Chapter IV: New Chemical Reactions Produced by Light

1868-69.

1 DECOMPOSITION BY LIGHT.

MEASURED by their power, not to excite vision, but to produce heat--in other words, measured by their absolute energy--the ultra-red waves of the sun and of the electric light, as shown in the preceding articles, far transcend the visible. In the domain of chemistry, however, there are numerous cases in which the more powerful waves are ineffectual, while the more minute waves, through what may be called their timeliness of application, are able to produce great effects. A series of these, of a novel and beautiful character, discovered in 1868, and further illustrated in subsequent years, may be exhibited by subjecting the vapours of volatile liquids to the action of concentrated sunlight, or to the concentrated beam of the electric light. Their investigation led up to the discourse on 'Dust and Disease' which follows in this volume; and for this reason some account of them is introduced here.

*****

A glass tube 3 feet long and 3 inches wide, which had been frequently employed in my researches on radiant heat, was supported horizontally on two stands. At one end of the tube was placed an electric lamp, the height and position of both being so arranged, that the axis of the tube, and that of the beam issuing from the lamp, were coincident. In the first experiments the two ends of the tube were closed by plates of rock-salt, and subsequently by plates of glass. For the sake of distinction, I call this tube the experimental tube. It was connected with an air-pump, and also with a series of drying and other tubes used for the purification of the air.

A number of test-tubes, like F, fig. 2 (I have used at least fifty of them), were converted into Woulf's flasks. Each of them was stopped by a cork, through which passed two glass tubes: one of these tubes (a) ended immediately below the cork, while the other (b) descended to the bottom of the flask, being drawn out at its lower end to an orifice about 0.03 of an inch in diameter. It was found necessary to coat the cork carefully with cement. In the later experiments corks of vulcanised India-rubber were invariably employed.

The little flask, thus formed, being partially filled with the liquid whose vapour was to be examined, was introduced into the path of the purified current of air. The experimental tube being exhausted, and the cock which cut off the supply of purified air being cautiously turned on, the air entered the flask through the tube b, and escaped by the small orifice at the lower end of b into the liquid. Through this it bubbled, loading itself with vapour, after which the mixed air and vapour, passing from the flask by the tube a, entered the experimental tube, where they were subjected to the action of light.

The whole arrangement is shown in fig. 3, where L represents the electric lamp, ss' the experimental tube, pp' the pipe leading to the air-pump, and F the test-tube containing the volatile liquid. The tube tt' is plugged with cotton-wool intended to intercept the floating matter of the air; the bent tube T' contains caustic potash, the tube T sulphuric acid, the one intended to remove the carbonic acid and the other the aqueous vapour of the air.

The power of the electric beam to reveal the existence of anything within the experimental tube, or the impurities of the tube itself, is extraordinary. When the experiments is made in a darkened room, a tube which in ordinary daylight appears absolutely clean, is often shown by the present mode of examination to be exceedingly filthy.

The following are some of the results obtained with this arrangement:

Nitrite of amyl. The vapour of this liquid was in the first instance permitted to enter the experimental tube, while the beam from the electric lamp was passing through it. Curious clouds, the cause of which was then unknown, were observed to form near the place of entry, being afterwards whirled through the tube.

The tube being again exhausted, the mixed air and vapour were allowed to enter it in the dark. The slightly convergent beam of the electric light was then sent through the mixture. For a moment the tube was _optically empty_, nothing whatever being seen within it; but before a second had elapsed a shower of particles was precipitated on the beam. The cloud thus generated became denser as the light continued to act, slowing at some places vivid iridescence.

The lens of the electric lamp was now placed so as to form within the tube a strongly convergent cone of rays. The tube was cleansed and again filled in darkness. When the light was sent through it, the precipitation upon the beam was so rapid and intense that the cone, which a moment before was invisible, flashed suddenly forth like a solid luminous spear. The effect was the same when the air and vapour were allowed to enter the tube in diffuse daylight. The cloud, however, which shone with such extraordinary radiance under the electric beam, was invisible in the ordinary light of the laboratory.

The quantity of mixed air and vapour within the experimental tube could of course be regulated at pleasure. The rapidity of the action diminished with the attenuation of the vapour. When, for example, the mercurial column associated with the experimental tube was depressed only five inches, the action was not nearly so rapid as when the tube was full. In such cases, however, it was exceedingly interesting to observe, after some seconds of waiting, a thin streamer of delicate bluish-white cloud slowly forming along the axis of the tube, and finally swelling so as to fill it.

Fig. 2.

Fig. 3.

When dry oxygen was employed to carry in the vapour the effect was the same as that obtained with air.

When dry hydrogen was used as a vehicle, the effect was also the same.

The effect, therefore, is not due to any interaction between the vapour of the nitrite and its vehicle.

This was further demonstrated by the deportment of the vapour itself. When it was permitted to enter the experimental tube unmixed with air or any other gas, the effect was substantially the same. Hence the seat of the observed action is the vapour.

This action is not to be ascribed to heat. As regards the glass of the experimental tube, and the air within the tube, the beam employed in these experiments was perfectly cold. It had been sifted by passing it through a solution of alum, and through the thick double-convex lens of the lamp. When the unsifted beam of the lamp was employed, the effect was still the same; the obscure calorific rays did not appear to interfere with the result.

My object here being simply to point out to chemists a method of experiments which reveals a new and beautiful series of reactions, I left to them the examination of the products of decomposition. The group of atoms forming the molecule of nitrite of amyl is obviously shaken asunder by certain specific waves of the electric beam, nitric oxide and other products, of which the _nitrate_ of amyl is probably one, being the result of the decomposition. The brown fumes of nitrous acid were seen mingling with the cloud within the experimental tube. The nitrate of amyl, being less volatile than the nitrite, and not being able to maintain itself in the condition of vapour, would be precipitated as a visible cloud along the track of the beam.

