Creative Chemistry Part 2

The apparatus which effects this transformation is essentially a gigantic arc light in a chimney through which a current of hot air is blown. The more thoroughly the air comes under the action of the electric arc the more molecules of nitrogen and oxygen will be broken up and rearranged, but on the other hand if the mixture of gases remains in the path of the discharge the NO molecules are also broken up and go back into their original form of NN and OO. So the object is to spread out the electric arc as widely as possible and then run the air through it rapidly. In the Schonherr process the electric arc is a spiral flame twenty-three feet long through which the air streams with a vortex motion. In the Birkeland-Eyde furnace there is a series of semi-circular arcs spread out by the repellent force of a powerful electric magnet in a flaming disc seven feet in diameter with a temperature of 6300 F. In the Pauling furnace the electrodes between which the current strikes are two cast iron tubes curving upward and outward like the horns of a Texas steer and cooled by a stream of water pa.s.sing through them. These electric furnaces produce two or three ounces of nitric acid for each kilowatt-hour of current consumed. Whether they can compete with the natural nitrates and the products of other processes depends upon how cheaply they can get their electricity. Before the war there were several large installations in Norway and elsewhere where abundant water power was available and now the Norwegians are using half a million horse power continuously in the fixation of nitrogen and the rest of the world as much again. The Germans had invested largely in these foreign oxidation plants, but shortly before the war they had sold out and turned their attention to other processes not requiring so much electrical energy, for their country is poorly provided with water power. The Haber process, that they made most of, is based upon as simple a reaction as that we have been considering, for it consists in uniting two elemental gases to make a compound, but the elements in this case are not nitrogen and oxygen, but nitrogen and hydrogen. This gives ammonia instead of nitric acid, but ammonia is useful for its own purposes and it can be converted into nitric acid if this is desired.

The reaction is:

NN + HH + HH + HH --> NHHH + NHHH Nitrogen hydrogen ammonia

The animals go in two by two, but they come out four by four. Four molecules of the mixed elements are turned into two molecules and so the gas shrinks to half its volume. At the same time it acquires an odor--familiar to us when we are curing a cold--that neither of the original gases had. The agent that effects the transformation in this case is not the electric spark--for this would tend to work the reaction backwards--but uranium, a rare metal, which has the peculiar property of helping along a reaction while seeming to take no part in it. Such a substance is called a catalyst. The action of a catalyst is rather mysterious and whenever we have a mystery we need an a.n.a.logy. We may, then, compare the catalyst to what is known as "a good mixer" in society. You know the sort of man I mean. He may not be brilliant or especially talkative, but somehow there is always "something doing" at a picnic or house-party when he is along. The tactful hostess, the salon leader, is a social catalyst. The trouble with catalysts, either human or metallic, is that they are rare and that sometimes they get sulky and won't work if the ingredients they are supposed to mix are unsuitable.

But the uranium, osmium, platinum or whatever metal is used as a catalyzing agent is expensive and although it is not used up it is easily "poisoned," as the chemists say, by impurities in the gases. The nitrogen and the hydrogen for the Haber process must then be prepared and purified before trying to combine them into ammonia. The nitrogen is obtained by liquefying air by cold and pressure and then boiling off the nitrogen at 194 C. The oxygen left is useful for other purposes. The hydrogen needed is extracted by a similar process of fractional distillation from "water-gas," the blue-flame burning gas used for heating. Then the nitrogen and hydrogen, mixed in the proportion of one to three, as shown in the reaction given above, are compressed to two hundred atmospheres, heated to 1300 F. and pa.s.sed over the finely divided uranium. The stream of gas that comes out contains about four per cent. of ammonia, which is condensed to a liquid by cooling and the uncombined hydrogen and nitrogen pa.s.sed again through the apparatus.

The ammonia can be employed in refrigeration and other ways but if it is desired to get the nitrogen into the form of nitric acid it has to be oxidized by the so-called Ostwald process. This is the reaction:

NH_{3} + 4O --> HNO_{3} + H_{2}O ammonia oxygen nitric acid water

The catalyst used to effect this combination is the metal platinum in the form of fine wire gauze, since the action takes place only on the surface. The ammonia gas is mixed with air which supplies the oxygen and the heated mixture run through the platinum gauze at the rate of several yards a second. Although the gases come in contact with the platinum only a five-hundredth part of a second yet eighty-five per cent. is converted into nitric acid.

