produced the spectrum colours, but it was found better to heat the plate till it assumed a rose tint. At a later date Niepce de St Victor chlorinized by chloride of lime, and made the surface more sensitive by applying a solution of lead chloride in dextrin G. W. Simpson also obtained coloured images on silver chloride emulsion in collodion, but they were less vivid and satisfactory than those obtained on daguerreotype plates. Poitevin obtained coloured images on ordinary silver chloride paper by preparing it in the usual manner and washing it and exposing it to light. It was afterwards treated with a solution of potassium bichromate and cupric sulphate, and dried in darkness. Sheets so prepared gave coloured images from coloured pictures, which he stated could be fixed by sulphuric acid (Comptes rendus, 1868, 61, p. 11). In the Bulletin de la Société Française (1874) Colonel St Florent described experiments which he made with the same object. He immersed ordinary or albuminized paper in silver nitrate and afterwards plunged it into a solution of uranium nitrate and zinc chloride acidulated with hydrochloric acid, it was then exposed to light till it took a violet, blue or lavender tint. Before exposure the paper was floated on a solution of mercuric nitrate, its surface dried, and exposed to a coloured image.
It is supposed—though it is very doubtful if it be so—that the nature of the chloride used to obtain the silver chloride has a great effect on the colours impressed; and Niepce in 1857 made some observations on the relationship which seemed to exist between the coloured flames produced by the metal and the colour impressed on a plate prepared with a chloride of such a metal. In 1880 Abney showed that the production of colour really resulted from the oxidation of the chloride that was coloured by light Plates immersed in a solution of hydrogen peroxide took the colours of the spectrum much more rapidly than when not immersed, and the size of the molecules seemed to regulate the colour He further stated that the whole of the spectrum colours might be derived from a mixture of two or at most three sizes of molecules
In l84l, Robert Hunt published some results of colour-photography by means of silver fluoride. A paper was washed with silver nitrate and with sodium fluoride, and afterwards exposed to the spectrum. The action of the spectrum commenced at the centre of the yellow ray and rapidly proceeded upwards, arriving at its maximum in the blue ray. As far as the indigo the action was uniform, whilst in the violet the paper took a brown tint. When it was previously exposed, however, a yellow space was occupied where the yellow rays had acted, a green band where the green had acted, whilst in the blue and indigo it took an intense blue, and over the violet there as a ruddy brown. In reference to these coloured images on paper it must not be forgotten that pure salts of silver are not being dealt with as a rule. An organic salt of silver is usually mixed with silver chloride paper, the organic salt being due to the sizing of the paper, which towards the red end of the spectrum is usually more sensitive than the chloride. If a piece of ordinary silver chloride paper is exposed to the spectrum till an impression is made, it wi11 usually be found that the blue colour of the darkened chloride is mixed with that due to the coloration of the darkened organic compound of silver in the violet region, whereas in the blue and green this organic compound IS alone affected, and is of a different colour from that of the darkened mixed chloride and organic compound This naturally gives an impression that the different rays yield different tints, whereas this result is simply owing to the different range of sensitiveness of the bodies. In the case of the silver chlorinized plate and of true collodio-chloride, in which no organic salt has been dissolved, we have a true coloration by the spectrum. At present there is no means of permanently fixing the coloured images which have been obtained, the effect of light being to destroy them. If protected from oxygen they last longer than if they have free access to it, as is the case when the surface is exposed to the air.
