Creative Chemistry: Descriptive of Recent Achievements in the Chemical Industries. Edwin E. Slosson
to form nitrates but the atoms are paired, like to like. Passing an electric spark through the air breaks up some of these pairs and in the confusion of the shock the lonely atoms seize on their nearest neighbor and so may get partners of the other sort. I have seen this same thing happen in a square dance where somebody made a blunder. It is easy to understand the reaction if we represent the atoms of oxygen and nitrogen by the initials of their names in this fashion:
NN + OO → NO + NO
nitrogen oxygen nitric oxide
The → represents Jove's thunderbolt, a stroke of artificial lightning. We see on the left the molecules of oxygen and nitrogen, before taking the electric treatment, as separate elemental pairs, and then to the right of the arrow we find them as compound molecules of nitric oxide. This takes up another atom of oxygen from the air and becomes NOO, or using a subscript figure to indicate the number of atoms and so avoid repeating the letter, NO2 which is the familiar nitro group of nitric acid (HO—NO2) and of its salts, the nitrates, and of its organic compounds, the high explosives. The NO2 is a brown and evil-smelling gas which when dissolved in water (HOH) and further oxidized is completely converted into nitric acid.
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 Schönherr 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 passing 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 analogy. 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 passed 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 passed 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:
NH3 + 4O → HNO3 + H2O 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 constituent 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 passed over hot calcium carbide it is taken up by the carbide according to the following equation:
CaC2 + N2 → CaCN2 + 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:
CaCN2