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PHOTOGRAPHIC ACTION STUDIED SPECTROSCOPICALLYby@scientificamerican

PHOTOGRAPHIC ACTION STUDIED SPECTROSCOPICALLY

by Scientific American November 13th, 2023
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At the last meeting of the Chemical Society Captain Abney gave a lecture on the above subject to a large audience. We may premise by saying that the demonstrations he gave were carried out principally by means of experiments on paper, to enable his hearers to understand the different points he wished to enforce. The lecture was commenced by insisting on the fact that all photographic action took place within the molecules of the compound acted upon and not on the molecule itself, and from this he deduced that the absorption of radiation which take place by such compounds is principally caused by the atoms composing the molecule. This was found to be the case in the organic liquids, which the lecturer to some extent had investigated, where he had further traced the absorption to the vibrating atoms of hydrogen in those bodies. In order to properly investigate the action of light it was necessary to ascertain which components of light in the spectrum were the chief agents in causing it, and this led him to consider the means to be employed to obtain a spectrum. The effects of diffraction gratings were first discussed, and in two which were shown it was found that in some spectra the visible portions were dimmed; in others the ultra-violet and the infra-red were almost entirely absent. It thus became necessary to investigate the condition of a grating before placing any confidence in the results obtained. This was the first pitfall into which an experimentalist was liable to fall. If prisms were used for obtaining the spectrum, then precautions had also to be taken, since all glass absorbed a portion of the ultra-violet rays and some the infra-red. On the whole, he considered that the best glass to use was pure white flint glass for the collimator, the prisms, and the camera lens. Another inquiry that was necessary was the source of radiation which it was proposed to use. Diagrams showed the unsatisfactory nature of solar radiation, and a photograph of the whole spectrum, taken with it under certain atmospheric conditions in which the effect of the green rays were almost nil, demonstrated the false conclusions that might be deduced as to the sensitiveness of any particular compound. Captain Abney also showed the satisfactory conditions which existed in using the crater of the positive pole of the electric arc light as a source, and by diagrams illustrated the inferiority of an incandescent light for the purpose, owing to the deficiency of violet and ultra-violet rays. Having thus settled the source of illumination and the kind of apparatus to employ, he next considered the conditions under which the sensitive salts were to be exposed. The action of ordinary sensitizers was explained and demonstrated by experiments, from which point the results of certain colored sensitizers were considered. Thus, various aniline dyes were proved to be bromine absorbents, and likewise, more or less, to be capable of being acted upon by light in those regions of the spectrum they absorbed. The result of the two effects was to produce a developable image of the spectrum just in those parts to which the salt of silver was sensitive, and also in the parts where the dye itself was acted upon. The latter effect was traced to the organic matter being oxidized in the presence of the sensitive silver salt.
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Scientific American Supplement, No. 392, July 7, 1883 by Various, is part of the HackerNoon Books Series. You can jump to any chapter in this book here. PHOTOGRAPHIC ACTION STUDIED SPECTROSCOPICALLY.

PHOTOGRAPHIC ACTION STUDIED SPECTROSCOPICALLY.

At the last meeting of the Chemical Society Captain Abney gave a lecture on the above subject to a large audience. We may premise by saying that the demonstrations he gave were carried out principally by means of experiments on paper, to enable his hearers to understand the different points he wished to enforce. The lecture was commenced by insisting on the fact that all photographic action took place within the molecules of the compound acted upon and not on the molecule itself, and from this he deduced that the absorption of radiation which take place by such compounds is principally caused by the atoms composing the molecule. This was found to be the case in the organic liquids, which the lecturer to some extent had investigated, where he had further traced the absorption to the vibrating atoms of hydrogen in those bodies. In order to properly investigate the action of light it was necessary to ascertain which components of light in the spectrum were the chief agents in causing it, and this led him to consider the means to be employed to obtain a spectrum.


The effects of diffraction gratings were first discussed, and in two which were shown it was found that in some spectra the visible portions were dimmed; in others the ultra-violet and the infra-red were almost entirely absent. It thus became necessary to investigate the condition of a grating before placing any confidence in the results obtained. This was the first pitfall into which an experimentalist was liable to fall. If prisms were used for obtaining the spectrum, then precautions had also to be taken, since all glass absorbed a portion of the ultra-violet rays and some the infra-red. On the whole, he considered that the best glass to use was pure white flint glass for the collimator, the prisms, and the camera lens. Another inquiry that was necessary was the source of radiation which it was proposed to use. Diagrams showed the unsatisfactory nature of solar radiation, and a photograph of the whole spectrum, taken with it under certain atmospheric conditions in which the effect of the green rays were almost nil, demonstrated the false conclusions that might be deduced as to the sensitiveness of any particular compound.