In the anterior portions of the tube a powerful sifting of the beam by the vapour occurs, which diminishes the chemical action in the posterior portions. In some experiments the precipitated cloud only extended halfway down the tube. When, under these circumstances, the lamp was shifted so as to send the beam through the other end of the tube, copious precipitation occurred there also.

Solar light also effects the decomposition of the nitrite-of-amyl vapour. On October 10, 1868, I partially darkened a small room in the Royal Institution, into which the sun shone, permitting the light to enter through an open portion of the window-shutter. In the track of the beam was placed a large plano-convex lens, which formed a fine convergent cone in the dust of the room behind it. The experimental tube was filled in the laboratory, covered with a black cloth, and carried into the partially darkened room. On thrusting one end of the tube into the cone of rays behind the lens, precipitation within the cone was copious and immediate. The vapour at the distant end of the tube was in part shielded by that in front, and was also more feebly acted on through the divergence of the rays. On reversing the tube, a second and similar cone was precipitated.

Physical Considerations.

I sought to determine the particular portion of the light which produced the foregoing effects. When, previous to entering the experimental tube, the beam was caused to pass through a red glass, the effect was greatly weakened, but not extinguished. This was also the case with various samples of yellow glass. A blue glass being introduced before the removal of the yellow or the red, on taking the latter away prompt precipitation occurred along the track of the blue beam. Hence, in this case, the more refrangible rays are the most chemically active. The colour of the liquid nitrite of amyl indicates that this must be the case; it is a feeble but distinct yellow: in other words, the yellow portion of the beam is most freely transmitted. It is not, however, the transmitted portion of any beam which produces chemical action, but the absorbed portion. Blue, as the complementary colour to yellow, is here absorbed, and hence the more energetic action of the blue rays.

This reasoning, however, assumes that the same rays are absorbed by the liquid and its vapour. The assumption is worth testing. A solution of the yellow chromate of potash, the colour of which may be made almost, if not altogether, identical with that of the liquid nitrite of amyl, was found far more effective in stopping the chemical rays than either the red or the yellow glass. But of all substances the liquid nitrite itself is most potent in arresting the rays which act upon its vapour. A layer one-eighth of an inch in thickness, which scarcely perceptibly affected the luminous intensity, absorbed the entire chemical energy of the concentrated beam of the electric light.

The close relation subsisting between a liquid and its vapour, as regards their action upon radiant heat, has been already amply demonstrated. [Footnote: 'Phil. Trans.' 1864; 'Heat, a Mode of Motion,' chap, xii; and P. 61 of this volume.] As regards the nitrite of amyl, this relation is more specific than in the cases hitherto adduced; for here the special constituent of the beam, which provokes the decomposition of the vapour, is shown to be arrested by the liquid.

A question of extreme importance in molecular physics here arises: What is the real mechanism of this absorption, and where is its seat? [Footnote: My attention was very forcibly directed to this subject some years ago by a conversation with my excellent friend Professor Clausius.]

I figure, as others do, a molecule as a group of atoms, held together by their mutual forces, but still capable of motion among themselves. The vapour of the nitrite of amyl is to be regarded as an assemblage of such molecules. The question now before us is this: In the act of absorption, is it the molecules that are effective, or is it their constituent atoms? Is the _vis viva_ of the intercepted light-waves transferred to the molecule as a whole, or to its constituent parts?

The molecule, as a whole, can only vibrate in virtue of the forces exerted between it and its neighbour molecules. The intensity of these forces, and consequently the rate of vibration, would, in this case, be a function of the distance between the molecules. Now the identical absorption of the liquid and of the vaporous nitrite of amyl indicates an identical vibrating period on the part of liquid and vapour, and this, to my mind, amounts to an experimental proof that the absorption occurs in the main _within_ the molecule. For it can hardly be supposed, if the absorption were the act of the molecule as a whole, that it could continue to affect waves of the same period after the substance had passed from the vaporous to the liquid state.

In point of fact, the decomposition of the nitrite of amyl is itself to some extent an illustration of this internal molecular absorption; for were the absorption the act of the molecule as a whole, the relative motions of its constituent atoms would remain unchanged, and there would be no mechanical cause for their separation. It is probably the synchronism of the vibrations of one portion of the molecule with the incident waves, that enables the amplitude of those vibrations to augment, until the chain which binds the parts of the molecule together is snapped asunder.

I anticipate wide, if not entire, generality for the fact that a liquid and its vapour absorb the same rays. A cell of liquid chlorine would, I imagine, deprive light more effectually of its power of causing chlorine and hydrogen to combine than any other filter of the luminous rays. The rays which give chlorine its colour have nothing to do with this combination, those that are absorbed by the chlorine being really effective rays. A highly sensitive bulb, containing chlorine and hydrogen, in the exact proportions necessary for the formation of hydrochloric acid, was placed at one end of an experimental tube, the beam of the electric lamp being sent through it from the other. The bulb did not explode when the tube was filled with chlorine, while the explosion was violent and immediate when the tube was filled with air. I anticipate for the liquid chlorine an action similar to, but still more energetic than, that exhibited by the gas. If this should prove to be the case, it will favour the view that chlorine itself is _molecular_ and not _monatomic_.

Production of Sky-blue by the Decomposition of Nitrite of Amyl.

When the quantity of nitrite vapour is considerable, and the light intense, the chemical action is exceedingly rapid, the particles precipitated being so large as to whiten the luminous beam. Not so, however, when a well-mixed and highly attenuated vapour fills the experimental tube. The effect now to be described was first obtained when the vapour of the nitrite was derived from a portion of its liquid which had been accidentally introduced into the passage through which the dry air flowed into the experimental tube.

In this case, the electric beam traversed the tube for several seconds before any action was visible. Decomposition then visibly commenced, and advanced slowly. When the light was very strong, the cloud appeared of a milky blue. When, on the contrary, the intensity was moderate, the blue was pure and deep. In Brücke's important experiments on the blue of the sky and the morning and evening red, pure mastic is dissolved in alcohol, and then dropped into water well stirred. When the proportion of mastic to alcohol is correct, the resin is precipitated so finely as to elude the highest microscopic power. By reflected light, such a medium appears bluish, by transmitted light yellowish, which latter colour, by augmenting the quantity of the precipitate, can be caused to pass into orange or red.

