On the Change of Refrangibility of Light.--No. II

Author(s) G. G. Stokes
Year 1853
Volume 143
Pages 13 pages
Language en
Journal Philosophical Transactions of the Royal Society of London

Full Text (OCR)

XVI. On the Change of Refrangibility of Light.—No. II. By G. G. Stokes, M.A., F.R.S., Fellow of Pembroke College, and Lucasian Professor of Mathematics in the University of Cambridge. Received June 16,—Read June 26, 1853. The chief object of the present communication is to describe a mode of observation, which occurred to me after the publication of my former paper, which is so convenient, and at the same time so delicate, as to supersede for many purposes methods requiring the use of sun-light. On account of the easiness of the new method, the cheapness of the small quantity of apparatus required, and above all, on account of its rendering the observer independent of the state of the weather, it might be immediately employed by chemists in discriminating between different substances. I have taken the present opportunity of mentioning some other matters connected with the subject of these researches. The articles are numbered in continuation of those of the former paper. Method of observing by the use of Absorbing Media. 241. Conceive that we had the power of producing at will media which should be perfectly opake with regard to rays belonging to any desired regions of the spectrum, from the extreme red to the most refrangible invisible rays, and perfectly transparent with regard to the remainder. Imagine two such media prepared, of which the second was opake with regard to those rays of the visible spectrum with regard to which the first was transparent, and vice versa. It is clear that if both media were held in front of the eye no light would be perceived. The same would still be the case if the first medium were removed from the eye, and placed so as to intercept all the rays which fell on certain objects, which were then viewed through the second, provided the objects did nothing more than reflect, refract, scatter, or absorb the incident rays. But if any of the objects had the property of emitting rays of one refrangibility under the influence of rays of another, it might happen that some of the rays so emitted were capable of passing through the second medium, in which case the object would appear luminous in a dark field. 242. Let us consider now how the media must be arranged so as to bring out to the utmost the sensibility of a given substance. To take a particular instance, suppose the substance to be glass coloured by uranium. In this case the sensibility of the medium begins, with almost absolute abruptness, near the fixed line $b$ of Fraunhofer, and continues from thence onwards. The dispersed light has the same, or at least almost rigorously the same, composition throughout, and consists exclusively of rays less refrangible than $b$. Consequently, we should have to prepare a first medium which was opake with regard to the visible rays less refrangible than $b$, and transparent with respect to the rays, whether visible or invisible, more refrangible, and a second medium complementary to the former in the manner described in the preceding article. If the pair of media were still strictly complementary in this manner, but the point of the spectrum at which the transparency of the first medium began and that of the second ended were situated at some distance from $b$, the sensibility of the glass would be exhibited as before, only the maximum effect would not be produced, on account of the absorption of a portion either of the active or of the dispersed rays, according as the point in question was situated above or below $b$. Now, although the commencement of the sensibility of canary glass is unusually abrupt, it generally happens that the sensibility of a medium, or at least the main part of it, comes on with great rapidity, and lasts throughout the rest of the spectrum, though frequently it is most considerable in a region extending not very greatly beyond the point where it commenced. In those cases in which the dispersion of different tints commenced at two or three different places in the spectrum, I have almost always had evidence of the independent presence of different sensitive principles, to which the observed effects were respectively due. Hence, if we could prepare absorbing media at pleasure, we should get ready for general use in these observations a few pairs of media complementary in the particular manner already described, but having the points of the spectrum at which the transparency of the first medium commenced and that of the second ended different in different pairs, situated say in the yellow for one pair, in the blue for another, in the extreme violet for a third. 243. It is not of course possible to prepare media in this manner at pleasure, and all we can do is to select from among those which occur in nature. Nevertheless it is useful, as a guide in the selection, to consider what constitutes the ideal perfection of absorbing media for this particular purpose. But before proceeding to mention the media which I have found convenient, I will describe the arrangement which I have adopted for admitting the light. A hole was cut in the window-shutter of a darkened room, and through this the light of the clouds and external objects entered in all directions. The diameter of the hole was four inches, and it might perhaps have been still larger with advantage. A small shelf, blackened on the top, which could be screwed on to the shutter immediately underneath the hole, served to support the objects to