although soluble in a dilute, is not so in the strong Acid, and hence it is preserved.

The property possessed by Oil of Vitriol of removing water from other bodies, is one with which it is well to be acquainted. A simple experiment will serve to illustrate it. Let a small vessel of any kind be filled to about two-thirds with Oil of Vitriol, and set aside for a few days; at the end of that time, and especially if the atmosphere be damp, it will have absorbed sufficient moisture to cause it to flow over the edge.

Now even the strongest reagents employed in chemistry contain, almost invariably, water in greater or lesser quantity. Pure Anhydrous Nitric Acid is a white, solid substance; Hydrochloric Acid is a gas: and the liquids sold under those names are merely solutions. The effect then of mixing strong Oil of Vitriol with aqueous Nitric Acid is to remove water in proportion to the amount used, and to produce a liquid containing Nitric Acid in a high state of concentration, and Sulphuric Acid more or less diluted. This liquid is the Nitro-Sulphuric Acid employed in the preparation of Pyroxyline.

Various forms of Pyroxyline.--Very soon after the first announcement of the discovery of Pyroxyline, most animated discussions arose amongst chemists with regard to its solubility and general properties. Some spoke of a "solution of Gun-Cotton in Ether;" whilst others denied its solubility in that menstruum; a third class, by following the process described, obtained a substance which was not explosive, and therefore could scarcely be termed Gun-Cotton.

On further investigations some of these anomalies were cleared up, and it was found that there were varieties of Pyroxyline, depending mainly upon the degree of strength of the Nitro-Sulphuric Acid employed in the preparation. Still the subject was obscure until the publication of researches by Mr. E. A. Hadow. These investigations, conducted in the Laboratory of King's College, London, were published in the Journal of the Chemical Society. Constant reference will be made to them in the following remarks.

We notice--first, the chemical constitution of Pyroxyline; secondly, its varieties; and thirdly, the means adopted to procure a Nitro-Sulphuric Acid of the proper strength.

a. Constitution of Pyroxyline.--Pyroxyline has been sometimes spoken of as a Salt of Nitric Acid, a Nitrate of Lignine. This view however is erroneous, since it can be shown that the substance present is not Nitric Acid, although analogous to it. It is the Peroxide of Nitrogen, which is intermediate in composition between Nitrous Acid (NO{3}) and Nitric Acid (NO{5}). Peroxide of Nitrogen (NO{4}) is a gaseous body of a dark red colour; it possesses no acid properties, and is incapable of forming a class of salts. In order to understand in what state this body is combined with cotton fibre to form Pyroxyline, it will be necessary to digress for a short time.

Law of Substitution.--By the careful study of the action of Chlorine, and of Nitric Acid, upon various organic substances, a remarkable series of compounds has been discovered, containing a portion of Chlorine or of Peroxide of Nitrogen in the place of Hydrogen. The peculiarity of these substances is, that they strongly resemble the originals in their physical, and often in their chemical properties. It might have been supposed that agents of such active chemical affinities as Chlorine and Oxide of Nitrogen would, by their mere presence in a body, produce a marked effect; yet it is not so in the case before us. The primitive type or constitution of the substance modified remains the same, even the crystalline form being often unaffected. It seems as if the body by which the Hydrogen had been displaced had stepped in quietly and taken up its position in the framework of the whole without disturbance. Many compounds of this kind are known; they are termed by chemists "substitution compounds." The law invariably observed is, that the substitution takes place in equal atoms: a single atom of Chlorine, for instance, displaces one of Hydrogen; two of Chlorine displace two of Hydrogen, and so on, until, in some cases, the whole of the latter element is separated.

In illustration of these remarks, take the following instances:--Acetic Acid contains Carbon, Hydrogen, and Oxygen; by the action of Chlorine the Hydrogen may be removed in the form of Hydrochloric Acid, and an equal number of atoms of Chlorine be substituted. In this way a new compound is formed, termed Chloracetic Acid, resembling in many important particulars the Acetic Acid itself. Notice particularly that the peculiar properties characteristic of Chlorine are completely masked in the substitution body, and no indication of its presence is obtained by the usual tests! A soluble Chloride gives with Nitrate of Silver a white precipitate of Chloride of Silver, unaffected by Acids, but the Chloracetic Acid does not; hence it is plain that the Chlorine exists in a peculiar and Ultimate state of combination different from what is usual.