Captain Abney also showed the satisfactory conditions which existed in using the crater of the positive pole of the electric arc light as a source, and by diagrams illustrated the inferiority of an incandescent light for the purpose, owing to the deficiency of violet and ultra-violet rays. Having thus settled the source of illumination and the kind of apparatus to employ, he next considered the conditions under which the sensitive salts were to be exposed. The action of ordinary sensitizers was explained and demonstrated by experiments, from which point the results of certain colored sensitizers were considered. Thus, various aniline dyes were proved to be bromine absorbents, and likewise, more or less, to be capable of being acted upon by light in those regions of the spectrum they absorbed. The result of the two effects was to produce a developable image of the spectrum just in those parts to which the salt of silver was sensitive, and also in the parts where the dye itself was acted upon. The latter effect was traced to the organic matter being oxidized in the presence of the sensitive silver salt.


The sensitizing effect of one silver compound upon another was then gone into, and experiments and photographs showed where two salts of silver were in contact with one another, and without an energetic sensitizer being at hand, that the one when acted upon by light absorbed the halogen liberated from the other through the same cause and that a new molecule was formed. This was of importance, since in photographic spectroscopic researches a conclusion might be arrived at that a body suffered absorption in those regions of the spectrum where this interesting reaction took place, whereas in reality the phenomenon might be due to the silver salts employed. This was another pitfall for the unwary. Again, it became necessary in studying photographic action to make sure that the effect of radiation was only a reducing action, and that the results were not vitiated by some other action.


The destruction by oxidizing agents of the effect produced by light was then experimentally demonstrated, and photographs of the spectrum showed that this effect was increased by the action of light itself. Thus, when immersing a plate sensitive to all radiations, visible and invisible, in a very dilute solution of nitric acid, bichromate of potash, or hydroxyl, it was shown that if the plate were exposed to light, first the parts acted upon by the red rays were reduced before the parts not acted upon at all by the spectrum, thus conclusively proving that light itself helped forward the oxidation or so-called solarization of the image. It thus became a struggle, under ordinary circumstances, between the reducing action on the normal salt and the oxidizing action on the altered salt as to which should gain the mastery. If the reducing action of any particular ray were the most active, then a negative image resulted, whereas if the oxidizing action were in the ascendant, a positive image resulted. Thus, in determining the action of light on a particular salt, this antagonism had to be taken into account, and exposure made with such precautions that no oxidizing action could occur, as would be the case if an inorganic sensitizer, such as sulphite of soda, were used.


The reversal of the image by soluble haloid salts, such as bromide of potassium, was then dwelt upon with experimental demonstration. It was shown that the merest trace of soluble haloid would reverse an image by the extraction of bromine from it, and the fact that the most refrangible part of the spectrum was principally efficacious in completing this action showed how necessary it was to avoid falling into error when analyzing photographic action by the spectroscope. A reference was next made to gelatine plates, in which, owing to their preparation, reversal through the above cause was most likely to take place, and a plate soaked in sulphite of soda and exposed in the camera for a couple of minutes--a time largely in excess of that necessary to give a reversal under ordinary circumstances--proved the efficacy of the oxygen absorber, the image remaining in its normal condition after development.


The lecturer closed his remarks by showing the different molecular states of iodide, bromide, and chloride of silver, as produced by different modes of preparation. The color of the film by transmitted light in every case indicated the effect which was likely to be produced on them, and the photographed spectrum in each of them showed the remarkable differences that were found. The points raised by Captain Abney at different times are well worthy the study of scientific photographers, since strict attention to the modes of exposure to the spectrum, to the instruments employed, and to the source of light used can alone insure accuracy in comparative experiments.--Br. Jour. of Photo.




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This book is part of the public domain. Various (2005). Scientific American Supplement, No. 392, July 7, 1883. Urbana, Illinois: Project Gutenberg. Retrieved https://www.gutenberg.org/cache/epub/8742/pg8742-images.html


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