Creative Chemistry Part 4

--From U S. Bureau of Mines Report, 1918.

This table shows how inadequate was the reaction of the United States to the war demand for pota.s.sium salts. The minimum yearly requirements of the United States are estimated to be 250,000 tons of potash.

This completes our survey of the visible sources of potash in America.

In 1917 under the pressure of the embargo and unprecedented prices the output of potash (K_{2}O) in various forms was raised to 32,573 tons, but this is only about a tenth as much as we needed. In 1918 potash production was further raised to 52,135 tons, chiefly through the increase of the output from natural brines to 39,255 tons, nearly twice what it was the year before. The rust in cotton and the resulting decrease in yield during the war are laid to lack of potash. Truck crops grown in soils deficient in potash do not stand transportation well. The Bureau of Animal Industry has shown in experiments in Aroostook County, Maine, that the addition of moderate amounts of potash doubled the yield of potatoes.

Professor Ostwald, the great Leipzig chemist, boasted in the war:

America went into the war like a man with a rope round his neck which is in his enemy's hands and is pretty tightly drawn. With its tremendous deposits Germany has a world monopoly in potash, a point of immense value which cannot be reckoned too highly when once this war is going to be settled. It is in Germany's power to dictate which of the nations shall have plenty of food and which shall starve.

If, indeed, some mineralogist or metallurgist will cut that rope by showing us a supply of cheap potash we will erect him a monument as big as Washington's. But Ostwald is wrong in supposing that America is as dependent as Germany upon potash. The bulk of our food crops are at present raised without the use of any fertilizers whatever.

As the cession of Lorraine in 1871 gave Germany the phosphates she needed for fertilizers so the retrocession of Alsace in 1919 gives France the potash she needed for fertilizers. Ten years before the war a bed of potash was discovered in the Forest of Monnebruck, near Hartmannsweilerkopf, the peak for which French and Germans contested so fiercely and so long. The layer of pota.s.sium salts is 16-1/2 feet thick and the total deposit is estimated to be 275,000,000 tons of potash. At any rate it is a formidable rival of Sta.s.sfurt and its acquisition by France breaks the German monopoly.

When we turn to the consideration of the third plant food we feel better. While the United States has no such monopoly of phosphates as Germany had of potash and Chile had of nitrates we have an abundance and to spare. Whereas we formerly _imported_ about $17,000,000 worth of potash from Germany and $20,000,000 worth of nitrates from Chile a year we _exported_ $7,000,000 worth of phosphates.

Whoever it was who first noticed that the gra.s.s grew thicker around a buried bone he lived so long ago that we cannot do honor to his powers of observation, but ever since then--whenever it was--old bones have been used as a fertilizer. But we long ago used up all the buffalo bones we could find on the prairies and our packing houses could not give us enough bone-meal to go around, so we have had to draw upon the old bone-yards of prehistoric animals. Deposits of lime phosphate of such origin were found in South Carolina in 1870 and in Florida in 1888.

Since then the industry has developed with amazing rapidity until in 1913 the United States produced over three million tons of phosphates, nearly half of which was sent abroad. The chief source at present is the Florida pebbles, which are dredged up from the bottoms of lakes and rivers or washed out from the banks of streams by a hydraulic jet. The gravel is washed free from the sand and clay, screened and dried, and then is ready for shipment. The rock deposits of Florida and South Carolina are more limited than the pebble beds and may be exhausted in twenty-five or thirty years, but Tennessee and Kentucky have a lot in reserve and behind them are Idaho, Wyoming and other western states with millions of acres of phosphate land, so in this respect we are independent.

But even here the war hit us hard. For the calcium phosphate as it comes from the ground is not altogether available because it is not very soluble and the plants can only use what they can get in the water that they suck up from the soil. But if the phosphate is treated with sulfuric acid it becomes more soluble and this product is sold as "superphosphate." The sulfuric acid is made mostly from iron pyrite and this we have been content to import, over 800,000 tons of it a year, largely from Spain, although we have an abundance at home. Since the shortage of shipping shut off the foreign supply we are using more of our own pyrite and also our deposits of native sulfur along the Gulf coast. But as a consequence of this sulfuric acid during the war went up from $5 to $25 a ton and acidulated phosphates rose correspondingly.