The substance we have been previously considering, viz. Pyroxyline, affords another illustration of the Law of Substitution. Omitting, for the sake of simplicity, the number of atoms concerned in the change, the action of concentrated Nitric Acid upon ligneous fibre may be thus explained:--

{ Carbon Cotton or { Hydrogen + Nitric Acid { Hydrogen { Oxygen

equals

{ Carbon Pyroxyline or { Hydrogen + Water { Peroxide Nitrogen { Oxygen

Or in symbols:--

CH{11}O + NO{5} = C (H{n-1}NO{4}) O + HO

By a reference to the formula, it is seen that the fifth atom of Oxygen contained in the Nitric Acid takes one of Hydrogen, and forms an atom of Water; the NO{4} then steps in, to fill the gap which the atom of Hydrogen has left. All this is done with so little disturbance that even the fibrous structure of the cotton remains as before.

b. Chemical Composition of the varieties of Pyroxyline.--Mr. Hadow has succeeded in establishing four different substitution compounds, which, as no distinctive nomenclature has been at present proposed, may be termed compounds A, B, C, and D.

Compound A is the most explosive Gun-Cotton, and contains the largest amount of Peroxide of Nitrogen. It dissolves only in Acetic Ether, and is left on evaporation as a white powder. It is produced by the strongest Nitro-Sulphuric Acid which can be made.

Compounds B and C, either separate or in a state of mixture, form the soluble material employed by the Photographer. They both dissolve in Acetic Ether, and also in a mixture of Ether and Alcohol. The latter, viz. C, also dissolves in glacial Acetic Acid. They are produced by a Nitro-Sulphuric Acid slightly weaker than that used for A, and contain a smaller amount of Peroxide of Nitrogen.

Compound D resembles what has been termed Xyloidine, that is, the substance produced by acting with Nitric Acid upon Starch. It contains less Peroxide of Nitrogen than the others, and dissolves in Ether and Alcohol, and also in Acetic Acid. The ethereal solution leaves, on evaporation, an opaque film, which is highly combustible, but not explosive.

By bearing in mind the properties of these compounds, many of the anomalies complained of in the manufacture of Gun-Cotton disappear. If the Nitro-Sulphuric Acid employed is too strong, the product will be insoluble in Ether; whilst if it is too weak, the fibres are gelatinized by the Acid and partly dissolved.

c. Means adopted to procure a Nitro-Sulphuric Acid of the requisite strength for preparing Pyroxyline.--This is a point of more difficulty than would at first appear. It is easy to determine an exact formula for the mixture, but not so easy to hit upon the proper proportions of the acids required to produce that formula; and a very slight departure from them altogether modifies the result. The main difficulty lies in the uncertain strength of commercial Nitric Acid. Oil of Vitriol is more to be depended upon, and has a tolerably uniform Sp. Gr. of 1·836; but Nitric Acid is constantly liable to variation; hence it becomes necessary to make a preliminary determination of its real strength, which is done either by taking the specific gravity and referring to tables, or, better still, by a direct analysis. As each atom of Sulphuric Acid removes only a given quantity of water, it follows that the weaker the Nitric Acid, the larger the amount of Sulphuric which will be required to bring it up to the proper degree of concentration.

The later experience of the writer induces him to believe, that the specific gravity of Oil of Vitriol cannot always be taken as an indication of its real strength; which is best ascertained by analysis.

To avoid the trouble necessarily attendant upon these preliminary operations, many prefer to use, in place of Nitric Acid itself, one of the salts formed by the combination of Nitric Acid with an alkaline base. The composition of these salts, provided they are pure and nicely crystallized, can be depended on.

