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On The Blue Color Of The Sky, And The Polarization Of Skylight

( Originally Published 1905 )



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 color of the sky, and the polarization 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 1/2 to 3 inches internal diameter. The vapor 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 vapors 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 vapor, 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 vapors 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 vapor. 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 endeavoring 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 vapor 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, polarized light was discharged, the direction of maximum polarization being at right angles to the illuminating beam; the plane of vibration of the polarized light was perpendicular to the beam.'

Thin plates of selenite or of quartz, placed between the Nicol and the actinic cloud, displayed the colors of polarized light, these colors 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 outward. When placed in its proper position between the Nicol and the cloud, it exhibited a system of splendidly-colored 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 vapor, 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 vapor, 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 vapor. The visible action of light upon the mixture after fifteen minutes' exposure was slight. The tube was afterward filled with half an atmosphere of the mixed air and vapor, 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 polarization. Looked at obliquely, the polarization was strong.

The experimental tube being again cleansed and exhausted, the mixed air and nitrite-of-butyl vapor was permitted to enter it until the associated mercury column was depressed 1/10th of an inch. In other words, the air and vapor, united, exercised a pressure not exceeding 1/800 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 polarized. It could be totally quenched by the Nicol. By degrees the cloud- became of whitish blue, and for a time the selenite colors, obtained by looking at it normally, were exceedingly brilliant. The direction of maximum polarization was distinctly at right angles to the illuminating beam. This continued to be the case as long as the cloud maintained a decided blue color, 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 polarized light in the direction of the perpendicular, while it continued to do so at both ends.

But the cloud which had thus ceased to polarize the light emitted normally, showed vivid selenite colors when looked at obliquely, proving that the direction of maxi-mum polarization 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 vapor 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 color rivalling that of the purest Italian sky. In all cases, moreover, this fine blue cloud polarizes perfectly the beam which illuminates it, the direction of polarization 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 polarization. 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 polarization begins to decay, a portion of the light passing through the prism in all its positions. It is worthy of note, that, for sometime after the cessation of perfect polarization, 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.' 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 polarization, in a direction perpendicular to the illuminating beam, is also illustrated by the following experiment: 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 polarized 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 down-ward, or vertically upward. 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 downward or upward. This truly fine experiment, 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 polarization of skylight, the greatest stumbling-block has hitherto been, that, in accordance with the law of Brewster, which makes the index of re-fraction the tangent of the polarizing angle, the reflection which produces perfect polarization 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.' I have, however, operated upon substances of widely different refractive indices, and therefore of very different polarizing angles as ordinarily defined, but the polarization of the beam, by the incipient cloud, has thus far proved itself to. be absolutely independent of the polarizing 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 polarization is at right angles to the illuminating beam, the polarizing 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.

But, as regards the polarization of the sky, we know that not only is the direction of maximum polarization 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 polarization, exist, on both sides of which the planes of atmospheric polarization 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 mat-ter 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 polarization obtained with the incipient clouds. The light discharged laterally from the track of the illuminating beam was polarized, though not perfectly, the direction of maximum polarization 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 polarization. Keeping the positions of the Nicol and the selenite constant, the same colors ,were observed throughout the entire beam, when the line of vision was perpendicular to its length.

The horizontal column of air, thus illuminated, was eighteen 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 colors fading until they disappeared. Augmenting the obliquity the colors 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 polarized 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 fourteen or fifteen 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 polarization.

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 polarized 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.' 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 polarization 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 polarized 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 polarization in M. Govi's experiment 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 polarization of the light discharged at right angles to the beam became weaker, the direction of maximum polarization 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 polarized light was discharged; but the direction of maximum polarization, 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°.

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

The laboratory was next filled with the fumes of gun-powder. 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°, 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 polarization enclosed, in this case, an angle of 12°, or thereabout, 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. Seeping 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 colors 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.'

By a puff of tobacco-smoke, or of condensed steam, blown into the illuminated beam, the brilliancy of the selenite colors 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 polarization 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 colors is exceedingly intensified; but in none of these cases is there any change in the character of the polarization.

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 polarization 90°, causing the centre of the ring-system to change, from black to white, and the rings themselves to emit their complementary colors.'

Almost all liquids have motes in them sufficiently numerous to polarize 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 polarized light is discharged, and scarcely any color 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 polarized light; and if the selenitc be employed, vivid colors 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 polarization of its suspended particles sensible. A much thinner slice suffices for common water; while, with Brucke's precipitated mastic, a slice too thin to produce any sensible effect with most other liquids, suffices to bring out vividly the selenite colors.



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