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LECTURE ON PLATINUM

[Delivered before the ROYAL INSTITUTION, on Friday, February 22, 1861.]

Whether I was to have the honour of appearing before you this evening or not, seemed to be doubtful upon one or two points. One of these I will mention immediately; the other may or may not appear during the course of the hour that follows. The first point is this. When I was tempted to promise this subject for your attention this evening, it was founded upon a promise, and a full intent of performing that promise, on the part of my friend Deville, of Paris, to come here to shew before you a phenomenon in metallurgic chemistry not common. In that I have been disappointed. His intention was to have fused here some thirty or forty pounds of platinum, and so to have made manifest, through my mouth and my statement, the principles of a new process in metallurgy, in relation to this beautiful, magnificent, and valuable metal; but circumstances over which neither he nor I, nor others concerned, have sufficient control, have prevented the fulfilment of that intention; and the period at which I learned the fact was so recent, that I could hardly leave my place here to be filled by another, or permit you, who in your kindness have come to hear what might be said, to remain unreceived in the best manner possible to me under the circumstances. I therefore propose to state, as well as I can, what the principles are on which M. Deville proceeds, by means of drawings, and some subordinate or inferior experiments. The metal platinum, of which you see some very fine specimens on the table, has been known to us about a hundred years. It has been wrought in a beautiful way in this country, in France, and elsewhere, and supplied to the consumer in ingots of this kind, or in plates, such as we have here, or in masses, that by their very fall upon the table indicate the great weight of the substance, which is, indeed, nearly at the head of all substances in that respect. This substance has been given to us hitherto mainly through the philosophy of Dr. Wollaston, whom many of us know, and it is obtained in great purity and beauty. It is a very remarkable metal in many points, besides its known special uses. It usually comes to us in grains. Here is a very fine specimen of native platinum in grains. Here is also a nugget or ingot, and here are some small pieces gathered out of certain alluvial soils in Brazil, Mexico, California, and the Uralian districts of Russia.

It is strange that this metal is almost always found associated with some four or five other metals, most curious in their qualities and characteristics. They are called platiniferous metals; and they have not only the relation of being always found associated in this manner, but they have other relations of a curious nature, which I shall point out to you by a reference to one of the tables behind me. This substance is always native—it is always in the metallic state; and the metals with which it is found connected, and which are rarely found elsewhere, are palladium, rhodium, iridium, osmium, and ruthenium. We have the names in one of the tables arranged in two columns, representing, as you see, two groups—platinum, iridium, and osmium constituting one group; and ruthenium, rhodium, and palladium the other. Three of these have the chemical equivalent of 98-1/2, and the others a chemical equivalent of about half that number. Then the metals of one group have an extreme specific gravity—platinum being, in fact, the lightest of the three, or as light as the lightest. Osmium has a specific gravity of 21.4, and is the heaviest body in nature; platinum is 21.15, and iridium the same; the specific gravity of the other three being only about half that, namely, 11.3, 12.1, and 11.8. Then there is this curious relation, that palladium and iridium are very much alike, so that you would scarcely know one from the other, though one has only half the weight of the other, and only half the equivalent power. So with iridium and rhodium, and osmium and ruthenium, which are so closely allied that they make pairs, being separated each from its own group. Then these metals are the most infusible that we possess. Osmium is the most difficult to fuse: indeed, I believe it never has been fused, while every other metal has. Ruthenium comes next, iridium next, rhodium next, platinum next (so that it ranks here as a pretty fusible metal, and yet we have been long accustomed to speak of the infusibility of platinum), and next comes palladium, which is the most fusible metal of the whole. It is a curious thing to see this fine association of physical properties coming out in metals which are grouped together somehow or other in nature, but, no doubt, by causes which are related to analogous properties in their situation on the surface of the earth, for it is in alluvial soils that these things are found.

