Part 57

This was the first synthesis of an organic compound from inorganic material, and it overthrew the prevailing view that vital forces were essential in the formation of organic substances. A great many natural organic compounds have been made artificially since that time, and some of them, such as artificial alizarin, indigo, oil of wintergreen, and vanillin, have more or less fully replaced the natural products. The preparation of a vast number of compounds not known in nature, many of which are of practical importance as medicines, dyes, explosives, etc., has been another great achievement of organic chemistry.

The development of our present formulas for organic compounds, by means of which in many cases the relative positions of the atoms can be shown with the greatest confidence, has been gradual. Formulas based on the dualistic idea of Berzelius were used for some time, type-formulas, with the employment of compound radicals, came later, the substitution of atoms or groups of atoms for others in chemical reactions came to be recognized, but one of the most important steps was the recognition of the quadrivalence of carbon and the general application of valency to atoms by Kekulé about 1858. This led directly to the use of modern structural formulas which have been of the greatest value in the theoretical interpretation of organic reactions. It was Kekulé also who proposed the hexagonal ring-formula for benzene, C{6}H{6}, which led to exceedingly important theoretical and practical developments. The details of the formulas for many other rings and complex structures have been established since that time, and there is no doubt that the remarkable achievements in organic chemistry during the past sixty years have been much facilitated by the use of these formulas.

Many important researches in organic chemistry have been carried out in the United States, and the activity in this direction has greatly increased in recent years. In this connection the large amount of work of this kind accomplished in the Sheffield Laboratory, at present under the guidance of Professor T. B. Johnson, should be mentioned.

It has happened that comparatively few publications on organic chemistry have appeared in the Journal, but it may be stated that the preparation of chloroform and its physiological effects were described by Guthrie (=21=, 64, 1832). Unknown to him, it had been prepared by Souberain, a French chemist, the previous year, but the former was the first to describe its physiological action. Silliman gave a sample to Doctor Eli Ives of the Yale Medical School, who used it to relieve a case of asthma. This was the first use of chloroform in medical practice (=21=, 405, 1832). Guthrie also described in the Journal (=21=, 284, 1832) his new process for converting potato starch into glucose, a method which is essentially the same as that used to-day in converting cornstarch into glucose. Lawrence Smith (=43=, 301, 1842 et seq.), Horsford (=3=, 369, 1847 et seq.), Sterry Hunt (=7=, 399, 1849), Carey Lea (=26=, 379, 1858 et seq.), Remsen (=5=, 179, 1873 et seq.), and others have contributed articles on organic chemistry.

Agricultural Chemistry.

Until near the middle of the nineteenth century, it was believed that plants, like animals, used organic matter for food, and depended chiefly upon the humus of the soil for their growth. This view was held even long after it was known that plant leaves absorb carbon dioxide and give off oxygen, and after the ashes of plants had been accurately analyzed.

This incorrect view was overthrown by the celebrated German chemist, Liebig, who made many investigations upon the subject, and, properly interpreting previous knowledge, published a book in 1840 upon the application of chemistry to agriculture and physiology in which he maintained that the nutritive materials of all green plants are inorganic substances, namely, carbon dioxide, water, ammonia (nitrates), sulphates, phosphates, silica, lime, magnesia, potash, iron, and sometimes common salt. He drew the vastly important conclusion that the effective fertilization of soils depends upon replenishing the inorganic substances that have been exhausted by the crops.

The fundamental principles set forth by Liebig have been confirmed, and it has been found that the fertilizing constituents most commonly lacking in soils are nitrogen compounds, phosphates, and potassium salts, so that these have formed the important constituents of artificial fertilizers. Liebig himself found that humus is valuable in soils, because it absorbs and retains the soluble salts.

The foundation established by Liebig in regard to artificial fertilizers has led to an enormous application of these materials, much to the advantage of the world’s food supply.

It was Liebig’s belief, in accordance with the prevailing views, that decay and putrefaction as well as alcoholic and other fermentations were spontaneous processes, and when the eminent French chemist, Pasteur, in 1857, explained fermentation as directly caused by yeast, an epoch-making discovery which led to the explanation of decay and putrefaction by bacterial action and to the germ-theory of disease, the explanation was violently opposed by Liebig and other German chemists. Pasteur’s view prevailed, however, and since that time it has been found that various kinds of bacteria are responsible for the formation of ammonia from nitrogenous organic matter and also for the change of ammonia into the nitrates that are available as plant-food.

The long-debated question as to the availability of atmospheric nitrogen for plant-food was settled in 1886 by the discovery of Hellriegel that bacteria contained in nodules on the roots, especially of leguminous plants, are capable of bringing nitrogen into combination and furnishing it to the plants.

No more than an allusion can be made to agricultural experiment stations where soils, fertilizers, foods and other products are examined, and where other problems connected with agriculture are studied.

The late S. W. Johnson of Yale studied with Liebig and subsequently did much service for agricultural chemistry in this country, by his investigations, his teaching, and his writings. His book, “How Crops Grow,” published in 1868, gave an excellent account of the principles of agricultural chemistry. He did much to bring about the establishment of agricultural experiment stations in this country, and for a long time he was the director of the Connecticut Station.