A method devised by Gabrielle Lippmann, of Paris, by which the natural colours of objects are reproduced by means of interference, may be briefly described as follows: A sensitive plate is placed in contact with a film of mercury, and the exposure to the spectrum, or to the image of coloured objects to be photographed, is made through the back of the plate. On development, the image appears coloured when viewed at one particular angle, the colours being approximately those of the object. The necessary exposure to produce this result was very prolonged in the first experiments in which the spectrum was photographed, and a longer exposure had to be given to the red than was required for the blue. Lippmann at first employed collodion dry plates, prepared, it is believed, with albumen, and it required considerable manipulation to bring out the colours correctly. A. Lumière used gelatin plates dyed with appropriate dyes (or the chromatic plates); the exposure was much diminished, and very excellent representations were produced of all natural colours. The main point to aim at in the preparation of the plate seems to be to obtain a very sensitive film without any, or, at all events, with the least possible, “grain” in the sensitive salt. A formula published by Lumière seems to attain this object. Viewed directly, the developed images appear like ordinary negatives, but when held at an angle to the light the colours are vivid. They are not pure monochromatic colours, but have very much the quality of colours obtained by polarized light. It appears that the are produced by what may be termed “nodes” of different-coloured lights acting within the film. Thus in photographing the spectrum, rays penetrate to the reflecting mercury and are reflected back from it, and these, with the incident waves of light, form nodes where no motion exists, in a somewhat similar way to those obtained in a cord stretched between two points when plucked. In the negative these nodal points are found in the thickness of the silver deposit. When white light is sent through the film after the image has been developed, theoretically only rays of the wavelengths which formed these nodes are reflected to the eye, and thus we get an impression of colour.
Action of Light on Chemical Compounds.
Reference has been made above to early investigations on the chemical action of light. In 1777 Karl Wilhelm Scheele (Hunt's Researches in Light) made the following experiments on silver salts:—
“I precipitated a solution of silver by sal-ammoniac; then I edulcorated it and dried the precipitate and exposed it to the beams of the sun for two weeks; after which I stirred the powder, and repeated the same several times. Hereupon I poured some caustic spirit of sal-ammoniac (strong ammonia) on this, in all appearance, black powder, and set it by for digestion. This menstruum dissolved a quantity of luna cornua (horn silver), though some black powder remained undissolved. The powder having been washed was, for the greater part, dissolved by a pure acid of nitre (nitric acid), which, by the operation, acquired volatility. This solution I precipitated again by means of sal-ammoniac into horn silver. Hence it follows that the blackness which the luna cornua acquires from the sun's light, and likewise the solution of silver poured on chalk, is silver by reduction. . . . I mixed so much of distilled water with well-edulcorated horn silver as would Just cover this powder. The half of this mixture I poured into a white crystal phial, exposed it to the beams of the sun, and shook it several times each day; the other half I set in a dark place. After having exposed the one mixture during the space of two weeks, I filtrated the water standing over the horn silver, grown already black; I let some of this water fall by drops in a solution of silver, which was immediately precipitated into horn silver.”
This, as far as we know, is the first intimation of the reducing action of light. From this it is evident that Scheele had found that the silver chloride was decomposed by the action of light liberating some form of chlorine. Others have repeated these experiments and found that chlorine is really liberated from the chloride; but it is necessary that some body should be present which would absorb the chlorine, or, at all events, that the chlorine should be free to escape. A tube of dried silver chloride, sealed up in vacuo, will not discolour in the light, but keeps its ordinary white colour. A pretty experiment is to seal up in vacuo, at one end of a bent tube, perfectly dry chloride, and at the other a drop of mercury. The mercury vapour volatilizes to a certain extent and fills the tube. When exposed to light chlorine is liberated from the chloride, and calomel forms on the sides of the tube. In this case the chloride darkens. Again, dried chloride sealed up in dry hydrogen discolours, owing to the combination of the chlorine with the hydrogen. Poitevin and H. W. Vogel first enunciated the law that for the reduction by light of the haloid salts of silver halogen absorbents were necessary, and it was by following out this law that the present rapidity in obtaining camera images has been rendered possible. To put it briefly, then, the visible action of light is a reducing action, which is aided by or entirely due to the fact that other bodies are present which will absorb the halogens.
In the above we have alluded to the visible results on silver salts. It by no means follows that the exposure of a silver salt to light for such a brief period as to leave no visible effect must be due to the same effect, that is, that any of the molecules are absolutely reduced or split up by the light. That this or some other action takes place is shown by the fact that the silver salt is capable of alkaline development, that is, the particles