Now, with regard to this substance, let me tell you briefly how we get it. The process used to be this. The ore which I shewed you just now was taken, and digested in nitro-muriatic acid of a certain strength, and partly converted into a solution, with the leaving behind of certain bodies that I have upon the table. The platinum being dissolved with care in acids, to the solution the muriate of ammonia was added, as I am about to add it here. A yellow precipitate was then thrown down, as you perceive is the case now; and this, carefully washed and cleansed, gave us that body [pointing to a specimen of the chloride of platinum and ammonium], the other elements, or nearly all, being ejected. This substance being heated, gave us what we call platinum sponge, or platinum in the metallic state, so finely divided as to form a kind of heavy mass or sponge, which, at the time that Dr. Wollaston first sent it forth, was not fusible for the market or in the manufacturers' workshops, inasmuch as the temperature required was so high, and there were no furnaces that could bring the mass into a globule, and cause the parts to adhere together. Most of our metals that we obtain from nature, and work in our shops, are brought at last into a mass by fusion. I am not aware that there is in the arts or sciences any other than iron which is not so. Soft iron we do not bring together by fusion, but by a process which is analogous to the one that was followed in the case of platinum, namely, welding; for these divided grains of spongy platinum having been well washed and sunk in water for the purpose of excluding air, and pressed together, and heated, and hammered, and pressed again, until they come into a pretty close, dense, compact mass, did so cohere, that when the mass was put into the furnace of charcoal, and raised to a high temperature, the particles, at first infinitely divided—for they were chemically divided—adhered the one to the other, each to all the rest, until they made that kind of substance which you see here, which will bear rolling and expansion of every kind. No other process than that has hitherto been adopted for the purpose of obtaining this substance from the particles by solution, precipitation, ignition, and welding. It certainly is a very fine thing to see that we may so fully depend upon the properties of the various substances we have to deal with; that we can, by carrying out our processes, obtain a material like this, allowing of division and extension under a rolling mill—a material of the finest possible kind, the parts being held together, not with interstices, not with porosity, but so continuous that no fluids can pass between them; and, as Dr. Wollaston beautifully shewed, a globule of platinum fused by the voltaic battery and the oxy-hydrogen blowpipe, when drawn into a wire, was not sounder or stronger than this wire made by the curious coalescence of the particles by the sticking power that they had at high temperatures. This is the process adopted by Messrs. Johnson and Matthey, to whose great kindness I am indebted for these ingots and for the valuable assistance I have received in the illustrations.

The treatment, however, that I have to bring before you is of another kind; and it is in the hope that we shall be able before long to have such a thing as the manufacture of platinum of this kind, that I am encouraged to come before you, and tell you how far Deville has gone in the matter, and to give you illustrations of the principles on which he proceeds. I think it is but fair that you should see an experiment shewing you the way in which we get the adhesion of platinum. Probably you all know of the welding of iron: you go into the smith's shop, and you see him put the handle of a poker on to the stem, and by a little management and the application of heat he makes them one. You have no doubt seen him put the iron into the fire and sprinkle a little sand upon it. He does not know the philosophy he calls into play when he sprinkles a little sand over the oxide of iron, but he has a fine philosophy there, or practises it, when he gets his welding. I can shew you here this beautiful circumstance of the sticking together of the particles up to the fullest possible intensity of their combination. If you were to go into the workshops of Mr. Matthey, and see them hammering and welding away, you would see the value of the experiment I am about to shew you. I have here some platinum-wire. This is a metal which resists the action of acids, resists oxidation by heat, and change of any sort; and which, therefore, I may heat in the atmosphere without any flux. I bend the wire so as to make the ends cross: these I make hot by means of the blowpipe, and then, by giving them a tap with a hammer, I shall make them into one piece. Now that the pieces are united, I shall have great difficulty in pulling them apart, though they are joined only at the point where the two cylindrical surfaces came together. And now I have succeeded in pulling the wire apart, the division is not at the point of welding, but where the force of the pincers has cut it, so that the junction we have effected is a complete one. This, then, is the principle of the manufacture and production of platinum in the old way.