The Haber process for the making of ammonia by direct synthesis from its const.i.tuent elements and the supplemental Ostwald process for the conversion of the ammonia into nitric acid were the salvation of Germany. As soon as the Germans saw that their dash toward Paris had been stopped at the Marne they knew that they were in for a long war and at once made plans for a supply of fixed nitrogen. The chief German dye factories, the Badische Anilin and Soda-Fabrik, promptly put $100,000,000 into enlarging its plant and raised its production of ammonium sulfate from 30,000 to 300,000 tons. One German electrical firm with aid from the city of Berlin contracted to provide 66,000,000 pounds of fixed nitrogen a year at a cost of three cents a pound for the next twenty-five years. The 750,000 tons of Chilean nitrate imported annually by Germany contained about 116,000 tons of the essential element nitrogen. The fourteen large plants erected during the war can fix in the form of nitrates 500,000 tons of nitrogen a year, which is more than twice the amount needed for internal consumption. So Germany is now not only independent of the outside world but will have a surplus of nitrogen products which could be sold even in America at about half what the farmer has been paying for South American saltpeter.

Besides the Haber or direct process there are other methods of making ammonia which are, at least outside of Germany, of more importance. Most prominent of these is the cyanamid process. This requires electrical power since it starts with a product of the electrical furnace, calcium carbide, familiar to us all as a source of acetylene gas.

If a stream of nitrogen is pa.s.sed over hot calcium carbide it is taken up by the carbide according to the following equation:

CaC_{2} + N_{2} --> CaCN_{2} + C calcium carbide nitrogen calcium cyanamid carbon

Calcium cyanamid was discovered in 1895 by Caro and Franke when they were trying to work out a new process for making cyanide to use in extracting gold. It looks like stone and, under the name of lime-nitrogen, or Kalkstickstoff, or nitrolim, is sold as a fertilizer.

If it is desired to get ammonia, it is treated with superheated steam.

The reaction produces heat and pressure, so it is necessary to carry it on in stout autoclaves or enclosed kettles. The cyanamid is completely and quickly converted into pure ammonia and calcium carbonate, which is the same as the limestone from which carbide was made. The reaction is:

CaCN_{2} + 3H_{2}O --> CaCO_{3} + 2NH_{3} calcium cyanamid water calcium carbonate ammonia

Another electrical furnace method, the Serpek process, uses aluminum instead of calcium for the fixation of nitrogen. Bauxite, or impure aluminum oxide, the ordinary mineral used in the manufacture of metallic aluminum, is mixed with coal and heated in a revolving electrical furnace through which nitrogen is pa.s.sing. The equation is:

Al_{2}O_{3} + 3C + N_{2} --> 2AlN + 3CO aluminum carbon nitrogen aluminum carbon oxide nitride monoxide

Then the aluminum nitride is treated with steam under pressure, which produces ammonia and gives back the original aluminum oxide, but in a purer form than the mineral from which was made

2AlN + 3H_{2}O --> 2NH_{3} + Al_{2}O_{3} Aluminum water ammonia aluminum oxide nitride

The Serpek process is employed to some extent in France in connection with the aluminum industry. These are the princ.i.p.al processes for the fixation of nitrogen now in use, but they by no means exhaust the possibilities. For instance, Professor John C. Bucher, of Brown University, created a sensation in 1917 by announcing a new process which he had worked out with admirable completeness and which has some very attractive features. It needs no electric power or high pressure retorts or liquid air apparatus. He simply fills a twenty-foot tube with briquets made out of soda ash, iron and c.o.ke and pa.s.ses producer gas through the heated tube. Producer gas contains nitrogen since it is made by pa.s.sing air over hot coal. The reaction is:

2Na_{2}CO_{3} + 4C + N_{2} = 2NaCN + 3CO sodium carbon nitrogen sodium carbon carbonate cyanide monoxide

The iron here acts as the catalyst and converts two harmless substances, sodium carbonate, which is common washing soda, and carbon, into two of the most deadly compounds known to man, cyanide and carbon monoxide, which is what kills you when you blow out the gas. Sodium cyanide is a salt of hydrocyanic acid, which for, some curious reason is called "Prussic acid." It is so violent a poison that, as the freshman said in a chemistry recitation, "a single drop of it placed on the tongue of a dog will kill a man."