Germany is short on natural phosphates as she is long on natural potash.

But she has made up for it by utilizing a by-product of her steelworks.

When phosphorus occurs in iron ore, even in minute amounts, it makes the steel brittle. Much of the iron ores of Alsace-Lorraine were formerly considered unworkable because of this impurity, but shortly after Germany took these provinces from France in 1871 a method was discovered by two British metallurgists, Thomas and Gilchrist, by which the phosphorus is removed from the iron in the process of converting it into steel. This consists in lining the crucible or converter with lime and magnesia, which takes up the phosphorus from the melted iron. This slag lining, now rich in phosphates, can be taken out and ground up for fertilizer. So the phosphorus which used to be a detriment is now an additional source of profit and this British invention has enabled Germany to make use of the territory she stole from France to outstrip England in the steel business. In 1910 Germany produced 2,000,000 tons of Thomas slag while only 160,000 tons were produced in the United Kingdom. The open hearth process now chiefly used in the United States gives an acid instead of a basic phosphate slag, not suitable as a fertilizer. The iron ore of America, with the exception of some of the southern ores, carries so small a percentage of phosphorus as to make a basic process inadvisable.

Recently the Germans have been experimenting with a combined fertilizer, Schroder's pota.s.sium phosphate, which is said to be as good as Thomas slag for phosphates and as good as Sta.s.sfurt salts for potash. The American Cyanamid Company is just putting out a similar product, "Ammo-Phos," in which the ammonia can be varied from thirteen to twenty per cent. and the phosphoric acid from twenty to forty-seven per cent.

so as to give the proportions desired for any crop. We have then the possibility of getting the three essential plant foods altogether in one compound with the elimination of most of the extraneous elements such as lime and magnesia, chlorids and sulfates.

For the last three hundred years the American people have been living on the unearned increment of the unoccupied land. But now that all our land has been staked out in homesteads and we cannot turn to new soil when we have used up the old, we must learn, as the older races have learned, how to keep up the supply of plant food. Only in this way can our population increase and prosper. As we have seen, the phosphate question need not bother us and we can see our way clear toward solving the nitrate question. We gave the Government $20,000,000 to experiment on the production of nitrates from the air and the results will serve for fields as well as firearms. But the question of an independent supply of cheap potash is still unsolved.

IV

COAL-TAR COLORS

If you put a bit of soft coal into a test tube (or, if you haven't a test tube, into a clay tobacco pipe and lute it over with clay) and heat it you will find a gas coming out of the end of the tube that will burn with a yellow smoky flame. After all the gas comes off you will find in the bottom of the test tube a chunk of dry, porous c.o.ke. These, then, are the two main products of the destructive distillation of coal. But if you are an unusually observant person, that is, if you are a born chemist with an eye to by-products, you will notice along in the middle of the tube where it is neither too hot nor too cold some dirty drops of water and some black sticky stuff. If you are just an ordinary person, you won't pay any attention to this because there is only a little of it and because what you are after is the c.o.ke and gas. You regard the nasty, smelly mess that comes in between as merely a nuisance because it clogs up and spoils your nice, clean tube.

Now that is the way the gas-makers and c.o.ke-makers--being for the most part ordinary persons and not born chemists--used to regard the water and tar that got into their pipes. They washed it out so as to have the gas clean and then ran it into the creek. But the neighbors--especially those who fished in the stream below the gas-works--made a fuss about spoiling the water, so the gas-men gave away the tar to the boys for use in celebrating the Fourth of July and election night or sold it for roofing.