The treatment which Deville proposes to carry out, and which he has carried out to a rather large extent in reference to the Russian supply of platinum, is one altogether by heat, having little or no reference to the use of acids. That you may know what the problem is, look at this table, which gives you the composition of such a piece of platinum ore as I shewed you just now. Wherever it comes from, the composition is as complicated, though the proportions vary:—

Platinum, . . . . . 76.4

Iridium,. . . . . . 4.3

Rhodium,. . . . . . 0.3

Palladium,. . . . . 1.4

Gold, . . . . . . . 0.4

Copper, . . . . . . 4.1

Iron, . . . . . . . 11.7

Osmide of Iridium,. 0.5

Sand, . . . . . . . 1.4

––

100.5

This refers to the Uralian ore. In that state of combination, as shewn in the table, the iridium and osmium are found combined in crystals, sometimes to the amount of 0.5 per cent., and sometimes 3 or 4 per cent. Now, this Deville proposes to deal with in the dry way, in the place of dealing with it by any acid.

I have here another kind of platinum; and I shew it to you for this reason. The Russian Government, having large stores of platinum in their dominions, have obtained it in a metallic state, and worked it into coin. The coin I have in my hand is a twelve silver rouble piece. The rouble is worth three shillings, and this coin is, therefore, of the value of thirty-six shillings. The smaller coin is worth half that sum; and the other, half of that. The metal, however, is unfit for coinage. When you have the two metals, gold and silver, used for coinage, you have a little confusion in the value of the two in the market; but when you have three precious metals (for you may call platinum a precious metal) worked into coin, they will be sure to run counter to one another. Indeed, the case did happen, that the price of platinum coin fixed by the Government was such, that it was worth while to purchase platinum in other countries, and make coin of it, and then take it into that country and circulate it. The result was, that the Russian Government stopped the issue. The composition of this coin is—platinum, 97.0; iridium, 1.2; rhodium, 0.5; palladium, 0.25; a little copper, and a little iron. It is, in fact, bad platinum: it scales, and it has an unfitness for commercial use and in the laboratory, which the other well-purified platinum has not. It wants working over again.

Now, Deville's process depends upon three points,—upon intense heat, blowpipe action, and the volatility of certain metals. We know that there are plenty of metals that are volatile; but this, I think, is the first time that it has been proposed to use the volatility of certain metals—such as gold and palladium—for the purpose of driving them off and leaving something else behind. He counts largely upon the volatility of metals which we have not been in the habit of considering volatile, but which we have rather looked upon as fixed; and I must endeavour to illustrate these three points by a few experiments. Perhaps I can best show you what is required in the process of heating platinum by using that source of heat which we have here, and which seems to be almost illimitable—namely, the voltaic battery; for it is only in consequence of the heat that the voltaic battery affects the platinum. By applying the two extremities of the battery to this piece of platinum-wire, you will see what result we shall obtain. You perceive that we can take about this heating agent wherever we like, and deal with it as we please, limiting it in any way. I am obliged to deal carefully with it; but even that circumstance will have an interest for you in watching the experiment. Contact is now made. The electric current, when compressed into thin conducting-wires offering resistance, evolves heat to a large extent; and this is the power by which we work. You see the intense glow immediately imparted to the wire; and if I applied the heat continuously, the effect of the current would be to melt the wire. As soon as the contact is broken, the wire resumes its former appearance; and now that we make contact again, you perceive the glow as before. [The experiment was repeated several times in rapid succession.] You can see a line of light, though you can scarcely perceive the wire; and now that it has melted with the great heat, if you examine it, you will perceive that it is indeed a set of irregularities from end to end—a set of little spheres, which are strung upon an axis of platinum running through it. It is that wire which Mr. Grove described as being produced at the moment when fusion of the whole mass is commencing. In the same manner, if I take a tolerably thick piece of platinum, and subject it to the heat that can be produced by this battery, you will see the brilliancy of the effect produced. I shall put on a pair of spectacles for the experiment, as there is an injurious effect of the voltaic spark upon the eyes, if the action is continued; and it is neither policy nor bravery to subject any organ to unnecessary danger; and I want, at all events, to keep the full use of my eyes to the end of the lecture.