But the development of colour in the attenuated nitrite-of-amyl vapour is doubtless more similar to what takes place in our atmosphere. The blue, moreover, is far purer and more sky-like than that obtained from Bruecke's turbid medium. Never, even in the skies of the Alps, have I seen a richer or a purer blue than that attainable by a suitable disposition of the light falling upon the precipitated vapour.

Iodide of Allyl.--Among the liquids hitherto subjected to the concentrated electric light, iodide of allyl, in point of rapidity and intensity of action, comes next to the nitrite of amyl. With the iodide I have employed both oxygen and hydrogen, as well as air, as a vehicle, and found the effect in all cases substantially the same. The cloud-column here was exquisitely beautiful. It revolved round the axis of the decomposing beam; it was nipped at certain places like an hour-glass, and round the two bells of the glass delicate cloud-filaments twisted themselves in spirals. It also folded itself into convolutions resembling those of shells. In certain conditions of the atmosphere in the Alps I have often observed clouds of a special pearly lustre; when hydrogen was made the vehicle of the iodide-of allyl vapour a similar lustre was most exquisitely shown. With a suitable disposition of the light, the purple hue of iodine-vapour came out very strongly in the tube.

The remark already made, as to the bearing of the decomposition of nitrite of amyl by light on the question of molecular absorption, applies here also; for were the absorption the work of the molecule as a whole, the iodine would not be dislodged from the allyl with which it is combined. The non-synchronism of iodine with the waves of obscure heat is illustrated by its marvellous transparency to such heat. May not its synchronism with the waves of light in the present instance be the cause of its divorce from the allyl?

Iodide of Isopropyl.--The action of light upon the vapour of this liquid is, at first, more languid than upon iodide of allyl; indeed many beautiful reactions may be overlooked, in consequence of this languor at the commencement. After some minutes' exposure, however, clouds begin to form, which grow in density and in beauty as the light continues to act. In every experiment hitherto made with this substance the column of cloud filling the experimental tube, was divided into two distinct parts near the middle of the tube. In one experiments a globe of cloud formed at the centre, from which, right and left, issued an axis uniting the globe with two adjacent cylinders. Both globe and cylinders were animated by a common motion of rotation. As the action continued, paroxysms of motion were manifested; the various parts of the cloud would rush through each other with sudden violence. During these motions beautiful and grotesque cloud-forms were developed. At some places the nebulous mass would become ribbed so as to resemble the graining of wood; a longitudinal motion would at times generate in it a series of curved, transverse bands, the retarding influence of the sides the tube causing an appearance resembling, on a small scale, the dirt-bands of the Mer de Glace. In the anterior portion of the tube those sudden commotion were most intense; here buds of cloud would sprout forth, and grow in a few seconds into perfect flower-like forms. The cloud of iodide of isopropyl had a character Of its own, and differed materially from all others that I had seen. A gorgeous mauve colour was observed in the last twelve inches of the tube; the vapour of iodine was present, and it may have been the sky-blue scattered by the precipitated particles which, mingling with the purple of the iodine, produced the mauve. As in all other cases here adduced, the effects were proved to be due to the light; they never occurred in darkness.

The forms assumed by some of those actinic clouds, as I propose to call them, in consequence of rotations and other motions, due to differences of temperature, are perfectly astounding. I content myself here with a meagre description of one more of them.

The tube being filled with the sensitive mixture, the beam was sent through it, the lens at the same time being so placed as to produce a cone of very intense light. Two minutes elapsed before anything was visible; but at the end of this time a faint bluish cloud appeared to hang itself on the most concentrated portion of the beam.

Soon afterwards a second cloud was formed five inches farther down the experimental tube. Both clouds were united by a slender cord of the same bluish tint as themselves.

As the action of the light continued, the first cloud gradually resolved itself into a series of parallel disks of exquisite delicacy, which rotated round an axis perpendicular to their surfaces, and finally blended to a screw surface with an inclined generatrix. This gradually changed into a filmy funnel, from the narrow end of which the 'cord' extended to the cloud in advance.

The latter also underwent slow but incessant modification. It first resolved itself into a series of strata resembling those of the electric discharge. After a little time, and through changes which it was difficult to follow, both clouds presented the appearance of a series of concentric funnels set one within the other, the interior ones being seen through the outer ones. Those of the distant cloud resembled claret-glasses in shape. As many as six funnels were thus concentrically set together, the two series being united by the delicate cord of cloud already referred to. Other cords and Blender tubes were afterwards formed, which coiled themselves in delicate spirals around the funnels.

Rendering the light along the connecting-cord more intense, it diminished in thickness and became whiter; this was a consequence of the enlargement of its particles. The cord finally disappeared, while the funnels melted into two ghost-like films, shaped like parasols. They were barely visible, being of an exceedingly delicate blue tint. They seemed woven of blue air. To compare them with cobweb or with gauze would be to liken them to something infinitely grosser than themselves.

In all cases a distant candle-flame, when looked at through the cloud, was sensibly undimmed.

2. ON THE BLUE COLOUR OF THE SKY, AND THE POLARISATION OF SKYLIGHT.

[Footnote: In my 'Lectures on Light' (Longman), the polarisation of light will be found briefly, but, I trust, clearly explained.]

1869.

After the communication to the Royal Society of the foregoing brief account of a new Series of Chemical Reactions produced by Light, the experiments upon this subject were continued, the number of substances thus acted on being considerably increased.

I now, however, beg to direct attention to two questions glanced at incidentally in the preceding pages--the blue colour of the sky, and the polarisation of skylight. Reserving the historic treatment of the subject for a more fitting occasion, I would merely mention now that these questions constitute, in the opinion of our most eminent authorities, the two great standing enigmas of meteorology. Indeed it was the interest manifested in them by Sir John Herschel, in a letter of singular speculative power, addressed to myself, that caused me to enter upon the consideration of these questions so soon.