[Ill.u.s.tration: THE PRODUCTION OF COAL TAR

A battery of Koppers by-product c.o.ke-ovens at the plant of the Bethlehem Steel Company, Sparrows Point, Maryland. The c.o.ke is being pushed out of one of the ovens into the waiting car. The vapors given off from the coal contain ammonia and the benzene compound used to make dyes and explosives]

[Ill.u.s.tration: IN THESE MIXING VATS AT THE BUFFALO WORKS, ANILINE DYES ARE PREPARED]

But this same tar, which for a hundred years was thrown away and nearly half of which is thrown away yet in the United States, turns out to be one of the most useful things in the world. It is one of the strategic points in war and commerce. It wounds and heals. It supplies munitions and medicines. It is like the magic purse of Fortunatus from which anything wished for could be drawn. The chemist puts his hand into the black ma.s.s and draws out all the colors of the rainbow. This evil-smelling substance beats the rose in the production of perfume and surpa.s.ses the honey-comb in sweetness.

Bishop Berkeley, after having proved that all matter was in your mind, wrote a book to prove that wood tar would cure all diseases. n.o.body reads it now. The name is enough to frighten them off: "Siris: A Chain of Philosophical Reflections and Inquiries Concerning the Virtues of Tar Water." He had a sort of mystical idea that tar contained the quintessence of the forest, the purified spirit of the trees, which could somehow revive the spirit of man. People said he was crazy on the subject, and doubtless he was, but the interesting thing about it is that not even his active and ingenious imagination could begin to suggest all of the strange things that can be got out of tar, whether wood or coal.

The reason why tar supplies all sorts of useful material is because it is indeed the quintessence of the forest, of the forests of untold millenniums if it is coal tar. If you are acquainted with a village tinker, one of those all-round mechanics who still survive in this age of specialization and can mend anything from a baby-carriage to an automobile, you will know that he has on the floor of his back shop a heap of broken machinery from which he can get almost anything he wants, a copper wire, a zinc plate, a bra.s.s screw or a steel rod. Now coal tar is the sc.r.a.p-heap of the vegetable kingdom. It contains a little of almost everything that makes up trees. But you must not imagine that all that comes out of coal tar is contained in it. There are only about a dozen primary products extracted from coal tar, but from these the chemist is able to build up hundreds of thousands of new substances.

This is true creative chemistry, for most of these compounds are not to be found in plants and never existed before they were made in the laboratory. It used to be thought that organic compounds, the products of vegetable and animal life, could only be produced by organized beings, that they were created out of inorganic matter by the magic touch of some "vital principle." But since the chemist has learned how, he finds it easier to make organic than inorganic substances and he is confident that he can reproduce any compound that he can a.n.a.lyze. He cannot only imitate the manufacturing processes of the plants and animals, but he can often beat them at their own game.

When coal is heated in the open air it is burned up and nothing but the ashes is left. But heat the coal in an enclosed vessel, say a big fireclay retort, and it cannot burn up because the oxygen of the air cannot get to it. So it breaks up. All parts of it that can be volatized at a high heat pa.s.s off through the outlet pipe and nothing is left in the retort but c.o.ke, that is carbon with the ash it contains. When the escaping vapors reach a cool part of the outlet pipe the oily and tarry matter condenses out. Then the gas is pa.s.sed up through a tower down which water spray is falling and thus is washed free from ammonia and everything else that is soluble in water.

This process is called "destructive distillation." What products come off depends not only upon the composition of the particular variety of coal used, but upon the heat, pressure and rapidity of distillation. The way you run it depends upon what you are most anxious to have. If you want illuminating gas you will leave in it the benzene. If you are after the greatest yield of tar products, you impoverish the gas by taking out the benzene and get a blue instead of a bright yellow flame. If all you are after is cheap c.o.ke, you do not bother about the by-products, but let them escape and burn as they please. The tourist pa.s.sing across the coal region at night could see through his car window the flames of hundreds of old-fashioned bee-hive c.o.ke-ovens and if he were of economical mind he might reflect that this display of fireworks was costing the country $75,000,000 a year besides consuming the irreplaceable fuel supply of the future. But since the gas was not needed outside of the cities and since the coal tar, if it could be sold at all, brought only a cent or two a gallon, how could the c.o.ke-makers be expected to throw out their old bee-hive ovens and put in the expensive retorts and towers necessary to the recovery of the by-products? But within the last ten years the by-product ovens have come into use and now nearly half our c.o.ke is made in them.