But sodium cyanide is not only useful in itself, for the extraction of gold and cleaning of silver, but can be converted into ammonia, and a variety of other compounds such as urea and oxamid, which are good fertilizers; sodium ferrocyanide, that makes Prussian blue; and oxalic acid used in dyeing. Professor Bucher claimed that his furnace could be set up in a day at a cost of less than $100 and could turn out 150 pounds of sodium cyanide in twenty-four hours. This process was placed freely at the disposal of the United States Government for the war and a 10-ton plant was built at Saltville, Va., by the Ordnance Department.

But the armistice put a stop to its operations and left the future of the process undetermined.

[Ill.u.s.tration: A CHEMICAL REACTION ON A LARGE SCALE

From the chemist's standpoint modern warfare consists in the rapid liberation of nitrogen from its compounds]

[Ill.u.s.tration: Courtesy of E.I. du Pont de Nemours Co.

BURNING AIR IN A BIRKELAND-EYDE FURNACE AT THE DU PONT PLANT

An electric arc consuming about 4000 horse-power of energy is pa.s.sing between the U-shaped electrodes which are made of copper tube cooled by an internal current of water. On the sides of the chamber are seen the openings through which the air pa.s.ses impinging directly on both sides of the surface of the disk of flame. This flame is approximately seven feet in diameter and appears to be continuous although an alternating current of fifty cycles a second is used. The electric arc is spread into this disk flame by the repellent power of an electro-magnet the pointed pole of which is seen at bottom of the picture. Under this intense heat a part of the nitrogen and oxygen of the air combine to form oxides of nitrogen which when dissolved in water form the nitric acid used in explosives.]

[Ill.u.s.tration: Courtesy of E.I. du Pont de Nemours Co.

A BATTERY OF BIRKELAND-EYDE FURNACES FOR THE FIXATION OF NITROGEN AT THE DU PONT PLANT]

We might have expected that the fixation of nitrogen by pa.s.sing an electrical spark through hot air would have been an American invention, since it was Franklin who s.n.a.t.c.hed the lightning from the heavens as well as the scepter from the tyrant and since our output of hot air is unequaled by any other nation. But little attention was paid to the nitrogen problem until 1916 when it became evident that we should soon be drawn into a war "with a first cla.s.s power." On June 3, 1916, Congress placed $20,000,000 at the disposal of the president for investigation of "the best, cheapest and most available means for the production of nitrate and other products for munitions of war and useful in the manufacture of fertilizers and other useful products by water power or any other power." But by the time war was declared on April 6, 1917, no definite program had been approved and by the time the armistice was signed on November 11, 1918, no plants were in active operation. But five plants had been started and two of them were nearly ready to begin work when they were closed by the ending of the war.

United States Nitrate Plant No. 1 was located at Sheffield, Alabama, and was designed for the production of ammonia by "direct action" from nitrogen and hydrogen according to the plans of the American Chemical Company. Its capacity was calculated at 60,000 pounds of anhydrous ammonia a day, half of which was to be oxidized to nitric acid. Plant No. 2 was erected at Muscle Shoals, Alabama, to use the process of the American Cyanamid Company. This was contracted to produce 110,000 tons of ammonium nitrate a year and later two other cyanamid plants of half that capacity were started at Toledo and Ancor, Ohio.

At Muscle Shoals a mushroom city of 20,000 sprang up on an Alabama cotton field in six months. The raw material, air, was as abundant there as anywhere and the power, water, could be obtained from the Government hydro-electric plant on the Tennessee River, but this was not available during the war, so steam was employed instead. The heat of the coal was used to cool the air down to the liquefying point. The principle of this process is simple. Everybody knows that heat expands and cold contracts, but not everybody has realized the converse of this rule, that expansion cools and compression heats. If air is forced into smaller s.p.a.ce, as in a tire pump, it heats up and if allowed to expand to ordinary pressure it cools off again. But if the air while compressed is cooled and then allowed to expand it must get still colder and the process can go on till it becomes cold enough to congeal. That is, by expanding a great deal of air, a little of it can be reduced to the liquefying point. At Muscle Shoals the plant for liquefying air, in order to get the nitrogen out of it, consisted of two dozen towers each capable of producing 1765 cubic feet of pure nitrogen per hour. The air was drawn in through two pipes, a yard across, and pa.s.sed through scrubbing towers to remove impurities. The air was then compressed to 600 pounds per square inch.