The apparatus with which I work consists, as already stated, of a glass tube about a yard in length, and from 2.5 to 3 inches internal diameter. The vapour to be examined is introduced into this tube in the manner already described, and upon it the condensed beam of the electric lamp is permitted to act, until the neutrality or the activity of the substance has been declared.

It has hitherto been my aim to render the chemical action of light upon vapours visible. For this purpose substances have been chosen, one at least of whose products of decomposition under light shall have a boiling-point so high, that as soon as the substance is formed it shall be precipitated. By graduating the quantity of the vapour, this precipitation may be rendered of any degree of fineness, forming particles distinguishable by the naked eye, or far beyond the reach of our highest microscopic powers. I have no reason to doubt that particles may be thus obtained, whose diameters constitute but a small fraction of the length of a wave of violet light.

In all cases when the vapours of the liquids employed are sufficiently attenuated, no matter what the liquid may be, the visible action commences with the formation of a _blue cloud_. But here I must guard myself against all misconception as to the use of this term. The 'cloud' here referred to is totally invisible in ordinary daylight. To be seen, it requires to be surrounded by darkness, _it only_ being illuminated by a powerful beam of light. This blue cloud differs in many important particulars from the finest ordinary clouds, and might justly have assigned to it an intermediate position between such clouds and true vapour. With this explanation, the term 'cloud,' or 'incipient cloud,' or 'actinic cloud,' as I propose to employ it, cannot, I think, be misunderstood.

I had been endeavouring to decompose carbonic acid gas by light. A faint bluish cloud, due it may be, or it may not be, to the residue of some vapour previously employed, was formed in the experimental tube. On looking across this cloud through a Nicol's prism, the line of vision being horizontal, it was found that when the short diagonal of the prism was vertical, the quantity of light reaching the eye was greater than when the long diagonal was vertical. When a plate of tourmaline was held between the eye and the bluish cloud, the quantity of light reaching the eye when the axis of the prism was perpendicular to the axis of the illuminating beam, was greater than when the axes of the crystal and of the beam were parallel to each other.

This was the result all round the experimental tube. Causing the crystal of tourmaline to revolve round the tube, with its axis perpendicular to the illuminating beam, the quantity of light that reached the eye was in all its positions a maximum. When the crystallographic axis was parallel to the axis of the beam, the quantity of light transmitted by the crystal was a minimum.

From the illuminated bluish cloud, therefore, polarised light was discharged, the direction of maximum polarisation being at right angles to the illuminating beam; the plane of vibration of the polarised light was perpendicular to the beam. [Footnote: This is still an undecided point; but the probabilities are so much in its favour, and it is in my opinion so much preferable to have a physical image on which the mind can rest, that I do not hesitate to employ the phraseology in the text.]

Thin plates of selenite or of quartz, placed between the Nicol and the actinic cloud, displayed the colours of polarised light, these colours being most vivid when the line of vision was at right angles to the experimental tube. The plate of selenite usually employed was a circle, thinnest at the centre, and augmenting uniformly in thickness from the centre outwards. When placed in its proper position between the Nicol and the cloud, it exhibited a system of splendidly-coloured rings.

The cloud here referred to was the first operated upon in the manner described. It may, however, be greatly improved upon by the choice of proper substances, and by the application, in proper quantities, of the substances chosen. Benzol, bisulphide of carbon, nitrite of amyl, nitrite of butyl, iodide of allyl, iodide of isopropyl, and many other substances may be employed. I will take the nitrite of butyl as illustrative of the means adopted to secure the best result, with reference to the present question.

And here it may be mentioned that a vapour, which when alone, or mixed with air in the experimental tube, resists the action of light, or shows but a feeble result of this action, may, when placed in proximity with another gas or vapour, exhibit vigorous, if not violent action. The case is similar to that of carbonic acid gas, which, diffused in the atmosphere, resists the decomposing action of solar light, but when placed in contiguity with chlorophyl in the leaves of plants, has its molecules shaken asunder.

Dry air was permitted to bubble through the liquid nitrite of butyl, until the experimental tube, which had been previously exhausted, was filled with the mixed air and vapour. The visible action of light upon the mixture after fifteen minutes' exposure was slight. The tube was afterwards filled with half an atmosphere of the mixed air and vapour, and a second half-atmosphere of air which had been permitted to bubble through fresh commercial hydrochloric acid. On sending the beam through this mixture, the tube, for a moment, was optically empty. But the pause amounted only to a small fraction of a second, a dense cloud being immediately precipitated upon the beam.

This cloud began blue, but the advance to whiteness was so rapid as almost to justify the application of the term instantaneous. The dense cloud, looked at perpendicularly to its axis, showed scarcely any signs of polarisation. Looked at obliquely the polarisation was strong.

The experimental tube being again cleansed and exhausted, the mixed air and nitrite-of-butyl vapour was permitted to enter it until the associated mercury column was depressed 1/10 of an inch. In other words, the air and vapour, united, exercised a pressure not exceeding 1/300th of an atmosphere. Air, passed through a solution of hydrochloric acid, was then added, till the mercury column was depressed three inches. The condensed beam of the electric light was passed for some time through this mixture without revealing anything within the tube competent to scatter the light. Soon, however, a superbly blue cloud was formed along, the track of the beam, and it continued blue sufficiently long to permit of its thorough examination. The light discharged from the cloud, at right angles to its own length, was at first perfectly polarised. It could be totally quenched by the Nicol. By degrees the cloud became of whitish blue, and for a time the selenite colours, obtained by looking at it normally, were exceedingly brilliant. The direction of maximum polarisation was distinctly at right angles to the illuminating beam. This continued to be the case as long as the cloud maintained a decided blue colour, and even for some time after the blue had changed to whitish blue. But, as the light continued to act, the cloud became coarser and whiter, particularly at its centre, where it at length ceased to discharge polarised light in the direction of the perpendicular, while it continued to do so at both ends.