be examined, as well as the first absorbing medium. This, with a few coloured glasses, forms all the apparatus which it is absolutely necessary to employ, though for the sake of some experiments it is well to be provided also with a small tablet of white porcelain, and an ordinary prism, and likewise with one or two vessels for holding fluids. In the observation, the first medium is placed resting on the shelf so as to cover the hole; the object is placed on the shelf immediately in front of the hole; the second medium is held anywhere between the eyes and the object. As it is not possible to obtain media which are strictly complementary, it will happen that a certain quantity of light is capable of passing through both media. This might no doubt be greatly reduced by increasing the absorbing power of the media, but it is by no means advisable to do so to any great extent, because it is important that the second medium should transmit as many as possible of the rays which are of such refrangibilities as to be stopped by the first. Accordingly, it might sometimes be doubtful whether the illumination perceived on the object were due merely to scattered light which had passed through both media, or to really "degraded" light*. To remove all doubt, it is generally sufficient to transfer the second medium from before the eyes to the front of the hole. The light merely scattered by the object will necessarily be the same as before, if the room be free from stray light; and even if there be a little stray light, the illumination, so far as it is concerned, will be increased instead of diminished; whereas if the illumination previously observed were due to fluorescence, and the media were properly chosen, the object which before was luminous will now be comparatively dark. Sometimes, in the case of substances which have only a low degree of sensibility, it is better to leave the second medium in front of the eyes, and use a third medium, which is held alternately in the path of the rays incident on the object and between the object and the eyes. Such a medium, though not at all necessary, may be used * This term, which was suggested to me by my friend Prof. Thomson, appears to me highly significant. The expression degradation of light might be substituted with advantage for true internal dispersion to designate the general phenomenon; but it is perhaps a little too wide in its signification, and might be taken to include phosphorescence (if indeed in this case the refrangibility be really always lowered), as well as the emission of non-luminous radiant heat by a body which had been exposed to the red rays of the spectrum. As to the term internal dispersion, though I employed it, following Sir David Brewster, I confess I never liked it. It seems especially awkward when applied to a washed paper or dyed cloth; it was adopted at a time when the phenomenon was confounded with opalescence; and, so far as it implies theoretical notions at all, it seems rather to point to a theory now no longer tenable: I allude to the theory of suspended particles. Indeed, this theory, as it seems to me, ceased to be tenable as soon as Sir John Herschel had discovered the peculiar analysis of light connected with epipolic dispersion, and Sir David Brewster had connected the phenomenon with internal dispersion, so far at least as the common appearance of a continuous and coloured dispersed beam formed a connexion. The expression dependent emission is awkward, but would be significant, because the light is emitted in the manner of self-luminous bodies, but only in dependence upon the active rays, and so long as the body is under their influence. In this respect the phenomenon differs notably from phosphorescence. It is quite conceivable that a continuous transition may hereafter be traced by experiment from the one phenomenon to the other, but no such transition has yet been traced, nor is it by any means certain that the phenomena are not radically distinct. On this account it would, I conceive, be highly objectionable to call true internal dispersion phosphorescence. In my former paper I suggested the term fluorescence, to denote the general appearance of a solution of sulphate of quinine and similar media. I have been encouraged to give this expression a wider signification, and henceforth, instead of true internal dispersion, I intend to use the term fluorescence, which is a single word not implying the adoption of any theory. also in the case of highly sensitive substances, for the sake of varying the experiment and rendering the result more striking. As it will be convenient to have names for the media fulfilling these different offices, I will call the first medium, or that with which the hole is covered, the principal absorbent, the second medium the complementary absorbent, and the third medium, when such is employed, the transfer medium. For the transfer medium we may choose a medium of the same nature as the complementary absorbent, but paler. This is perhaps the best kind to employ in the methodical examination of various substances; but if the object of the observer be merely to illustrate the phenomena of the change of refrangibility of light, he may vary the experiments by using other media. 