You now see the action of the heat upon the piece of platinum—heat so great as to break in pieces the plate on which the drops of metal fall. You perceive, then, that we have sufficiently powerful sources of heat in nature to deal with platinum. I have here an apparatus by which the same thing can be shewn. Here is a piece of platinum, which is put into a crucible of carbon made at the end of one pole of the battery, and you will see the brilliant light that will be produced. There is our furnace, and the platinum is rapidly getting heated; and now you perceive that it is melted, and throwing off little particles. What a magnificent philosophical instrument this is. When you look at the result, which is lying upon the charcoal, you will see a beautifully fused piece of platinum. It is now a fiery globule, with a surface so bright, and smooth, and reflecting, that I cannot tell whether it is transparent, or opaque, or what. This, then, will give you an idea of what has to be done by any process that pretends to deal with thirty, or forty, or fifty pounds of platinum at once.

Let me now tell you briefly what Deville proposes to do. First of all, he takes this ore, with its impurities, and mixes it (as he finds it essential and best) with its own weight of sulphuret of lead—lead combined with sulphur. Both the lead and the sulphur are wanted; for the iron that is there present, as you see by the table, is one of the most annoying substances in the treatment that you can imagine, because it is not volatile; and while the iron remains adhering to the platinum, the platinum will not flow readily. It cannot be sent away by a high temperature—sent into the atmosphere so as to leave the platinum behind. Well, then, a hundred parts of ore and a hundred parts of sulphuret of lead, with about fifty parts of metallic lead, being all mingled together in a crucible, the sulphur of the sulphuret takes the iron, the copper, and some of the other metals and impurities, and combines with them to form a slag; and as it goes on boiling and oxidising, it carries off the iron, and so a great cleansing takes place.

Now, you ought to know that these metals, such as platinum, iridium, and palladium, have a strong affinity for such metals as lead and tin, and upon this a great deal depends. Very much depends upon the platinum throwing out its impurities of iron and so forth, by being taken up with the lead present in it. That you may have a notion of the great power that platinum has of combining with other metals, I will refer you to a little of the chemist's experience—his bad experience. He knows very well that if he takes a piece of platinum-foil, and heats a piece of lead upon it, or if he takes a piece of platinum-foil, such as we have here, and heats things upon it that have lead in them, his platinum is destroyed. I have here a piece of platinum, and if I apply the heat of the spirit-lamp to it, in consequence of the presence of this little piece of lead which I will place on it, I shall make a hole in the metal. The heat of the lamp itself would do no harm to the platinum, nor would other chemical means; but because there is a little lead present, and there is an affinity between the two substances, the bodies fuse together at once. You see the hole I have made. It is large enough to put your finger in, though the platinum itself was, as you saw, almost infusible, except by the voltaic battery. For the purpose of shewing this fact in a more striking manner, I have taken pieces of platinum-foil, tin-foil, and lead-foil, and rolled them together; and if I apply the blowpipe to them, you will have, in fact, a repetition on a larger scale of the experiment you saw just now when the lead and platinum came together, and one spoiled the other. When the metals are laid one upon the other, and folded together and heat applied, you will not only see that the platinum runs to waste, but that at the time when the platinum and lead are combined there is ignition produced—there is a power of sustaining combustion. I have taken a large piece, that you may see the phenomenon on a large scale. You saw the ignition and the explosion which followed, of which we have here the results—the consequence of the chemical affinity between the platinum and the metals combined with it, which is the thing upon which Deville founds his first result.

When he has melted these substances and stirred them well up, and so obtained a complete mixture, he throws in air upon the surface to burn off all the sulphur from the remaining sulphuret of lead; and at last he gets an ingot of lead with platinum—much lead, comparatively, and little platinum. He gets that in the crucible with a lot of scoriæ and other things, which he treats afterwards. It is that platiniferous lead which we have to deal with in our future process. Now, let me tell you what he does with it. His first object is to get rid of the lead. He has thrown out all the iron, and a number of other things, and he has got this kind of compound indicated in the table. He may get it as high as 78 per cent. of platinum, and 22 of lead; or 5, or 10, or 15 of platinum, and 95, or 90, or 85 of lead (which he calls weak platinum), and he then places it in the kind of vessel that you see before you. Suppose we had the mixture here; we should have to make it hot, and then throw in air upon the surface. The combustible metal—that is, the lead—and the part that will oxidise, are thoroughly oxidised; the litharge would flow out in a fused state into a vessel placed to receive it, and the platinum remains behind.