Nine tenths of the air was permitted to expand to 50 pounds and this expansion cooled down the other tenth, still under high pressure, to the liquefying point. Rectifying towers 24 feet high were stacked with trays of liquid air from which the nitrogen was continually bubbling off since its boiling point is twelve degrees centigrade lower than that of oxygen. Pure nitrogen gas collected at the top of the tower and the residual liquid air, now about half oxygen, was allowed to escape at the bottom.

The nitrogen was then run through pipes into the lime-nitrogen ovens.

There were 1536 of these about four feet square and each holding 1600 pounds of pulverized calcium carbide. This is at first heated by an electrical current to start the reaction which afterwards produces enough heat to keep it going. As the stream of nitrogen gas pa.s.ses over the finely divided carbide it is absorbed to form calcium cyanamid as described on a previous page. This product is cooled, powdered and wet to destroy any quicklime or carbide left unchanged. Then it is charged into autoclaves and steam at high temperature and pressure is admitted.

The steam acting on the cyanamid sets free ammonia gas which is carried to towers down which cold water is sprayed, giving the ammonia water, familiar to the kitchen and the bathroom.

But since nitric acid rather than ammonia was needed for munitions, the oxygen of the air had to be called into play. This process, as already explained, is carried on by aid of a catalyzer, in this case platinum wire. At Muscle Shoals there were 696 of these catalyzer boxes. The ammonia gas, mixed with air to provide the necessary oxygen, was admitted at the top and pa.s.sed down through a sheet of platinum gauze of 80 mesh to the inch, heated to incandescence by electricity. In contact with this the ammonia is converted into gaseous oxides of nitrogen (the familiar red fumes of the laboratory) which, carried off in pipes, cooled and dissolved in water, form nitric acid.

But since none of the national plants could be got into action during the war, the United States was compelled to draw upon South America for its supply. The imports of Chilean saltpeter rose from half a million tons in 1914 to a million and a half in 1917. After peace was made the Department of War turned over to the Department of Agriculture its surplus of saltpeter, 150,000 tons, and it was sold to American farmers at cost, $81 a ton.

For nitrogen plays a double role in human economy. It appears like Brahma in two aspects, Vishnu the Preserver and Siva the Destroyer. Here I have been considering nitrogen in its maleficent aspect, its use in war. We now turn to its beneficent aspect, its use in peace.

III

FEEDING THE SOIL

The Great War not only starved people: it starved the land. Enough nitrogen was thrown away in some indecisive battle on the Aisne to save India from a famine. The population of Europe as a whole has not been lessened by the war, but the soil has been robbed of its power to support the population. A plant requires certain chemical elements for its growth and all of these must be within reach of its rootlets, for it will accept no subst.i.tutes. A wheat stalk in France before the war had placed at its feet nitrates from Chile, phosphates from Florida and potash from Germany. All these were shut off by the firing line and the shortage of shipping.

Out of the eighty elements only thirteen are necessary for crops. Four of these are gases: hydrogen, oxygen, nitrogen and chlorine. Five are metals: pota.s.sium, magnesium, calcium, iron and sodium. Four are non-metallic solids: carbon, sulfur, phosphorus and silicon. Three of these, hydrogen, oxygen and carbon, making up the bulk of the plant, are obtainable _ad libitum_ from the air and water. The other ten in the form of salts are dissolved in the water that is sucked up from the soil. The quant.i.ty needed by the plant is so small and the quant.i.ty contained in the soil is so great that ordinarily we need not bother about the supply except in case of three of them. They are nitrogen, pota.s.sium and phosphorus. These would be useless or fatal to plant life in the elemental form, but fixed in neutral salt they are essential plant foods. A ton of wheat takes away from the soil about 47 pounds of nitrogen, 18 pounds of phosphoric acid and 12 pounds of potash. If then the farmer does not restore this much to his field every year he is drawing upon his capital and this must lead to bankruptcy in the long run.