245. I have hitherto spoken only of the increase of illumination due to the sensibility of the substance under examination. But independently of illumination, the colour of the emitted light affords in most cases a ready means of detecting fluorescence. Thus, suppose the principal absorbent to transmit no visible rays but deep blue and violet, and the substance examined to appear, when viewed through the complementary absorbent, of a bright orange colour. Since no combination of the rays transmitted by the principal absorbent can make an orange, we may instantly conclude that the substance is sensitive. However, I do not consider it safe, at least for a beginner, to trust very much to absolute colour, for few who have not been used to optical experiments can be aware to what an extent the eye under certain circumstances is liable to be deceived. The relative colour of two objects seen at the same time under similar circumstances may usually be judged of safely enough; that is, of two such colours it may be possible to say with certainty that one inclines more to blue or to red than the other. Of course in many cases the change of colour is so great that there can be no mistake; still I think it a safe rule for a person employing these modes of observation without having been previously used to optical experiments, to require some other proof of a change of refrangibility than merely a change of colour. Experience will soon show what appearances may safely be relied on. 246. If it be desired to view the object isolated as much as possible, it may be placed directly on the shelf, or better still, on black velvet. But it is generally preferable to have for comparison a standard object which reflects freely the visible rays, of whatever kind, incident upon it, and does not possess any sensible degree of fluorescence. It is in this way that the white porcelain tablet is useful; and in observing, I generally place the tablet on the shelf and the object on it. A white plate would answer, but a tablet is better, on account both of its shape and of the comparative dullness of its surface. It is true that the tablet used exhibited a very sensible amount of fluorescence when examined in a linear spectrum formed by a quartz train; still the effect was so small, and so much of it was due to those highly refrangible rays which are stopped by glass, that for practical purposes the tablet may be regarded as insensible. However, an observer is not obliged either to assume that all tablets are alike, or to apply to the particular tablet which he proposes to use, methods of observation requiring the use of apparatus which he is not supposed to possess. The methods of observation described in the present paper are complete in themselves; the observer has it in his power to test for himself the tablet he proposes to employ; and he is bound to do so before taking it for a standard of comparison. It may easily be tested by means of a prism, as will be explained presently. 247. The following are the combinations of media which I have chiefly employed: First combination.—In this combination the principal absorbent is a glass coloured deep violet by manganese with a little cobalt, or else a glass coloured deep purple by manganese alone, combined with a rather pale blue glass coloured by cobalt, or with a deeper blue glass in case the day be bright. It is very easy to tell by means of a prism, with candle-light, whether a purple glass contains any sensible quantity of cobalt, on account of the very peculiar mode of absorption which is characteristic of this metal. In the examination of substances by this combination no complementary absorbent is usually required; but if it be wished to employ one, a pale yellow glass, of the kind mentioned in connexion with the next combination, may be used. Second combination.—In this case the principal absorbent is a solution of the ammoniaco-sulphate of copper, employed in such thickness as to give a deep blue. In my experiments the fluid was contained in a cell with parallel sides of glass, which was closed at the top for greater convenience; but a very broad flat bottle would answer as well, because in the case of the principal absorbent the regularity of refraction of rays across it is of no consequence. Such a bottle, however, would have to be ordered expressly. The complementary absorbent in this combination is a yellow glass coloured by silver, and slightly overburnt. These glasses, as commonly prepared, are opake with regard to most of the violet, but become transparent again with regard to the invisible rays beyond; and, in the case of a pale glass, the commencing transparency in the extreme violet may even be perceived by means of light received directly into the eye. I have got a glass of a pretty deep orange-yellow colour, which is more transparent than common window-glass with regard to rays of such high refrangibility as to be situated near the end of the region of the solar spectrum which it requires a quartz train to show. But when too much heat is used in the preparation, the glass acquires, on the interior of the coloured face, a delicate blue appearance, having a good deal of the aspect of a solution of sulphate of quinine, though it has in reality nothing to do with fluorescence; and in this state the glass is nearly opake with regard to the invisible rays of the solar spectrum beyond the violet, though it still transmits a few among those which are nearly the most refrangible. Of course, if the complementary absorbent were always left in its position between the eyes and the object, its transparency or opacity with regard to invisible rays would be a matter of indifference; but as it is desirable that its transference from that position to the front of the hole should produce as much difference as possible, it is important that it should be opake, or nearly so, with regard to the ultra-violet rays transmitted by the principal absorbent. Hence one of these slightly over-burnt glasses should be selected for the present purpose, and such are very commonly met with. **Third combination.