But the cloud which had thus ceased to polarise the light emitted normally, showed vivid selenite colours when looked at obliquely, proving that the direction of maximum polarisation changed with the texture of the cloud. This point shall receive further illustration subsequently.

A blue, equally rich and more durable, was obtained by employing the nitrite-of-butyl vapour in a still more attenuated condition. The instance here cited is representative. In all cases, and with all substances, the cloud formed at the commencement, when the precipitated particles are sufficiently fine, is _blue_, and it can be made to display a colour rivalling that of the purest Italian sky. In all cases, moreover, this fine blue cloud polarises _perfectly_ the beam which illuminates it, the direction of polarisation enclosing an angle of 90° with the axis of the illuminating beam.

It is exceedingly interesting to observe both the perfection and the decay of this polarisation. For ten or fifteen minutes after its first appearance the light from a vividly illuminated actinic cloud, looked at perpendicularly, is absolutely quenched by a Nicol's prism with its longer diagonal vertical. But as the sky-blue is gradually rendered impure by the growth of the particles--in other words, as real clouds begin to be formed--the polarisation begins to decay, a portion of the light passing through the prism in all its positions. It is worthy of note, that for some time after the cessation of perfect polarisation, the residual light which passes, when the Nicol is in its position of minimum transmission, is of a gorgeous blue, the whiter light of the cloud being extinguished. [Footnote: This shows that particles too large to polarise the blue, polarise perfectly light of lower refrangibility.] When the cloud texture has become sufficiently coarse to approximate to that of ordinary clouds, the rotation of the Nicol ceases to have any sensible effect on the quantity of light discharged normally.

The perfection of the polarisation, in a direction perpendicular to the illuminating beam, is also illustrated by the following experiments: A Nicol's prism, large enough to embrace the entire beam of the electric lamp, was placed between the lamp and the experimental tube. A few bubbles of air, carried through the liquid nitrite of butyl, were introduced into the tube, and they were followed by about three inches (measured by the mercurial gauge) of air which had passed through aqueous hydrochloric acid. Sending the polarised beam through the tube, I placed myself in front of it, my eye being on a level with its axis, my assistant occupying a similar position behind the tube. The short diagonal of the large Nicol was in the first instance vertical, the plane of vibration of the emergent beam being therefore also vertical. As the light continued to act, a superb blue cloud, visible to both my assistant and myself, was slowly formed. But this cloud, so deep and rich when looked at from the positions mentioned, _utterly disappeared when looked at vertically downwards, or vertically upwards_. Reflection from the cloud was not possible in these directions. When the large Nicol was slowly turned round its axis, the eye of the observer being on the level of the beam, and the line of vision perpendicular to it, entire extinction of the light emitted horizontally occurred when the longer diagonal of the large Nicol was vertical. But now a vivid blue cloud was seen when looked at downwards or upwards. This truly fine experiments, which I contemplated making on my own account, was first definitely suggested by a remark in a letter addressed to me by Professor Stokes.

As regards the polarisation of skylight, the greatest stumbling-block has hitherto been, that, in accordance with the law of Brewster, which makes the index of refraction the tangent of the polarising angle, the reflection which produces perfect polarisation would require to be made in air upon air; and indeed this led many of our most eminent men, Brewster himself among the number, to entertain the idea of aerial molecular reflection. [Footnote: 'The cause of the polarisation is evidently a reflection of the sun's light upon something. The question is on what? Were the angle of maximum polarisation 76°, we should look to water or ice as the reflecting body, however inconceivable the existence in a cloudless atmosphere and a hot summer's day of unevaporated molecules (particles?) of water. But though we were once of this opinion, careful observation has satisfied us that 90°, or thereabouts, is the correct angle, and that therefore whatever be the body on which the light has been reflected, if polarised by a single reflection, the polarising angle must be 45°, and the index of refraction, which is the tangent of that angle, unity; in other words, the reflection would require to be made in air upon air!' (Sir John Herschel, 'Meteorology,' par. 233.)

Any particles, if small enough, will produce both the colour and the polarisation of the sky. But is the existence of small water-particles on a hot summer's day in the higher regions of our atmosphere inconceivable? It is to be remembered that the oxygen and nitrogen of the air behave as a vacuum to radiant heat, the exceedingly attenuated vapour of the higher atmosphere being therefore in practical contact with the cold of space.]

I have, however, operated upon substances of widely different refractive indices, and therefore of very different polarising angles as ordinarily defined, but the polarisation of the beam, by the incipient cloud, has thus far proved itself to be absolutely independent of the polarising angle. The law of Brewster does not apply to matter in this condition, and it rests with the undulatory theory to explain why. Whenever the precipitated particles are sufficiently fine, no matter what the substance forming the particles may be, the direction of maximum polarisation is at right angles to the illuminating beam, the polarising angle for matter in this condition being invariably 45°.

Suppose our atmosphere surrounded by an envelope impervious to light, but with an aperture on the sunward side through which a parallel beam of solar light could enter and traverse the atmosphere. Surrounded by air not directly illuminated, the track of such a beam would resemble that of the parallel beam of the electric lamp through an incipient cloud. The sunbeam would be blue, and it would discharge laterally light in precisely the same condition as that discharged by the incipient cloud. In fact, the azure revealed by such a beam would be to all intents and purposes that which I have called a 'blue cloud.' Conversely our 'blue cloud' is, to all intents and purposes, an _artificial sky_.' [Footnote: The opinion of Sir John Herschel, connecting the polarisation and the blue colour of the sky, is verified by the foregoing results. 'The more the subject [the polarisation of skylight] is considered,' writes this eminent philosopher, 'the more it will be found beset with difficulties, and its explanation when arrived at will probably be found to carry with it that of the blue colour of the sky itself, and of the great quantity of light it actually does send down to us.' 'We may observe, too,' he adds, 'that it is only where the purity of the sky is most absolute that the polarisation is developed in its highest degree, and that where there is the slightest perceptible tendency to cirrus it is materially impaired.' This applies word for word to our 'incipient clouds.']

