Part 8

Thus, in brief outline, have been brought before you a few of the results of recent enquiry. If you ask me what is the use of them, I can hardly answer you, unless you define the term use. If you meant to ask whether those dark rays which clear away the Alpine snows, will ever be applied to the roasting of turkeys, or the driving of steam-engines--while affirming their power to do both, I would frankly confess that they are not at present capable of competing profitably with coal in these particulars. Still they may have great uses unknown to me; and when our coal-fields are exhausted, it is possible that a more aethereal race than we are may cook their victuals, and perform their work, in this transcendental way. But is it necessary that the student of science should have his labours tested by their possible practical applications? What is the practical value of Homer's Iliad? You smile, and possibly think that Homer's Iliad is good as a means of culture. There's the rub. The people who demand of science practical uses, forget, or do not know, that it also is great as a means of culture--that the knowledge of this wonderful universe is a thing profitable in itself, and requiring no practical application to justify its pursuit.

But while the student of Nature distinctly refuses to have his labours judged by their practical issues, unless the term practical be made to include mental as well as material good, he knows full well that the greatest practical triumphs have been episodes in the search after pure natural truth. The electric telegraph is the standing wonder of this age, and the men whose scientific knowledge, and mechanical skill, have made the telegraph what it is, are deserving of all honour. In fact, they have had their reward, both in reputation and in those more substantial benefits which the direct service of the public always carries in its train. But who, I would ask, put the soul into this telegraphic body? Who snatched from heaven the fire that flashes along the line? This, I am bound to say, was done by two men, the one a dweller in Italy, [Footnote: Volta] the other a dweller in England, [Footnote: Faraday] who never in their enquiries consciously set a practical object before them--whose only stimulus was the fascination which draws the climber to a never-trodden peak, and would have made Caesar quit his victories for the sources of the Nile. That the knowledge brought to us by those prophets, priests, and kings of science is what the world calls 'useful knowledge,' the triumphant application of their discoveries proves. But science has another function to fulfil, in the storing and the training of the human mind; and I would base my appeal to you on the specimen which has this evening been brought before you, whether any system of education at the present day can be deemed even approximately complete, in which the knowledge of Nature is neglected or ignored.

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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.

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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.