**—In this case everything is the same as in the preceding combination, except that the fluid is replaced by a glass of a pretty deep blue, coloured by cobalt. **Fourth combination.**—In this the principal absorbent is a solution of nitrate of copper, and the complementary absorbent a light red or deep orange glass. 248. In the first combination the darkness is tolerably complete without the use of any complementary absorbent, since no visible rays are transmitted except violet and some extreme red. The latter are no inconvenience, but rather help to set off the tint of the light due to fluorescence. This is, I think, the best combination to employ when the fluorescent light is blue, or at least deep blue; because in that case much of the light is lost by absorption in the yellow glass employed in the second combination. It has the advantage, too, of allowing the fluorescent light to enter the eye without being modified by absorption. Nevertheless no correct estimate can be formed of the absolute colour of the fluorescent light without making very great allowance for the effects of contrast, especially when the body, instead of being isolated as far as possible, is placed on the porcelain tablet. The second combination is on the whole the most powerful. The media in this case make a very fair approach towards the ideal perfection explained in Art. 242. The darkness is so far complete, or else may easily be made so by increasing a little the strength of either absorbent, that if the tablet be written on with ink, and placed on the shelf between the media, the writing cannot be read. It forms a striking experiment, after having treated the tablet in this manner, to introduce between the media a piece of canary glass or a similar medium. The glass is not only luminous itself, but it emits so much light as to illuminate the whole tablet, so that the writing is instantly visible. In those cases in which the fluorescent light is yellow, orange, or red, it is shown a good deal more strongly by this combination than by the preceding. The third combination is applicable to the same cases as the second. The blue glass answers extremely well, but is not quite so good as the blue fluid. The darkness is less complete, on account of the red and yellow transmitted by the glass. Nevertheless this combination is sometimes useful in observing with a prism, and at any rate it may very well be employed by a person who does not happen to have a vessel of the proper shape for holding the fluid. In the second and third combinations the point of the spectrum at which the transparency of the principal absorbent begins, and that of the complementary absorbent ends, or rather the point which most nearly possesses this character, is situated in the blue. Thinking that the fluorescence of those substances which emit light of low refrangibility might be better brought out if this point were situated lower down in the spectrum, I tried the fourth combination. In this case the media have very fairly the required complementary character; the darkness is pretty com- plete, and the fluorescence of scarlet cloth and similar substances is very well exhibited. However, the effect in these cases is shown so well by the second combination, that, except it be for the sake of varying the experiment, I do not think it worth while to employ the fourth combination, more especially as it has the disadvantage of leaving the observer in doubt whether the red or orange light perceived constitutes the whole of the fluorescent light, or only that part of it which alone has been able to get through the complementary absorbent. 249. The mode of observation may be altered in various ways which afford pleasing illustrations of the theory, though in the regular examination of a set of substances it is best to proceed in a more methodical manner. Thus, if nothing but a violet or blue glass or a blue fluid be used as a principal absorbent, and the substances under examination be highly sensitive, their appearance will be remarkably changed if the coloured medium be transferred from before the hole to before the eyes. Again, if the complementary absorbent be made to exchange places with the principal absorbent, the result will be similar, although the very same media are merely interposed in different parts of the compound path of the light from the clouds to the eye. If a transfer medium be employed, and it be, as has hitherto been supposed, of the same general nature as the complementary absorbent, it will not produce much effect when it is interposed between the object and the eyes, but when it is placed in the path of the rays incident on the object, the fluorescent light will be nearly if not entirely cut off. If, however, we take for a transfer medium a glass or fluid having the same general character as the principal absorbent, the effect will be just the reverse. This is strikingly shown in the case of a substance, which, like scarlet cloth, emits a red fluorescent light, by taking for a transfer medium a solution of nitrate of copper, and in the case of turmeric paper or yellow uranite, by taking the same solution, or else a blue glass. In the case of the two substances last mentioned, if we take for a transfer medium a red solution of mineral chameleon, diluted so as to be merely pink, the intensity of the light emitted will, under certain conditions, be not much different in the two positions of the medium, because a portion of the active rays in one position and a portion of the degraded rays in the other will be absorbed; but the colour of the portion of the emitted light which reaches the eye will be altogether different in the two positions of the transfer medium. Mode of observing by means of a Prism. 