But, as regards the polarisation of the sky, we know that not only is the direction of maximum polarisation at right angles to the track of the solar beams, but that at certain angular distances, probably variable ones, from the sun, 'neutral points,' or points of no polarisation, exist, on both sides of which the planes of atmospheric polarisation are at right angles to each other. I have made various observations upon this subject which are reserved for the present; but, pending the more complete examination of the question, the following facts bearing upon it may be submitted.

The parallel beam employed in these experiments tracked its way through the laboratory air, exactly as sunbeams are seen to do in the dusty air of London. I have reason to believe that a great portion of the matter thus floating in the laboratory air consists of organic particles, which are capable of imparting a perceptibly bluish tint to the air. These also showed, though far less vividly, all the effects of polarisation obtained with the incipient clouds. The light discharged laterally from the track of the illuminating beam was polarised, though not perfectly, the direction of maximum polarisation being at right angles to the beam. At all points of the beam, moreover, throughout its entire length, the light emitted normally was in the same state of polarisation. Keeping the positions of the Nicol and the selenite constant, the same colours were observed throughout the entire beam, when the line of vision was perpendicular to its length.

The horizontal column of air, thus illuminated, was 18 feet long, and could therefore be looked at very obliquely. I placed myself near the end of the beam, as it issued from the electric lamp, and, looking through the Nicol and selenite more and more obliquely at the beam, observed the colours fading until they disappeared. Augmenting the obliquity the colours appeared once more, but they were now complementary to the former ones.

Hence this beam, like the sky, exhibited a neutral point, on opposite sides of which the light was polarised in planes at right angles to each other.

Thinking that the action observed in the laboratory might be caused, in some way, by the vaporous fumes diffused in its air, I had the light removed to a room at the top of the Royal Institution. The track of the beam was seen very finely in the air of this room, a length of 14 or 15 feet being attainable. This beam exhibited all the effects observed with the beam in the laboratory. Even the uncondensed electric light falling on the floating matter showed, though faintly, the effects of polarisation.

When the air was so sifted as to entirely remove the visible floating matter, it no longer exerted any sensible action upon the light, but behaved like a vacuum. The light is scattered and polarised by _particles_, not by molecules or atoms.

By operating upon the fumes of chloride of ammonium, the smoke of brown paper, and tobacco-smoke, I had varied and confirmed in many ways those experiments on neutral points, when my attention was drawn by Sir Charles Wheatstone to an important observation communicated to the Paris Academy in 1860 by Professor Govi, of Turin. [Footnote: Comptes Rendus,' tome li, pp. 360 and 669.] M. Govi had been led to examine a beam of light sent through a room in which were successively diffused the smoke of incense, and tobacco-smoke. His first brief communication stated the fact of polarisation by such smoke; but in his second communication he announced the discovery of a neutral point in the beam, at the opposite sides of which the light was polarised in planes at right angles to each other.

But unlike my observations on the laboratory air, and unlike the action of the sky, the direction of maximum polarisation in M. Govi's experiments enclosed a very small angle with the axis of the illuminating beam. The question was left in this condition, and I am not aware that M. Govi or any other investigator has pursued it further.

I had noticed, as before stated, that as the clouds formed in the experimental tube became denser, the polarisation of the light discharged at right angles to the beam became weaker, the direction of maximum polarisation becoming oblique to the beam. Experiments on the fumes of chloride of ammonium gave me also reason to suspect that the position of the neutral point was not constant, but that it varied with the density of the illuminated fumes.

The examination of these questions led to the following new and remarkable results: The laboratory being well filled with the fumes of incense, and sufficient time being allowed for their uniform diffusion, the electric beam was sent through the smoke. From the track of the beam polarised light was discharged; but the direction of maximum polarisation, instead of being perpendicular, now enclosed an angle of only 12° or 13° with the axis of the beam.

A neutral point, with complementary effects at opposite sides of it, was also exhibited by the beam. The angle enclosed by the axis of the beam, and a line drawn from the neutral point to the observer's eye, measured in the first instance 66°.

The windows of the laboratory were now opened for some minutes, a portion of the incense-smoke being permitted to escape. On again darkening the room and turning on the light, the line of vision to the neutral point was found to enclose, with the axis of the beam, an angle of 63°.

The windows were again opened for a few minutes, more of the smoke being permitted to escape. Measured as before, the angle referred to was found to be 54°.

This process was repeated three additional times the neutral point was found to recede lower and lower down the beam, the angle between a line drawn from the eye to the neutral point and the axis of the beam falling successively from 54° to 49°, 43° and 33°.

The distances, roughly measured, of the neutral point from the lamp, corresponding to the foregoing series of observations, were these:

1st observation 2 feet 2 inches.

2nd observation 2 feet 6 inches.

3rd observation 2 feet 10 inches.

4th observation 3 feet 2 inches.

5th observation 3 feet 7 inches.

6th observation 4 feet 6 inches.

At the end of this series of experiments the direction of maximum polarisation had again become normal to the beam.

The laboratory was next filled with the fumes of gunpowder. In five successive experiments, corresponding to five different densities of the gunpowder-smoke, the angles enclosed between the line of vision to the neutral point and the axis of the beam, were 63 degrees, 50°, 47°, 42°, and 38° respectively.

After the clouds of gunpowder had cleared away, the laboratory was filled with the fumes of common resin, rendered so dense as to be very irritating to the lungs. The direction of maximum polarisation enclosed, in this case, an angle of 12°, or thereabouts, with the axis of the beam. Looked at, as in the former instances, from a position near the electric lamp, no neutral point was observed throughout the entire extent of the beam.

When this beam was looked at normally through the selenite and Nicol, the ring-system, though not brilliant, was distinct. Keeping the eye upon the plate of selenite, and the line of vision perpendicular, the windows were opened, the blinds remaining undrawn. The resinous fumes slowly diminished, and as they did so the ring-system became paler. It finally disappeared. Continuing to look in the same direction, the rings revived, but now the colours were complementary to the former ones. _The neutral point had passed me in its motion down the beam, consequent upon the attenuation of the fumes of resin_.

