papers in the Journal of Physical Chemistry for 1908 and 1909, has applied it generally to the reactions under consideration. Any electrolytic action demands a certain minimum electromotive force, this, however, can be diminished by suitable depolarizers, which generally act by combining with a product of the decomposition. Similarly, in some photochemical reactions the low electromotive force of the light is sufficient to induce decomposition, but in other cases a depolarize must be present. For example, ferric chloride in aqueous solution is unchanged by light, but in alcoholic solution reduction to ferrous chloride occurs, the liberated chlorine combining with the alcohol. In the same way Bancroft showed that the solvent media employed in photographic plates act as depolarizers. The same theory explains the action of sensitizers, which may act optically or chemically. In the first case they are substances having selective absorption, and hence alter the sensitivity of the system to certain rays. In the second case there are no strong absorption bands, and the substances act by combining with the decomposition products. Bancroft applied his theory to the explanation of photochemical oxidation, and also to the chlorination and bromination of hydrocarbons. In the latter case it is supposed that the halogen produces ions; if the positive ions are in excess side chains are substituted, if the negative the nucleus.
Standard treatises are: J. M. Eder, Handbuch der Photographie, vol 1 pt. 2 (1906); H. W. Vogel, Photochemie (1906). An account of the action of light on organic compounds is given in A. W. Stewart, Recent Advances in Organic Chemistry (1908).
PHOTOGRAPHY (Gr. φῶς, light, and γράφειν, to write),
the science and art of producing pictures by the action of light
on chemically prepared (sensitized) plates or films.
History.
It would be somewhat difficult to fix a date when what we now know as “photographic action” was first recorded. No doubt the tanning of the skin by the sun’s rays was what was first noticed, and this is as truly the effect of solar radiation as is the darkening of the sensitive paper which is now in use in photographic printing operations. We may take it that K. W. Scheele was the first to investigate the darkening action of sunlight on silver chloride. He found that when silver chloride was exposed to the action of light beneath water there was dissolved in the fluid a substance which, on the addition of lunar caustic (silver nitrate), caused the precipitation of new silver chloride, and that on applying a solution of ammonia to the blackened chloride an insoluble residue of metallic silver was left behind He also noticed that of the rays of the spectrum the violet most readily blackened the silver chloride. In Scheele, then, we have the first who applied combined chemical and spectrum analysis to the science of photography. In 1782 J. Senebier repeated Scheele’s experiments, and found that in fifteen seconds the violet rays blackened silver chloride as much as the red rays did in twenty minutes.[1] In 1798 Count Rumford contributed a paper to the Philosophical Transactions entitled “An inquiry concerning the chemical properties that have been attributed to light,” in which he tried to demonstrate that all effects produced on metallic solution could be brought about by a temperature somewhat less than that of boiling water. Robert Harrup in 1802, however, conclusively showed in Nicholson’s Journal that, at all events, salts of mercury were reduced by visible radiation and not by change of temperature.
In 1801 we come to the next decided step in the study of photographic action, when Johann Wilhelm Ritter (1776–1810) proved the existence of rays lying beyond the violet, and found that they had the power of blackening silver chloride. Such a discovery naturally gave a direction to the investigations of others, and Thomas Johann Seebeck (1770–1831) (between 1802 and 1808) and, in 1812, Jacques Etienne Bérard (1789–1869) turned their attention to this particular subject, eliciting valuable information. We need only mention two or three other cases where the influence of light was noticed at the beginning of the 19th century. William Hyde Wollaston observed the conversion of yellow gum guaiacum into a green tint by the violet rays, and the restoration of the colour by the red rays—both of which are the effect of absorption of light, the original yellow colour of the gum absorbing the violet rays, whilst the green colour to which it is changed absorbs the red rays. Sir Humphry Davy found that puce-coloured lead oxide, when damp, became red in the red rays, whilst it blackened in the violet rays, and that the green mercury oxide became red in the red rays-again an example of the necessity of absorption to effect a molecular or chemical change in a substance. U. R. T. Le Bouvier Desmorties in 1801 observed the change effected in Prussian blue, and Carl Wilhelm Bockman noted the action of the two ends of the spectrum on phosphorus, a research which John William Draper extended farther in America at a later date.
To England belongs the honour of first producing a photograph by utilizing Scheele's observations on silver chloride. In June 1802 Thomas Wedgwood (1771–1805) published in the Journal of the Royal Institution the paper—“An account of a method of copying paintings upon glass and of making profiles by the agency of light upon nitrate of silver, with observations by H. Davy.” He remarks that white paper or white leather moistened with a solution of silver nitrate undergoes no change when kept in a dark place, but on being exposed to the daylight it speedily changes colour, and, after passing through various shades of grey and brown, becomes at length nearly black. The alteration of colour takes place more speedily in proportion as the light is more intense.
“In the direct beam of the sun two or three minutes are sufficient to produce the full effect, in the shade several hours are required, an light transmitted through different-coloured glasses acts upon it with different degrees of intensity. Thus it is found that red rays, or the common sunbeams passed through red glass, have very little action upon it; yellow and green are more efficacious, but blue and violet light produce the most decided and powerful effects.”
Wedgwood goes on to describe the method of using this prepared paper by throwing shadows on it, and inferentially by what we now call “contact printing.” He states that he has been unable to fix his prints, no washing being sufficient to eliminate the traces of the silver salt which occupied the unexposed or shaded portions. Davy in a note states that he has found that, though the images formed by an ordinary camera obscura were too faint to print out in the solar microscope, the images of small objects could easily be copied on such paper.
“In comparing the effects produced by light upon muriate of silver (silver chloride) with those upon the nitrate it seemed evident that the muriate was the more susceptible, and both were more readily acted upon when moist than when dry—a fact long ago known. Even in the twilight the colour of the moist muriate of silver, spread upon paper, slowly changed from white to faint violet; though under similar circumstances no intermediate alteration was produced upon the nitrate. . . . Nothing but a method of preventing the unshaded parts of the delineations from being coloured by exposure to the day is wanting to render this process as useful as it is elegant.”
In this method of preparing the paper lies the germ of the silver-printing processes of modern times, and it was only by the spread of chemical knowledge that the hiatus which was to render the “process as useful as it is elegant” was filled up—when sodium thiosulphate (hyposulphite of soda), discovered by Francois Chaussier in 1799, or three years before Wedgwood published his paper, was used for making the print permanent. Here we must call attention to an important observation by Seebeck of Jena in 1810. In the Farbenlehre of Goethe he says:—
“When a spectrum produced by a properly constructed prism is thrown upon moist chloride of silver paper, if the printing be continued for from fifteen to twenty minutes, whilst a constant position for the spectrum is maintained by any means, I observe the following. In the violet the chloride is a reddish brown (sometimes more violet, sometimes more blue), and this coloration extends well beyond the limit of the violet; in the blue the chloride takes a clear blue tint, which fades away, becoming lighter in the green. In the yellow usually found the chloride unaltered; sometimes, however, it had a light yellow tint; in the red and beyond the red it took a rose or lilac tint. This image of the spectrum shows beyond the red and the violet a region more or less light and uncoloured, This is how the decomposition of the silver chloride is seen in this region. Beyond
- ↑ It may here be remarked that had he used a pure spectrum he would have found that the red rays did not blacken the material in the slightest degree.