250. In this method no absorbing medium is required except the principal absorbent. The white tablet being laid on the shelf, a slit is first held in such a position as to be seen projected against the sky, and the light thus coming directly into the eye, after having passed through the principal absorbent, is analysed by a prism held in the other hand. The slit is now held so that the tablet is seen through it, and the light coming from the tablet is analysed. It will be found that the spectrum seen in the first instance is faithfully reproduced, being merely less lumi- nous, as must necessarily happen. At least, this was the case in those tablets which I have examined; and in this way each observer ought to test for himself the tablet he proposes to employ. After having been thus tested, the tablet may be used as a standard of comparison. Suppose now that it is wished to examine a slip of turmeric paper, or a riband, or other similar object. The object is laid on the tablet, and the slit held immediately in front of it, in such a manner that one part, suppose the central portion, of the slit is seen projected on the object, and the remainder on the tablet. The light coming through the slit is then analysed by the prism, and the fluorescence, if any, of the object is indicated by light appearing in those regions of the spectrum in which, in the case of the light scattered by the tablet, there is nothing but darkness. Occasionally in these observations a blue glass is preferable to a solution of the ammoniac-sulphate of copper, because the extreme red and the greenish yellow bands transmitted by the glass, while too faint to interfere with the fluorescent light, are useful as points of reference. 251. The general appearance of the spectrum in this mode of observation may be gathered from the accompanying figures, of which the first represents turmeric paper seen under the blue glass, and the second represents a mass of crystals of nitrate of uranium seen under the copper solution. In fig. 1, RR', YY' are the red and yellow bands transmitted by the glass, which are seen equally in the light scattered by the tablet and that scattered by the paper. BVB'V' is the blue and violet light transmitted by the glass. Of this a considerable portion, especially in the more refrangible part, is absorbed by the turmeric paper, which on the other hand emits a quantity of red, yellow, and green light, not found among the incident rays. Fig. 2 sufficiently explains itself. In this case the fluorescent light is decomposed by the prism into bright bands, of which six may be readily made out. No blue or violet light enters the eye from the part of the slit which is seen projected on the mass of crystals, except where a crystalline face happens to be situated in such a position as to reflect the light of the sky into the eye, as represented in the figure. In the case of a substance so highly sensitive as nitrate of uranium, and which does not, like a slip of paper, lie flat on the tablet, the spectrum of the fluorescent light in reality extends, at least on the side next the window, though with less intensity, to some distance beyond the part of the slit which corresponds to the object, because the tablet is lighted up by the rays emitted by the object; but this is not represented in the figure. 252. The mode of using the prism just explained is that by which the phenomenon of the change of refrangibility is most strikingly illustrated; but in the actual examination of substances the chief use of the prism is to determine, in the case of substances which are sufficiently sensitive to admit with advantage of such a mode of observation, the composition of the fluorescent light. For this purpose it is often better to isolate the object by placing it on black velvet. This is especially the case with very minute crystals, or other objects, which are best placed on black velvet, and viewed through the prism as a whole, no slit being required. Examples of the application of the preceding methods of observation. 253. The peculiar properties of paper washed with tincture of turmeric or stramonium seeds, of yellow uranite, and other highly sensitive substances, come out in a remarkable manner under the modes of examination described in this paper. I need not say that such is the case with solutions of sulphate of quinine, or horse-chestnut bark, or other clear and highly sensitive media, seeing that in this case the appearance due to fluorescence is obvious to common observation. If a piece of horse-chestnut bark be put to float in a glass of water close to the hole covered by the principal absorbent, the appearance of the descending streams of solution of esculine is very singular and beautiful. My present object is however rather to illustrate the power of these methods by their application to substances which stand much lower in the scale. By the use of absorbing media alone, as well by a principal absorbent and a prism, I have been able to detect without difficulty the sensibility of white paper on a day of continuous clouds and rain. Even cotton wool, which stands very much lower in the scale, is shown by the use of absorbing media with ordinary daylight to be sensitive. In the case of such substances as bone, ivory, white leather, the white part of a quill, which stand much higher in the scale, the most inexperienced