With the fumes of chloride of ammonium substantially the same results were obtained. Sufficient, however, has been here stated to illustrate the variability of the position of the neutral point. [Footnote: Brewster has proved the variability of the position of the neutral point for skylight with the sun's altitude, a result obviously connected with the foregoing experiments.]

By a puff of tobacco-smoke, or of condensed steam, blown into the illuminated beam, the brilliancy of the selenite colours may be greatly enhanced. But with different clouds two different effects are produced. Let the ring-system observed in the common air be brought to its maximum strength, and then let an attenuated cloud of chloride of ammonium be thrown into the beam at the point looked at; the ring system flashes out with augmented brilliancy, but the character of the polarisation remains unchanged. This is also the case when phosphorus, or sulphur, is burned underneath the beam, so as to cause the fine particles of phosphorus or of sulphur to rise into the light. With the sulphur-fumes the brilliancy of the colours is exceedingly intensified; but in none of these cases is there any change in the character of the polarisation.

But when a puff of the fumes of hydrochloric acid, hydriodic acid, or nitric acid is thrown into the beam, there is a complete reversal of the selenite tints. Each of these clouds twists the plane of polarisation 90°, causing the centre of the ring-system to change from black to white, and the rings themselves to emit their complementary colours. [Footnote: Sir John Herschel suggested to me that this change of the polarisation from positive to negative may indicate a change from polarisation by reflection to polarisation by refraction. This thought repeatedly occurred to me while looking at the effects; but it will require much following up before it emerges into clearness.]

Almost all liquids have motes in them sufficiently numerous to polarise sensibly the light, and very beautiful effects may be obtained by simple artificial devices. When, for example, a cell of distilled water is placed in front of the electric lamp, and a thin slice of the beam is permitted to pass through it, scarcely any polarised light is discharged, and scarcely any colour produced with a plate of selenite. But if a bit of soap be agitated in the water above the beam, the moment the infinitesimal particles reach the light the liquid sends forth laterally almost perfectly polarised light; and if the selenite be employed, vivid colours flash into existence. A still more brilliant result is obtained with mastic dissolved in a great excess of alcohol.

The selenite rings, in fact, constitute an extremely delicate test as to the collective quantity of individually invisible particles in a liquid. Commencing with distilled water, for example, a thick slice of light is necessary to make the polarisation of its suspended particles sensible. A much thinner slice suffices for common water; while, with Bruecke's precipitated mastic, a slice too thin to produce any sensible effect with most other liquids, suffices to bring out vividly the selenite colours.

3. THE SKY OF THE ALPS.

The vision of an object always implies a differential action on the retina of the observer. The object is distinguished from surrounding space by its excess or defect of light in relation to that space. By altering the illumination, either of the object itself or of its environment, we alter the appearance of the object. Take the case of clouds floating in the atmosphere with patches of blue between them. Anything that changes the illumination of either alters the appearance of both, that appearance depending, as stated, upon differential action.

Now the light of the sky, being polarised, may, as the reader of the foregoing pages knows, be in great part quenched by a Nicol's prism, while the light of a common cloud, being unpolarised, cannot be thus extinguished. Hence the possibility of very remarkable variations, not only in the aspect of the firmament, which is really changed, but also in the aspect of the clouds, which have that firmament as a background. It is possible, for example, to choose clouds of such a depth of shade that when the Nicol quenches the light behind them, they shall vanish, being undistinguishable from the residual dull tint which outlives the extinction of the brilliancy of the sky. A cloud less deeply shaded, but still deep enough, when viewed with the naked eye, to appear dark on a bright ground, is suddenly changed to a white cloud on a dark ground by the quenching of the light behind it. When a reddish cloud at sunset chances to float in the region of maximum polarisation, the quenching of the surrounding light causes it to flash with a brighter crimson. Last Easter eve the Dartmoor sky, which had just been cleansed by a snow-storm, wore a very wild appearance. Round the horizon it was of steely brilliancy, while reddish cumuli and cirri floated southwards. When the sky was quenched behind them these floating masses seemed like dull embers suddenly blown upon; they brightened like a fire.

In the Alps we have the most magnificent examples of crimson clouds and snows, so that the effects just referred to may be here studied under the best possible conditions. On August 23, 1869, the evening Alpenglow was very fine, though it did not reach its maximum depth and splendour. The side of the Weisshorn seen from the Bel Alp, being turned from the sun, was tinted mauve; but I wished to observe one of the rose-coloured buttresses of the mountain. Such a one was visible from a point a few hundred feet above the hotel. The Matterhorn also, though for the most part in shade, had a crimson projection, while a deep ruddy red lingered along its western shoulder. Four distinct peaks and buttresses of the Dom, in addition to its dominant head--all covered with pure snow--were reddened by the light of sunset. The shoulder of the Alphubel was similarly coloured, while the great mass of the Fletschorn was all a-glow, and so was the snowy spine of the Monte Leone.

Looking at the Weisshorn through the Nicol, the glow of its protuberance was strong or weak according to the position of the prism. The summit also underwent striking changes. In one position of the prism it exhibited a pale white against a dark background; in the rectangular position it was a dark mauve against a light background. The red of the Matterhorn changed in a similar manner; but the whole mountain also passed through wonderful changes of definition. The air at the time was filled with a silvery haze, in which the Matterhorn almost disappeared. This could be wholly quenched by the Nicol, and then the mountain sprang forth with astonishing solidity and detachment from the surrounding air. The changes of the Dom were still more wonderful. A vast amounts of light could be removed from the sky behind it, for it occupied the position of maximum polarisation. By a little practice with the Nicol it was easy to render the extinction of the light, or its restoration, almost instantaneous. When the sky was quenched, the four minor peaks and buttresses, and the summit of the Dom, together with the shoulder of the Alphubel, glowed as if set suddenly on fire. This was immediately dimmed by turning the Nicol through an angle of 90°. It was not the stoppage of the light of the sky behind the mountains alone which produced this startling effect; the air between them and me was highly opalescent, and the quenching of this intermediate glare augmented remarkably the distinctness of the mountains.