Although the products of destructive distillation vary within wide limits, yet the following table may serve to give an approximate idea of what may be got from a ton of soft coal:

1 ton of coal may give Gas, 12,000 cubic feet Liquor (Washings) ammonium sulfate (7-25 pounds) Tar (120 pounds) benzene (10-20 pounds) toluene (3 pounds) xylene (1-1/2 pounds) phenol (1/2 pound) naphthalene (3/8 pound) anthracene (1/4 pound) pitch (80 pounds) c.o.ke (1200-1500 pounds)

When the tar is redistilled we get, among other things, the ten "crudes"

which are fundamental material for making dyes. Their names are: benzene, toluene, xylene, phenol, cresol, naphthalene, anthracene, methyl anthracene, phenanthrene and carbazol.

There! I had to introduce you to the whole receiving line, but now that that ceremony is over we are at liberty to do as we do at a reception, meet our old friends, get acquainted with one or two more and turn our backs on the rest. Two of them, I am sure, you've met before, phenol, which is common carbolic acid, and naphthalene, which we use for mothb.a.l.l.s. But notice one thing in pa.s.sing, that not one of them is a dye. They are all colorless liquids or white solids. Also they all have an indescribable odor--all odors that you don't know are indescribable--which gives them and their progeny, even when odorless, the name of "aromatic compounds."

[Ill.u.s.tration: Fig. 8. Diagram of the products obtained from coal and some of their uses.]

The most important of the ten because he is the father of the family is benzene, otherwise called benzol, but must not be confused with "benzine" spelled with an _i_ which we used to burn and clean our clothes with. "Benzine" is a kind of gasoline, but benzene _alias_ benzol has quite another const.i.tution, although it looks and burns the same. Now the search for the const.i.tution of benzene is one of the most exciting chapters in chemistry; also one of the most intricate chapters, but, in spite of that, I believe I can make the main point of it clear even to those who have never studied chemistry--provided they retain their childish liking for puzzles. It is really much like putting together the old six-block Chinese puzzle. The chemist can work better if he has a picture of what he is working with. Now his unit is the molecule, which is too small even to a.n.a.lyze with the microscope, no matter how high powered. So he makes up a sort of diagram of the molecule, and since he knows the number of atoms and that they are somehow attached to one another, he represents each atom by the first letter of its name and the points of attachment or bonds by straight lines connecting the atoms of the different elements. Now it is one of the rules of the game that all the bonds must be connected or hooked up with atoms at both ends, that there shall be no free hands reaching out into empty s.p.a.ce. Carbon, for instance, has four bonds and hydrogen only one. They unite, therefore, in the proportion of one atom of carbon to four of hydrogen, or CH_{4}, which is methane or marsh gas and obviously the simplest of the hydrocarbons. But we have more complex hydrocarbons such as C_{6}H_{14}, known as hexane. Now if you try to draw the diagrams or structural formulas of these two compounds you will easily get

H H H H H H H | | | | | | | H-C-H H-C-C-C-C-C-C-H | | | | | | | H H H H H H H methane hexane

Each carbon atom, you see, has its four hands outstretched and duly grasped by one-handed hydrogen atoms or by neighboring carbon atoms in the chain. We can have such chains as long as you please, thirty or more in a chain; they are all contained in kerosene and paraffin.

So far the chemist found it east to construct diagrams that would satisfy his sense of the fitness of things, but when he found that benzene had the compostion C_{6}H_{6} he was puzzled. If you try to draw the picture of C_{6}H_{6} you will get something like this:

| | | | | | -C-C-C-C-C-C- | | | | | | H H H H H H

which is an absurdity because more than half of the carbon hands are waving wildly around asking to be held by something. Benzene, C_{6}H_{6}, evidently is like hexane, C_{6}H_{14}, in having a chain of six carbon atoms, but it has dropped its H's like an Englishman. Eight of the H's are missing.

