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 a.s.semblage 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 const.i.tuent atoms? Is the _vis viva_ of the intercepted light-waves transferred to the molecule as a whole, or to its const.i.tuent 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 Junction 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 pa.s.sed from the vaporous to the liquid state.

In point of fact, the decomposition of the nitrite of amyl is itself to some extent an ill.u.s.tration of this internal molecular absorption; for were the absorption the act of the molecule as a whole, the relative motions of its const.i.tuent 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 antic.i.p.ate 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 antic.i.p.ate 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 quant.i.ty 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 pa.s.sage 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 Brucke'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 quant.i.ty of the precipitate, can be caused to pa.s.s 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. .h.i.therto 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-gla.s.s, and round the two bells of the gla.s.s delicate cloud-filaments twisted themselves in spirals. It also folded itself into convolutions resembling those of sh.e.l.ls. In certain conditions of the atmosphere in the Alps I have often observed clouds of a special pearly l.u.s.tre; when hydrogen was made the vehicle of the iodide-of allyl vapour a similar l.u.s.tre 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 ill.u.s.trated 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 experiments. .h.i.therto 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 ma.s.s 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 r.e.t.a.r.ding 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 a.s.sumed 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-gla.s.ses 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 const.i.tute, 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 gla.s.s 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. .h.i.therto 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 quant.i.ty 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 const.i.tute 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 a.s.signed 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 quant.i.ty 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 quant.i.ty 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 quant.i.ty 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 quant.i.ty 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 quant.i.ties, 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 ill.u.s.trative 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 a.s.sociated 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, pa.s.sed 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 pa.s.sed 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 coa.r.s.er 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 ill.u.s.tration 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 pa.s.sing 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 pa.s.ses, 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 coa.r.s.e to approximate to that of ordinary clouds, the rotation of the Nicol ceases to have any sensible effect on the quant.i.ty of light discharged normally.

The perfection of the polarisation, in a direction perpendicular to the illuminating beam, is also ill.u.s.trated 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 pa.s.sed 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 a.s.sistant 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 a.s.sistant 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. .h.i.therto 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 s.p.a.ce.]

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 quant.i.ty 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.