Nitrate of Potash, or Saltpetre, contains a single atom of Nitric Acid united with one of Potash. It is an anhydrous salt, that is, it has no water of crystallization. When strong Sulphuric Acid is poured upon Nitrate of Potash in a state of fine powder, in virtue of its superior chemical affinities it appropriates to itself the Alkali and liberates the Nitric Acid. If care be taken to add a sufficient excess of the Sulphuric Acid, a solution is obtained containing Sulphate of Potash dissolved in Sulphuric Acid, and free Nitric Acid. The presence of the Sulphate of Potash (or, more strictly speaking, of the Bi-Sulphate) does not in any way interfere with the result, and the effect is the same as if the mixed acids themselves had been used.

The reaction may be thus represented:--

Nitrate of Potash plus Sulphuric Acid in excess = Bisulphate Potash plus Nitro-Sulphuric Acid.

CHEMISTRY OF THE SOLUTION OF PYROXYLINE IN ETHER AND ALCOHOL, OR "COLLODION."

The substitution compounds B and C, already alluded to as forming the Soluble Cotton of Photographers, are both abundantly soluble in Acetic Ether. This liquid however is not adapted for the purpose required, inasmuch as on evaporation it leaves the Pyroxyline in the form of a white powder, and not as a transparent layer.

The rectified Ether of commerce has been found to answer better than any other liquid as a solvent for Pyroxyline.

If the sp. gravity be about ·750, it contains invariably a small proportion of Alcohol, which appears to be necessary; the solution not taking place with absolutely pure Ether. The Pyroxyline, if properly prepared, begins almost immediately to gelatinize by the action of the Ether, and is soon completely dissolved. In this state it forms a slimy solution, which, when poured out on a glass plate, dries up into a horny transparent layer.

In preparing Collodion for Photographic purposes, we find that its physical properties are liable to considerable variation. Sometimes it appears very thin and fluid, flowing on the glass almost like water, whilst at others it is thick and glutinous. The causes of these differences will now engage our attention. They may be divided into two classes: first, those relating to the Pyroxyline; second, to the solvents employed.

a. Variation of Properties in different Samples of soluble Pyroxyline.--The substitution compounds A, B, C, and D differ, as already shown, in the percentage amount of Peroxide of Nitrogen present, and the former are more explosive and insoluble than the latter. But it often happens in preparing Pyroxyline, that two portions of Nitro-Sulphuric Acid taken from the same bottle yield products which vary in properties, although they are necessarily the same in composition.

Taking extremes in illustration, we notice two principal modifications of soluble Pyroxyline.

The first, when treated with the mixture of Ether and Alcohol, sinks down to a gummy or gelatinous mass, which gradually dissolves on agitation The solution is very fluid in proportion to the number of grains used, and when poured out spreads into a beautifully smooth and glassy surface, which is quite structureless, even when highly magnified. The film adheres tightly to the glass, and when the finger is drawn across it, separates in short fragments, and broken pieces.

The second variety produces a Collodion which is thick and glutinous, flowing over the glass in a slimy manner, and soon setting into numerous small waves and cellular spaces. The film lies loose upon the glass, is apt to contract on drying, and may be pushed off by the finger in the form of a connected skin.

This subject is not thoroughly understood, but it is known that the temperature of the Nitro-Sulphuric Acid at the time of immersing the Cotton influences the result. The soluble variety is produced by hot acids; the second, or glutinous, by the same acids employed cold, or only slightly warm. The best temperature appears to be from 130° to 155° Fahrenheit; if it rises much beyond that point, the acids act upon and dissolve the Cotton.

b. The physical properties of Collodion affected by the proportions and purity of the Solvents.--Pyroxyline of the varieties termed B and C dissolves freely in a mixture of Ether and Alcohol; but the characters of the resulting solution vary with the relative proportions of the two solvents.

When the Ether is in large excess, the film is inclined to be strong and tough, so that it can often be raised by one corner and lifted completely off the plate without tearing. It is also very contractile, so that a portion of the Collodion poured on the hand draws together and puckers the skin as it dries. If spread upon a glass plate in the usual way, the same property of contractility causes it to retract and separate from the sides of the glass.