observer could hardly fail instantly to detect the fluorescence. All plates of colourless glass which I have examined, and other pieces which were of such a shape as to admit of being looked into edgeways to a considerable depth, were found by the second combination to be sensitive. Crystals of sulphate of quinine, which may be readily prepared from the disulphate of commerce, show their fluorescence extremely well by the first combination. These crystals are much less sensitive than their solution, and the light which they emit is of a much deeper blue. It must in reality be of a very deep blue colour; for it nearly matches the fluorescent light of fluor-spar, although when the crystals are viewed under the violet glass the tint in both cases appears comparatively pale, from contrast with the violet. A solution of nitrate of uranium on the other hand has only a low degree of sensibility compared with the crystals of that salt. If a drop of the solution be placed on the porcelain tablet when the hole is covered with the deep blue copper solution, it appears comparatively dark, because much more illumination is lost by the absorption of the indigo and violet than is gained by the fluorescence of the solution. But when the tablet is viewed through the complementary absorbent, the solution is seen to be more luminous than the tablet, and to emit yellow rays, which are not found in the incident light. The reactions of quinine mentioned in my former paper (Arts. 205–208), may very conveniently be observed by means of drops of the solution placed on the tablet; and in this way it is possible to work in a perfectly satisfactory manner with excessively minute quantities of quinine. The statement there made, that the blue colour was destroyed by hydrochloric acid, &c., must be understood only with reference to the mode of observation there supposed to be adopted, which was sufficient for the object in view. When the solutions are examined in a pure spectrum formed by sunlight, or even by the method described in the present paper, it is seen that the blue colour is not absolutely destroyed by hydrochloric acid, and is even developed to a slight extent on the addition of hydrochloric acid to a previously alkaline solution. Still there is a broad distinction between the two classes of solutions, which is all that is required. I have since extended a good deal these results, and mean to pursue the subject further. Meanwhile I may be permitted to correct an error in Art. 205, relative to the effect of hydrocyanic acid, which was there stated to develope the blue colour. The experiment was made with the acid of commerce, containing a foreign acid, to which the effect was probably due. Comparison of the relative advantages of different modes of observation. 254. At first sight it might have been supposed that daylight could never be more than a poor substitute for sunlight in any observations relating to fluorescence. Such, however, I consider to be by no means the case. In the first place, when sunlight is used it is made to enter a room in a definite direction; whereas in using absorbing media all the rays are employed whose directions lie within a solid angle having the object examined for vertex, and the hole for base. If we leave out the part of this solid angle which corresponds to trees or houses, the part which corresponds to sky will still be so large as to make up in a good measure for the superior brilliancy of the light of the sun. In the second place, stray light is much more perfectly excluded than when a beam of sunlight, containing rays of all kinds, is admitted into a room. When indeed the use of sunlight is combined with that of absorbing media, it is possible to detect very minute degrees of sensibility. Still for general purposes I consider the methods depending upon the use of absorbing media with ordinary daylight quite comparable with, if not equal to, those methods involving the use of sunlight which are applicable to opake bodies; I allude especially to the method of a linear spectrum. The peculiarities in the composition of the fluorescent light, when such exist, can be made out about equally well by both methods. But when the substance to be investigated is a solution, or a clear solid of sufficient size to be examined as such, methods of observation can be put in practice with sunlight which surpass anything that can be done merely by the use of absorbing media. In consequence of the absence of stray light, which would otherwise dazzle the eye, an amount of concentration of the rays can be brought to bear on the object, which enables the observer to detect excessively minute degrees of sensibility. Thus, when the sun’s light is condensed by a rather large lens, and made to pass through a strong solution of the ammoniaco-sulphate of copper, the condensed beam of violet and invisible rays serves to detect fluorescence in almost all fluids. This, however, is no great advantage; the method is in fact too powerful; and the observer is left in doubt whether the effect perceived be due to the fluid deemed to be examined, or to some impurity which it contains in an amount otherwise perhaps inappreciable. The great advantage which sunlight observations possess in the examination of substances, which, however, is only applicable to clear media, is that they enable the observer to make out the distribution of activity in the incident spectrum. In some cases this constitutes the chief peculiarity in the mode of fluorescence of a particular substance; in other cases it enables the observer to see, as it were, independently of each