Here is the process which Deville adopts for the purpose of casting off the lead, after he has got out the platinum from the ore. (Having made use of your friend, you get rid of him as quickly as you can.) He gets his heat by applying the combination of oxygen and hydrogen, or of carburetted fuel, for the purpose of producing a fire. I have here a source of coal-gas; there I have a source of hydrogen; and here I have a source of oxygen. I have here also one of the blowpipes used by Deville in his process for working platinum in the way I have spoken of. There are two pipes, and one of them goes to the source of coal-gas, and the other to the supply of oxygen.

By uniting these we obtain a flame of such a heat as to melt platinum. You will, perhaps, hardly imagine what the heat is, unless you have some proof of it; but you will soon see that I have actually the power of melting platinum. Here is a piece of platinum-foil running like wax under the flame which I am bringing to bear against it. The question, however, is whether we shall get heat enough to melt, not this small quantity, but large masses—many pounds of the metal. Having obtained heat like this, the next consideration is what vessel is he to employ which could retain the platinum when so heated, or bear the effects of the flame? Such vessels are happily well supplied at Paris, and are formed of a substance which surrounds Paris; it is a kind of chalk (called, I believe, by geologists, calcaire grossière), and it has the property of enduring an extreme degree of heat. I am now going to get the highest heat that we can obtain. First, I shew you the combustion of hydrogen by itself. I have not a large supply, because the coal-gas is sufficient for most of our purposes. If I put a piece of lime obtained from this chalk into the gas, you see we get a pretty hot flame, which would burn one's fingers a good deal But now let me subject a piece of it to the joint action of oxygen and hydrogen. I do this for the purpose of shewing you the value of lime as a material for the furnaces and chambers that are to contain the substances to be operated on, and that are consequently to sustain the action of this extreme heat. Here we have the hydrogen and the oxygen, which will give the most intense heat that can be obtained by chemical action; and if I put a piece of lime into the flame, we get what is called the lime-light. Now, with all the beauty and intensity of action which you perceive, there is no sensible deterioration of the lime except by the mechanical force of the current of gases rushing from the jet against the lime, sweeping away such particles as are not strongly aggregated. "Vapour of lime" some call it; and it may be so, but there is no other change of the lime than that under the action of heat of this highly-exalted chemical condition, though almost any other substance would melt at once.

Then, as to the way in which the heat is applied to the substance. It is all very well for me to take a piece of antimony, and fuse it in the flame of a blowpipe. But if I tried this piece in the ordinary lamp flame, I should do nothing; if I tried a smaller piece, I should do little or nothing; and if I tried a still smaller piece, I should do little or nothing; yet I have a condition which will represent what Deville carries to the highest possible extent, and which we all carry to the highest extent, in the use of the blowpipe. Suppose I take this piece of antimony: I shall not be able to melt it in that flame of the candle by merely holding it there; yet, by taking pains, we can even melt a piece of platinum there. This is a preparation which I made for the purpose of proving the fusibility of platinum in a common candle. There is a piece of wire, drawn by that ingenious process of Dr. Wollaston's, not more than the three-thousandth part of an inch in diameter. He put the wire into the middle of a cylinder of silver, and drew both together until the whole compound was exceedingly thin; and then he dissolved away the silver by nitric acid. There was left in the centre a substance which I can scarcely see with an eye-glass, but which I know is there, and which I can make visible, as you see, by putting it into the candle, where the heat makes it glow like a spark. I have again and again tried this experiment up-stairs in my own room, and have easily fused this platinum-wire by a common candle. You see we have, therefore, heat enough in the candle, as in the voltaic battery, or in the highly-exalted combustion of the blowpipe, but we do not supply a continuous source of heat. In the very act of this becoming ignited, the heat radiates so fast that you cannot accumulate enough to cause the fusion of the wire, except under the most careful arrangement. Thus I cannot melt that piece of antimony by simply putting it into the candle; but if I put it upon charcoal, and drive the fiery current against it, there will be heat enough to melt it. The beauty of the blowpipe is, that it sends hot air (making hot air by the combustion of the flame) against the thing to be heated. I have only to hold the antimony in the course of that current, and particle by particle of the current impinges upon the antimony, and so we get it melted. You now see it red-hot, and I have no doubt it will continue to burn if I withdraw it from the flame and continue to force the air on it. Now, you see it burning without any heat but that of its own combustion, which I am keeping up by sending the air against it. It would go out in a moment if I took away the current of air from it; but there it is burning, and the more air I give it, by this or any other action, the better it is. So, then, we have here not merely a mighty source of heat, but a means of driving the heat forcibly against substances.