These properties, produced by Ether in large proportion, disappear entirely on the addition of more Alcohol. The transparent layer is now soft and easily torn, possessing but little coherency. It adheres to the surface of the glass more firmly, and exhibits no tendency to contract and separate from the sides.

From these remarks it will be gathered that an excess of Ether, and a low temperature in preparing the Pyroxyline, both favour the production of a contractile Collodion; whilst on the other hand an abundance of Alcohol, and a hot Nitro-Sulphuric Acid, tend to produce a short and non-contractile Collodion.

The physical properties of Collodion are affected by another cause, viz. by the strength and purity of the solvents, or, in other words, their freedom from dilution with water. If a few drops of water be purposely added to a sample of Collodion, the effect is seen to be to precipitate the Pyroxyline in flakes to the bottom of the bottle. There are many substances known in chemistry which are soluble in spirituous liquids, but behave in the same manner as Pyroxyline in this respect.

The manner in which water gains entrance into the Photographic Collodion is usually by the employment of Alcohol or Spirit of Wine which has not been highly rectified. In that case the Collodion is thicker, and flows less readily than if the Alcohol were stronger. Sometimes the texture of the film left upon evaporation is injured; it is no longer homogeneous and transparent, but semi-opaque, reticulated, or honeycombed, and so rotten that a stream of water projected upon the plate washes it away.

These effects are to be attributed not to the Alcohol, but to the water introduced with it; and the remedy will be to procure a stronger spirit, or, if that cannot be done, to increase the amount of Ether. Collodion prepared with a large proportion of Ether, and water, but a small quantity of Alcohol, is often very fluid and structureless at first, adhering to the glass with some tenacity and having a short texture; but it tends to become rotten when used to coat many plates successively, the water on account of its lesser volatility accumulating in injurious quantity in the last portions.

THE COLORATION OF IODIZED COLLODION EXPLAINED.

Collodion iodized with the Iodides of Potassium, Ammonium, or Zinc, soon assumes a yellow tint, which in the course of a few days or weeks, according to the temperature of the atmosphere, deepens to a full brown. This gradual coloration, due to a development of Iodine, is caused partly by the Ether and partly by the Pyroxyline.

Ether may, with proper precautions, be preserved for a long time in a pure state, but on exposure to the joint action of air and light it undergoes a slow process of oxidation, attended with formation of Acetic Acid and a peculiar principle resembling in properties ozone, or Oxygen in an allotropic and active condition. Iodide of Potassium or Ammonium is decomposed by Ether in this state. Acetate of the Alkali, and Hydriodic Acid (HI), being first produced. The ozonized substance then removes Hydrogen from the latter compound, and liberates Iodine, which dissolves and tinges the liquid yellow.

A simple solution of an Alkaline Iodide in Alcohol and Ether does not, however, become so quickly coloured as Iodized Collodion; and hence it is evident that the presence of the Pyroxyline produces an effect. It may be shown that Alkaline Iodides slowly decompose Pyroxyline, and that a portion of Peroxide of Nitrogen is set free: this body, containing loosely combined oxygen, tends powerfully to eliminate Iodine, as may be seen by adding a few drops of the yellow commercial Nitrous acid to a solution of Iodide of Potassium.

The stability of the particular Iodide used in Iodizing Collodion, influences mainly the rate of coloration, though elevation of temperature and exposure to light are not without effect. Iodide of Ammonium is the least stable, and Iodide of Cadmium the most so; Iodide of Potassium being intermediate. Collodion iodized with pure Iodide of Cadmium usually remains nearly colourless to the last drop, if kept in a cool and dark place.

As the presence of free Iodine in Collodion affects its photographic properties, it may sometimes be necessary to remove it. This is done by inserting a strip of Silver-foil; which decolorizes the liquid, by forming Iodide of Silver, soluble in the excess of Alkaline Iodide (p. 42). Metallic Cadmium, and metallic Zinc, have the same effect.

When Methylated Spirits are employed in the manufacture of Collodion, the Iodine first liberated is afterwards either partially or entirely reabsorbed, the liquid acquiring at the same time an acid reaction to test-paper.