So much is easy to see, but actually the question is extremely complicated. When the German chemist, Justus von Liebig, pointed out in 1840 the possibility of maintaining soil fertility by the application of chemicals it seemed at first as though the question were practically solved. Chemists a.s.sumed that all they had to do was to a.n.a.lyze the soil and a.n.a.lyze the crop and from this figure out, as easily as balancing a bank book, just how much of each ingredient would have to be restored to the soil every year. But somehow it did not work out that way and the practical agriculturist, finding that the formulas did not fit his farm, sneered at the professors and whenever they cited Liebig to him he irreverently transposed the syllables of the name. The chemist when he went deeper into the subject saw that he had to deal with the colloids, damp, unpleasant, gummy bodies that he had hitherto fought shy of because they would not crystallize or filter. So the chemist called to his aid the physicist on the one hand and the biologist on the other and then they both had their hands full. The physicist found that he had to deal with a polyvariant system of solids, liquids and gases mutually miscible in phases too numerous to be handled by Gibbs's Rule. The biologist found that he had to deal with the invisible flora and fauna of a new world.

Plants obey the injunction of Tennyson and rise on the stepping stones of their dead selves to higher things. Each successive generation lives on what is left of the last in the soil plus what it adds from the air and sunshine. As soon as a leaf or tree trunk falls to the ground it is taken in charge by a wrecking crew composed of a myriad of microscopic organisms who proceed to break it up into its component parts so these can be used for building a new edifice. The process is called "rotting"

and the product, the black, gummy stuff of a fertile soil, is called "humus." The plants, that is, the higher plants, are not able to live on their own proteids as the animals are. But there are lower plants, certain kinds of bacteria, that can break up the big complicated proteid molecules into their component parts and reduce the nitrogen in them to ammonia or ammonia-like compounds. Having done this they stop and turn over the job to another set of bacteria to be carried through the next step. For you must know that soil society is as complex and specialized as that above ground and the tiniest bacterium would die rather than violate the union rules. The second set of bacteria change the ammonia over to nitrites and then a third set, the Amalgamated Union of Nitrate Workers, steps in and completes the process of oxidation with an efficiency that Ostwald might envy, for ninety-six per cent. of the ammonia of the soil is converted into nitrates. But if the conditions are not just right, if the food is insufficient or unwholesome or if the air that circulates through the soil is contaminated with poison gases, the bacteria go on a strike. The farmer, not seeing the thing from the standpoint of the bacteria, says the soil is "sick" and he proceeds to doctor it according to his own notion of what ails it. First perhaps he tries running in strike breakers. He goes to one of the firms that makes a business of supplying nitrogen-fixing bacteria from the scabs or nodules of the clover roots and scatters these colonies over the field. But if the living conditions remain bad the newcomers will soon quit work too and the farmer loses his money. If he is wise, then, he will remedy the conditions, putting a better ventilation system in his soil perhaps or neutralizing the sourness by means of lime or killing off the ameboid banditti that prey upon the peaceful bacteria engaged in the nitrogen industry. It is not an easy job that the farmer has in keeping billions of billions of subterranean servants contented and working together, but if he does not succeed at this he wastes his seed and labor.

The layman regards the soil as a platform or anchoring place on which to set plants. He measures its value by its superficial area without considering its contents, which is as absurd as to estimate a man's wealth by the size of his safe. The difference in point of view is well ill.u.s.trated by the old story of the city chap who was showing his farmer uncle the sights of New York. When he took him to Central Park he tried to astonish him by saying "This land is worth $500,000 an acre." The old farmer dug his toe into the ground, kicked out a clod, broke it open, looked at it, spit on it and squeezed it in his hand and then said, "Don't you believe it; 'tain't worth ten dollars an acre. Mighty poor soil I call it." Both were right.

[Ill.u.s.tration: Courtesy of American Cyanamid Co.

FIXING NITROGEN BY CALCIUM CARBIDE

A view of the oven room in the plant of the American Cyanamid Company.