Let me shew you another experiment with a piece of iron. It will serve two purposes—shewing you what the blowpipe does as a source of heat, and what it does by sending that heat where it is wanted. I have taken iron in contrast with silver or other metals, that you may see the difference of action, and so be more interested in the experiment. Here is our fuel, the coal-gas; and here our oxygen. Having thus my power of heat, I apply it to the iron, which, as you see, soon gets red-hot. It is now flowing about like a globule of melted mercury. But observe, I cannot raise any vapour: it is now covered with a coat of melted oxide, and unless I have a great power in my blowpipe, it is hardly possible to break through it. Now, then, you see these beautiful sparks: you have not only a beautiful kind of combustion, but you see the iron is being driven off, not producing smoke, but burning in a fixed condition. How different this is from the action of some other metals—that piece of antimony, for instance, which we saw just now throwing off abundance of fumes. We can, of course, burn away this iron by giving plenty of air to it; but with the bodies which Deville wants to expose to this intense heat he has not that means: the gas itself must have power enough to drive off the slag which forms on the surface of the metal, and power to impinge upon the platinum so as to get the full contact that he wants for the fusion to take place. We see here, then, the means to which he resorts—oxygen, and either coal-gas or water-gas¹⁹, or pure hydrogen, for producing heat, and the blowpipe for the purpose of impelling the heated current upon the metals.

I have two or three rough drawings here, representing the kind of furnaces which he employs. They are larger, however, than the actual furnaces he uses. Even the furnace in which he carries on that most serious operation of fusing fifty pounds of platinum at once is not much more than half the size of the drawing. It is made of a piece of lime below and a piece of lime above. You see how beautifully lime sustains heat without altering in shape; and you may have thought how beautifully it prevents the dissipation of the heat by its very bad conducting powers.

While the front part of the lime which you saw here was so highly ignited, I could at any moment touch the back of it without feeling any annoyance from the heat So, by having a chamber of lime of this sort, he is able to get a vessel to contain these metals with scarcely any loss of heat. He puts the blowpipes through these apertures, and sends down these gases upon the metals, which are gradually melted. He then puts in more metal through a hole at the top. The results of the combustion issue out of the aperture which you see represented. If there be strips of platinum, he pushes them through the mouth out of which the heated current is coming, and there they get red-hot and white-hot before they get into the bath of platinum. So he is able to fuse a large body of platinum in this manner. When the platinum is melted, he takes off the top and pours out from the bottom piece, like a crucible, and makes his cast. This is the furnace by which he fuses his forty pounds or fifty pounds of platinum at once. The metal is raised to a heat that no eye can bear. There is no light and shadow, no chiaro-oscuro there; all is the same intensity of glow. You look in, and you cannot see where the metal or the lime is; it is all as one. We have, therefore, a platform with a handle, which turns upon an axis, that coincides with the gutter that is formed for the pouring of the metal; and when all is known to be ready, by means of dark glasses, the workmen take off the top piece and lift up the handle, and the mould being then placed in a proper position, he knows that the issue of the metal will be exactly in the line of the axis. No injury has ever happened from the use of this plan. You know with what care it is necessary to carry such a vessel of mercury as we have here, for fear of turning it over on one side or the other; but if it be a vessel of melted platinum, the very greatest care must be used, because the substance is twice as heavy: yet no injury has been done to any of the workmen in this operation.