Creative Chemistry: Descriptive of Recent Achievements in the Chemical Industries. Edwin E. Slosson
+ 3H2O → CaCO3 + 2NH3 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 passing. The equation is:
Al2O3 + 3C + N2 → 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 + 3H2O → 2NH3 + Al2O3 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 principal 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 coke and passes producer gas through the heated tube. Producer gas contains nitrogen since it is made by passing air over hot coal. The reaction is:
2Na2CO3 + 4C + N2 = 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.
From the chemist's standpoint modern warfare consists in the rapid liberation of nitrogen from its compounds
BURNING AIR IN A BIRKELAND-EYDE FURNACE AT THE DU PONT PLANT
An electric arc consuming about 4000 horse-power of energy is passing 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 passes 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.
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 passing an electrical spark through hot air would have been an American invention, since it was Franklin who snatched 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 class 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 space, 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 passed 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 passes 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