Now one of the men who was worried over this benzene puzzle was the German chemist, Kekule. One evening after working over the problem all day he was sitting by the fire trying to rest, but he could not throw it off his mind. The carbon and the hydrogen atoms danced like imps on the carpet and as he watched them through his half-closed eyes he suddenly saw that the chain of six carbon atoms had joined at the ends and formed a ring while the six hydrogen atoms were holding on to the outside hands, in this fashion:

H | C / H-C C-H || | H-C C-H // C | H

Professor Kekule saw at once that the demons of his subconscious self had furnished him with a clue to the labyrinth, and so it proved. We need not suppose that the benzene molecule if we could see it would look anything like this diagram of it, but the theory works and that is all the scientist asks of any theory. By its use thousands of new compounds have been constructed which have proved of inestimable value to man. The modern chemist is not a discoverer, he is an inventor. He sits down at his desk and draws a "Kekule ring" or rather hexagon. Then he rubs out an H and hooks a nitro group (NO_{2}) on to the carbon in place of it; next he rubs out the O_{2} of the nitro group and puts in H_{2}; then he hitches on such other elements, or carbon chains and rings as he likes.

He works like an architect designing a house and when he gets a picture of the proposed compounds to suit him he goes into the laboratory to make it. First he takes down the bottle of benzene and boils up some of this with nitric acid and sulfuric acid. This he puts in the nitro group and makes nitro-benzene, C_{6}H_{5}NO_{2}. He treats this with hydrogen, which displaces the oxygen and gives C_{6}H_{5}NH_{2} or aniline, which is the basis of so many of these compounds that they are all commonly called "the aniline dyes." But aniline itself is not a dye. It is a colorless or brownish oil.

It is not necessary to follow our chemist any farther now that we have seen how he works, but before we pa.s.s on we will just look at one of his products, not one of the most complicated but still complicated enough.

[Ill.u.s.tration: A molecule of a coal-tar dye]

The name of this is sodium ditolyl-disazo-beta-naphthylamine- 6-sulfonic-beta-naphthylamine-3.6-disulfonate.

These chemical names of organic compounds are discouraging to the beginner and amusing to the layman, but that is because neither of them realizes that they are not really words but formulas. They are hyphenated because they come from Germany. The name given above is no more of a mouthful than "a-square-plus-two-a-b-plus-b-square" or "Third a.s.sistant Secretary of War to the President of the United States of America." The trade name of this dye is Brilliant Congo, but while that is handier to say it does not mean anything. n.o.body but an expert in dyes would know what it was, while from the formula name any chemist familiar with such compounds could draw its picture, tell how it would behave and what it was made from, or even make it. The old alchemist was a secretive and pretentious person and used to invent queer names for the purpose of mystifying and awing the ignorant. But the chemist in dropping the al- has dropped the idea of secrecy and his names, though equally appalling to the layman, are designed to reveal and not to conceal.

From this brief explanation the reader who has not studied chemistry will, I think, be able to get some idea of how these very intricate compounds are built up step by step. A completed house is hard to understand, but when we see the mason laying one brick on top of another it does not seem so difficult, although if we tried to do it we should not find it so easy as we think. Anyhow, let me give you a hint. If you want to make a good impression on a chemist don't tell him that he seems to you a sort of magician, master of a black art, and all that nonsense. The chemist has been trying for three hundred years to live down the reputation of being inspired of the devil and it makes him mad to have his past thrown up at him in this fashion. If his tactless admirers would stop saying "it is all a mystery and a miracle to me, and I cannot understand it" and pay attention to what he is telling them they would understand it and would find that it is no more of a mystery or a miracle than anything else. You can make an electrician mad in the same way by interrupting his explanation of a dynamo by asking: "But you cannot tell me what electricity really is." The electrician does not care a rap what electricity "really is"--if there really is any meaning to that phrase. All he wants to know is what he can do with it.