On the morning of August 24 similar effects were finely shown. At 10 A.M. all three mountains, the Dom, the Matterhorn, and the Weisshorn, were powerfully affected by the Nicol. But in this instance also, the line drawn to the Dom being very nearly perpendicular to the solar beams, the effects on this mountain were most striking. The grey summit of the Matterhorn, at the same time, could scarcely be distinguished from the opalescent haze around it; but when the Nicol quenched the haze, the summit became instantly isolated, and stood out in bold definition. It is to be remembered that in the production of these effects the only things changed are the sky behind, and the luminous haze in front of the mountains; that these are changed because the light emitted from the sky and from the haze is plane polarised light, and that the light from the snows and from the mountains, being sensibly unpolarised, is not directly affected by the Nicol. It will also be understood that it is not the interposition of the haze _as an opaque body_ that renders the mountains indistinct, but that it is the _light_ of the haze which dims and bewilders the eye, and thus weakens the definition of objects seen through it.

These results have a direct bearing upon what artists call 'aerial perspective.' As we look from the summit of Mont Blanc, or from a lower elevation, at the serried crowd of peaks, especially if the mountains be darkly coloured--covered with pines, for example--every peak and ridge is separated from the mountains behind it by a thin blue haze which renders the relations of the mountains as to distance unmistakable. When this haze is regarded through the Nicol perpendicular to the sun's rays, it is in many cases wholly quenched, because the light which it emits in this direction is wholly polarised. When this happens, aerial perspective is abolished, and mountains very differently distant appear to rise in the same vertical plane. Close to the Bel Alp for instance, is the gorge of the Massa, and beyond the gorge is a high ridge darkened by pines. This ridge may be projected upon the dark slopes at the opposite side of the Rhone valley, and between both we have the blue haze referred to, throwing the distant mountains far away. But at certain hours of the day the haze may be quenched, and then the Massa ridge and the mountains beyond the Rhone seem almost equally distant from the eye. The one appears, as it were, a vertical continuation of the other. The haze varies with the temperature and humidity of the atmosphere. At certain times and places it is almost as blue as the sky itself; but to see its colour, the attention must be withdrawn from the mountains and from the trees which cover them. In point of fact, the haze is a piece of more or less perfect sky; it is produced in the same manner, and is subject to the same laws, as the firmament itself. We live _in_ the sky, not _under_ it.

These points were further elucidated by the deportment of the selenite, plate, with which the readers of the foregoing pages are so well acquainted. On some of the sunny days of August the haze in the valley of the Rhone, as looked at from the Bel Alp, was very remarkable. Towards evening the sky above the mountains opposite to my place of observation yielded a series of the most splendidly-coloured iris-rings; but on lowering the selenite until it had the darkness of the pines at the opposite side of the Rhone 'valley, instead of the darkness of space, as a background, the colours were not much diminished in brilliancy. I should estimate the distance across the valley, as the crow flies, to the opposite mountain, at nine miles; so that a body of air of this thickness can, under favourable circumstances, produce chromatic effects of polarisation almost as vivid as those produced by the sky itself.

Again: the light of a landscape, as of most other things, consists of two parts; the one, coming purely from superficial reflection, is always of the same colour as the light which falls upon the landscape; the other part reaches us from a certain depth within the objects which compose the landscape, and it is this portion of the total light which gives these objects their distinctive colours. The white light of the sun enters all substances to a certain depth, and is partly ejected by internal reflection; each distinct substance absorbing and reflecting the light, in accordance with the laws of its own molecular constitution. Thus the solar light is _sifted_ by the landscape, which appears in such colours and variations of colour as, after the sifting process, reach the observer's eye. Thus the bright green of grass, or the darker colour of the pine, never comes to us alone, but is always mingled with an amounts of light derived from superficial reflection. A certain hard brilliancy is conferred upon the woods and meadows by this superficially-reflected light. Under certain circumstances, it may be quenched by a Nicol's prism, and we then obtain the true colour of the grass and foliage. Trees and meadows, thus regarded, exhibit a richness and softness of tint which they never show as long as the superficial light is permitted to mingle with the true interior emission. The needles of the pines show this effect very well, large-leaved trees still better; while a glimmering field of maize exhibits the most extraordinary variations when looked at through the rotating Nicol.

Thoughts and questions like those here referred to took me, in August 1869, to the top of the Aletschhorn. The effects described in the foregoing paragraphs were for the most part reproduced on the summit of the mountain. I scanned the whole of the sky with my Nicol. Both alone, and in conjunction with the selenite, it pronounced the perpendicular to the solar beams to be the direction of maximum polarisation.

But at no portion of the firmament was the polarisation complete. The artificial sky produced in the experiments recorded in the preceding pages could, in this respect, be rendered far more perfect than the natural one; while the gorgeous 'residual blue' which makes its appearance when the polarisation of the artificial sky ceases to be perfect, was strongly contrasted with the lack-lustre hue which, in the case of the firmament, outlived the extinction of the brilliancy. With certain substances, however, artificially treated, this dull residue may also be obtained.

All along the arc from the Matterhorn to Mont Blanc the light of the sky immediately above the mountains was powerfully acted upon by the Nicol. In some cases the variations of intensity were astonishing. I have already said that a little practice enables the observer to shift the Nicol from one position to another so rapidly as to render the alternative extinction and restoration of the light immediate. When this was done along the arc to which I have referred, the alternations of light and darkness resembled the play of sheet lightning behind the mountains. There was an element of awe connected with the suddenness with which the mighty masses, ranged along the line referred to, changed their aspect and definition under the operation of the prism.

*****

The physical reason of the blueness of both natural and artificial skies is, I trust, correctly given in the essay on the Scientific use of the Imagination published in the second volume of these Fragments.

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