In the Journal, as early as 1827, Amos Eaton (=12=, 370) published a simple method for the mechanical analysis of soils to determine their suitability for wheat-culture, and Hilgard, between 1872 and 1874, described an elaborate study of soil-analysis. J. P. Norton, a Yale professor, in 1847 (=3=, 322) published an investigation on the analysis of the oat, which was awarded a prize of fifty sovereigns by a Scotch agricultural society, while Johnson, Atwater, and others have contributed articles on the analysis of various farm products.

Industrial Acids and Alkalies.

One hundred years ago sulphuric acid was manufactured on a comparatively very small scale in lead chambers. In 1818, an English manufacturer of the acid introduced the modern feature of using pyrites in the place of brimstone, while the Gay-Lussac tower in 1827 and the Glover tower in 1859 began to be applied as great improvements in the chamber process. Within about twenty years the contact process, employing platinized asbestos, has replaced the old chamber process to a large extent. It has the advantage of producing the concentrated acid, or the fuming acid, directly.

During our period the manufacture of sulphuric acid has increased enormously. Very large quantities of it have been used in connection with the Leblanc soda process in its rapid development. It came to be employed extensively for absorbing ammonia in the illuminating-gas industry, which was in its infancy one hundred years ago. New industries such as the manufacture of “superphosphates” as artificial fertilizers, the refining of petroleum, the manufacture of artificial dyestuffs and many other modern chemical products have greatly increased the demand for it, while its employment in the production of nitric and other acids, and for many other purposes not already mentioned, has been very great.

The manufacture of nitric acid has been greatly extended during our period on account of its employment for producing explosives, artificial dyestuffs, and for many other purposes. Chile saltpeter became available for making it about 1852. This acid has been manufactured recently from atmospheric nitrogen and oxygen by combining them by the aid of powerful electric discharges. This process has been used chiefly in Norway where water-power is abundant, as it requires a large expenditure of energy. A still more recent method for the production of nitric acid depends upon the oxidation of ammonia by air with the aid of a contact substance, such as platinized asbestos.

The production of ammonia, which was very small a hundred years ago, has been vastly increased in connection with the development of the illuminating-gas industry and the employment of by-product coke ovens. This substance is very extensively used in refrigerating machines and also in a great many chemical operations, including the Solvay soda process. Ammonium salts are of great importance also as fertilizers in agriculture. The conversion of atmospheric nitrogen into ammonia on a commercial scale is a recent achievement. It has been accomplished by heating calcium carbide, an electric-furnace product made from lime and coke, with nitrogen gas, thus producing calcium cyanamide, and then treating this cyanamide with water under proper conditions. Another method devised by Haber consists in directly combining nitrogen and hydrogen gases under high pressure with the aid of a contact substance.

Leblanc’s method for obtaining sodium carbonate from sodium chloride by first converting the latter into the sulphate by means of sulphuric acid and then heating the sulphate with lime and coal in a furnace was invented as early as 1791, but it was not rapidly developed and did not gain a foothold in England until 1826 on account of a high duty on salt up to that time. Afterwards the process flourished greatly in connection with the sulphuric acid industry upon which it depended, and with the bleaching-powder industry which utilized the hydrochloric acid incidentally produced by it, and, of course, in connection with soap manufacture and many other industries in which the soda itself was employed.

About 1866 the Solvay process appeared as a rival to the Leblanc process. This depends upon the precipitation of sodium bicarbonate from salt solutions by means of carbon dioxide and ammonia, with the subsequent recovery of the ammonia. It has displaced the older process to a large extent, and it is carried on extensively in this country, for instance, at Syracuse, New York.

Other processes for soda depend upon the electrolysis of sodium chloride solutions. In this case caustic soda and chlorine are the direct products, and the chlorine thus produced and liquefied by pressure in steel cylinders, has become an important commercial article.

In earlier times wood-ashes were the source of potash and potassium salts. Wurtz in the Journal (=10=, 326, 1850) suggested the availability of New Jersey greensand as a source of potash and showed how this mineral could be decomposed, but it does not appear that this mineral has ever been utilized for the purpose. About 1861 the German potash-salt deposits began to be developed, and these have since become the chief source of this material. At present many efforts are being made to obtain potassium compounds from other sources, such as brines, cement-kiln dust, and feldspar and other minerals but thus far the results have not satisfied the demand.

Conclusion.

This account of chemical progress has given only a limited view of small portions of the subject, because the amount of available material is so vast in comparison with the space allowed for its presentation. Since the Journal has published comparatively little organic chemistry, it was decided to make room for a better presentation of other things by giving only a brief discussion of this exceedingly active and important branch of the science. For similar reasons industrial and metallurgical chemistry, and other branches besides, in spite of their great growth and importance, have been neglected, except for some incidental references to them, and some account of a few of the more important industrial chemicals.

It appears that we have much reason to be proud of the advances in chemistry that have been made during the Journal’s period, and of the part that the Journal has taken in connection with them, and there seems to be no doubt that this progress has not diminished during more recent times.

The present tendency of chemical research is evidently towards a still greater development of organic chemistry, and an increased application of physics and mathematics to chemical theory and practice.

The very great improvements that have been made in chemical education, both in the number of students and the quality of instruction, during the period under discussion, and particularly in rather recent times, gives promise for excellent future progress.