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48
[ORGANIC
CHEMISTRY

This dogma was shaken by Wöhler’s synthesis of urea in 1828. But the belief died hard; the synthesis of urea remained isolated for many years; and many explanations were attempted by the vitalists (as, for instance, that urea was halfway between the inorganic and organic kingdoms, or that the carbon, from which it was obtained, retained the essentials of this hypothetical vital force), but only to succumb at a later date to the indubitable fact that the same laws of chemical combination prevail in both the animate and inanimate kingdoms, and that the artificial or laboratory synthesis of any substance, either inorganic or organic, is but a question of time, once its constitution is determined.[1]

The exact delimitation of inorganic and organic chemistry engrossed many minds for many years; and on this point there existed considerable divergence of opinion for several decades. In addition to the vitalistic doctrine of the origin of organic compounds, views based on purely chemical considerations were advanced. The atomic theory, and its correlatives—the laws of constant and multiple proportions—had been shown to possess absolute validity so far as well-characterized inorganic compounds were concerned; but it was open to question whether organic compounds obeyed the same laws. Berzelius, in 1813 and 1814, by improved methods of analysis, established that the Daltonian laws of combination held in both the inorganic and organic kingdoms; and he adopted the view of Lavoisier that organic compounds were oxides of compound radicals, and therefore necessarily contained at least three elements—carbon, hydrogen and oxygen. This view was accepted in 1817 by Leopold Gmelin, who, in his Handbuch der Chemie, regarded inorganic compounds as being of binary composition (the simplest being oxides both acid and basic, which by combination form salts also of binary form), and organic compounds as ternary, i.e. composed of three elements; furthermore, he concluded that inorganic compounds could be synthesized, whereas organic compounds could not. A consequence of this empirical division was that marsh gas, ethylene and cyanogen were regarded as inorganic, and at a later date many other hydrocarbons of undoubtedly organic nature had to be included in the same division.

The binary conception of compounds held by Berzelius received apparent support from the observations of Gay Lussac, in 1815, on the vapour densities of alcohol and ether, which pointed to the conclusion that these substances consisted of one molecule of water and one and two of ethylene respectively; and from Pierre Jean Robiquet and Jean Jacques Colin, showing, in 1816, that ethyl chloride (hydrochloric ether) could be regarded as a compound of ethylene and hydrochloric acid.[2] Compound radicals came to be regarded as the immediate constituents of organic compounds; and, at first, a determination of their empirical composition was supposed to be sufficient to characterize them. To this problem there was added another in about the third decade of the 19th century—namely, to determine the manner in which the atoms composing the radical were combined; this supplementary requisite was due to the discovery of the isomerism of silver fulminate and silver cyanate by Justus von Liebig in 1823, and to M. Faraday’s discovery of butylene, isomeric with ethylene, in 1825.

The classical investigation of Liebig and Friedrich Wohler on the radical of benzoic acid (“Über das Radikal der Benzoë-säure,” Ann. Chem., 1832, 3, p. 249) is to be regarded as a most important contribution to the radical theory, for it was shown that a radical containing the elements carbon, hydrogen and oxygen, which they named benzoyl (the termination yl coming from the Gr. ὔλη, matter), formed the basis of benzaldehyde, benzoic acid, benzoyl chloride, benzoyl bromide and benzoyl sulphide, benzamide and benzoic ether. Berzelius immediately appreciated the importance of this discovery, notwithstanding that he was compelled to reject the theory that oxygen could not play any part in a compound radical—a view which he previously considered as axiomatic; and he suggested the names “proin” or “orthrin” (from the Gr. πρωί and ὀρθρός, at dawn). However, in 1833, Berzelius reverted to his earlier opinion that oxygenated radicals were incompatible with his electrochemical theory; he regarded benzoyl as an oxide of the radical C14H10, which he named “picramyl” (from πικρός, bitter, and ἀμυγδάλη, almond), the peroxide being anhydrous benzoic acid; and he dismissed the views of Gay Lussac and Dumas that ethylene was the radical of ether, alcohol and ethyl chloride, setting up in their place the idea that ether was a suboxide of ethyl, (C2H5)2O, which was analogous to K2O, while alcohol was an oxide of a radical C2H6; thus annihilating any relation between these two compounds. This view was modified by Liebig, who regarded ether as ethyl oxide, and alcohol as the hydrate of ethyl oxide; here, however, he was in error, for he attributed to alcohol a molecular weight double its true value. Notwithstanding these errors, the value of the “ethyl theory” was perceived; other radicals—formyl, methyl, amyl, acetyl, &c.—were characterized; Dumas, in 1837, admitted the failure of the etherin theory; and, in company with Liebig, he defined organic chemistry as the “chemistry of compound radicals.” The knowledge of compound radicals received further increment at the hands of Robert W. Bunsen, the discoverer of the cacodyl compounds.

The radical theory, essentially dualistic in nature in view of its similarity to the electrochemical theory of Berzelius, was destined to succumb to a unitary theory. Instances had already been recorded of cases where a halogen element replaced hydrogen with the production of a closely allied substance: Gay Lussac had prepared cyanogen chloride from hydrocyanic acid; Faraday, hexachlorethane from ethylene dichloride, &c. Here the electro-negative halogens exercised a function similar to electro-positive hydrogen. Dumas gave especial attention to such substitutions, named metalepsy (μετάληψις, exchange); and framed the following empirical laws to explain the reactions:—(1) a body containing hydrogen when substituted by a halogen loses one atom of hydrogen for every atom of halogen introduced; (2) the same holds if oxygen be present, except that when the oxygen is present as water the latter first loses its hydrogen without replacement, and then substitution according to (1) ensues. Dumas went no further that thus epitomizing his observations; and the next development was made in 1836 by Auguste Laurent, who, having amplified and discussed the applicability of Dumas’ views, promulgated his Nucleus Theory, which assumed the existence of “original nuclei or radicals” (radicaux or noyaux fondamentaux) composed of carbon and hydrogen, and “derived nuclei” (radicaux or noyaux dérivés) formed from the original nuclei by the substitution of hydrogen or the addition of other elements, and having properties closely related to the primary nuclei.

Vigorous opposition was made by Liebig and Berzelius, the latter directing his attack against Dumas, whom he erroneously believed to be the author of what was, in his opinion, a pernicious theory. Dumas repudiated the accusation, affirming that he held exactly contrary views to Laurent; but only to admit their correctness in 1839, when, from his own researches and those of Laurent, Malaguti and Regnault, he formulated his type theory. According to this theory a “chemical type” embraced compounds containing the same number of equivalents combined in a like manner and exhibiting similar properties; thus acetic and trichloracetic acids, aldehyde and chloral, marsh gas and chloroform are pairs of compounds referable to the same type. He also postulated, with Regnault, the existence of “molecular or mechanical types” containing substances which, although having the same number of equivalents, are essentially different in characters. His unitary conceptions may be summarized: every chemical compound forms a complete whole, and cannot therefore consist of two parts; and its chemical character depends primarily upon the arrangement and number of the atoms, and, in a lesser degree, upon their chemical nature.

  1. The reader is specially referred to the articles Alizarin; Indigo; Purin and Terpenes for illustrations of the manner in which chemists have artificially prepared important animal and vegetable products.
  2. These observations were generalized by J. B. Dumas and Polydore Boullay (1806–1835) in their “etherin theory” (vide infra).