other, different sensitive substances existing together in solution. Another advantage of sunlight, which applies equally to clear and to opake media, is that it enables the observer, with the assistance of a quartz train, to make out fluorescence which does not commence till that region of the spectrum which it requires a quartz train to show. But such cases are too rare to render this a point of much consequence. Of course there are observations such as those which relate to the fixed lines of the invisible rays, or to the determination of the absorbing action of a medium with regard to invisible rays of each degree of refrangibility in particular, which imperatively require sunlight: I am speaking at present only with reference to those observations of which the object is to investigate the mode of fluorescence of a particular substance. As to the method of observation in which a prism is combined with a principal absorbent, its chief use is to determine, in the case of the more sensitive substances, the composition of the fluorescent light. It is not generally so convenient as the method which involves the use of absorbing media alone for determining which among a group of objects are sensitive, and which not, especially when the objects are minute. 255. Although the description of the mode of observing by means of absorbing media has run to some little length, the reader must not suppose that the observations are at all difficult. Of course observations of all kinds become more or less difficult when they are pushed to the extreme limit of refinement of which they are susceptible. But in the case of substances which are at all highly sensitive, and this comprises almost all the more interesting instances, the observations are extremely easy. I have spoken of a darkened room, which is certainly the most convenient when it can be had. But I have no doubt that an observer who could not procure such might easily arrange for himself a darkened box, which would answer the purpose. Indeed the fluorescence of highly sensitive substances, though they be opake, may be exhibited by means of absorbing media in broad daylight. Platinocyanides. 256. In the Report of the Twentieth Meeting of the British Association (Edinburgh, 1850, Transactions of the Sections, p. 5), is a notice by Sir David Brewster of "The Optical Properties of the Cyanurets of Platinum and Magnesia, and of Barytes and Platinum," salts which he had received from M. Haidinger of Vienna. The notice is chiefly devoted to the properties of the reflected light; but with respect to the latter of the salts, Sir David remarks that "it possesses the property of internal dispersion, the dispersed light being a brilliant green, while the transmitted light is yellow." Although the distinction between true internal dispersion and opalescence was not at the time understood, there could be little doubt from the nature of the case that the internal dispersion mentioned by Sir David Brewster was, in fact, an instance of the former of these phenomena; but I could not try for want of a specimen of the salt. Some months ago I received from M. Haidinger a specimen of the first of the salts mentioned at the beginning of this paragraph, namely M. Quadrat's cyanide of platinum and magnesium, a salt of great optical interest on account of the remarkable metallic reflexion which it exhibits. On examining the salt, I was greatly interested by finding that it was highly sensitive, the fluorescent light being red. This induced me to form some of Gmelin's platinocyanide of potassium, and I found that the blue light which this salt exhibits in certain aspects is, in fact, due to fluorescence, a property which the salt possesses in an eminent degree. Having afterwards received some of the same salt pure from Professor Gregory, I applied it to the formation, on a small scale, of the platinocyanides of calcium, barium, strontium, and two or three others. The three salts last named, of which the second is that mentioned by Sir David Brewster, are all eminently sensitive, the fluorescent light being of different shades of green. It is only in the solid state that the platinocyanides are sensitive; their solutions look like mere water. The precipitates which a solution of platinocyanide of potassium gives with salts of the heavy metals are, in most cases that I have yet observed, insensible. With a solution of pernitrate of mercury, however, a bright yellow precipitate is produced which is exceedingly sensitive, so as to look brighter than even yellow uranite. The light emitted is yellow. It forms a very striking experiment to place side by side on the tablet with the second combination a drop of a solution of platinocyanide of potassium, and another of pernitrate of mercury. The drops look like water on the dark field of view; but when they are mixed, a precipitate is produced which glows like a self-luminous body with a yellow light. The precipitate with nitrate of silver is also sensitive, though not in so high a degree. The platinocyanides are extremely interesting; first, as forming a third case, or rather class of cases, in which the property of fluorescence is attached to substances chemically isolated in a satisfactory manner (though I believe chemists are acquainted with a few other organic compounds to which the property belongs), the other two cases being salts of quinine and of peroxide of uranium; and secondly, as exhibiting a new and remarkable feature, which consists in the polarization of the fluorescent light. I content myself at present with this notice; the salts require a more extended study.