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CHEMISTRY (formerly "chymistry"; Gr. ...

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Originally appearing in Volume V06, Page 52 of the 1911 Encyclopedia Britannica.
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CHEMISTRY (formerly "chymistry"; Gr. xvµela; for derivation see ALCHEMY), the natural science which has for its province the study of the composition of substances. In common with physics it includes the determination of properties or characters which serve to distinguish one substance from another, but while the physicist is concerned with properties possessed by all substances and with processes in which the molecules remain intact, the chemist is restricted to those processes in which the molecules undergo some change. For example, the physicist determines the density, elasticity, hardness, electrical and thermal conductivity, thermal expansion, &c.; the chemist, on the other hand, investigates changes in composition, such as .nay be effected by an electric current, by heat, or when two or more substances are mixed. A further differentiation of the provinces of chemistry and physics is shown by the classifications of matter. To the physicist matter is presented in three leading forms—solids, liquids and gases; and although further sub-divisions have been rendered necessary with the growth of knowledge the same principle is retained, namely, a classification based on properties having no relation to composition. The fundamental chemical classification of matter, on the other hand, recognizes two groups of substances, namely, elements, which are substances not admitting of analysis into other substances, and compounds, which do admit of analysis into simpler substances and also of synthesis from simpler substances. Chemistry and physics, however, meet on common ground in a well-defined branch of science, named physical chemistry, which is primarily concerned with the correlation of physical properties and chemical composition, and, more generally, with the elucidation of natural phenomena on the molecular theory. It may be convenient here to state how the whole subject of chemistry is treated in this edition of the Encyclopaedia Britannica. The present article includes the following sections: I. History.—T his section is confined to tracing the general trend of the science from its infancy to the foundations of the modern theory. The history of the alchemical period is treated in more detail in the article ALCHEMY, and of the iatrochemical in the article MEDICINE. The evolution of the notion of elements is treated under ELEMENT; the molecular hypothesis of matter under MOLECULE; and the genesis of, and deductions from, the atomic theory of Dalton receive detailed analysis in the article ATOM. II. Principles.—This section treats of such subjects as nomenclature, formulae, chemical equations, chemical change and similar subjects. It is intended to provide an introduction, necessarily brief, to the terminology and machinery of the chemist. VI. 2 IV. Organic Chemistry.—This section includes a brief history of the subject, and proceeds to treat of the principles underlying the structure and interrelations of organic compounds. V. Analytical Chemistry.—This section treats of the qualitative detection and separation of the metals, and the commoner methods employed in quantitative analysis. The analysis of organic tom-pounds is also noticed. VI. Physical Chemistry.—This section is restricted to an account of the relations existing between physical properties and chemical composition. Other branches of this subject are treated in the articles CHEMICAL ACTION; ENERGETICS; SOLUTION; Annoys; THERMOCHEMISTRY. I. HISTORY Although chemical actions must have been observed by man in the most remote times, and also utilized in such processes as the extraction of metals from their ores and in the arts of tanning and dyeing, there is no evidence to show that, beyond an unordered accuml}lation of facts, the early developments of these industries were attended by any real knowledge of the nature of the processes involved. All observations were the result of accident or chance, or possibly in some cases of experimental trial, but there is no record of a theory or even a general classification of the phenomena involved, although there is no doubt that the ancients .had a fair knowledge of the properties and uses of the commoner substances. The origin of chemistry is intimately bound up with the arts which we have indicated; in this respect it is essentially an experimental science. A unifying principle of chemical and physical changes was provided by metaphysical conceptions of the structure of matter. We find the notion of " elements," or primary qualities, which confer upon all species of matter their distinctive qualities by appropriate combination, and also the doctrine that Greek matter is composed of minute discrete particles, plum. prevailing in the Greek schools. These " elements, sophy. sops however, had not the significance of the elements of to-day; they connoted physical appearances or qualities rather than chemical relations; and the atomic theory of the ancients is a speculation based upon metaphysical considerations, having, in its origin, nothing in common with the modern molecular theory, which was based upon experimentally observed properties of gases (see ELEMENT; MOLECULE). Although such hypotheses could contribute nothing directly to the development of a science which laid especial claim to experimental investigations, yet indirectly they stimulated inquiry into the nature of the " essence " with which the four " elements " were associated. This quinta essentia had been speculated upon by the Greeks, some regarding it as immaterial or aethereal, and others as material; and a school of philosophers termed alchemists arose who attempted the isolation of this essence. The existence of a fundamental principle, unalterable and indestructible, prevailing alike through physical and chemical changes, was generally accepted. Any change which a substance may chance to undergo was simply due to the discarding or taking up of some proportion of the primary " elements " or qualities: of these coverings " water," " air," " earth " and " fire " were regarded as clinging most tenaciously to the essence, while " cold," " heat," " moistness " and " dryness " were more easily cast aside or assumed. Several origins have been suggested for the word alchemy, and there seems to Alchemy. have been some doubt as to the exact nature and import of the alchemical doctrines. According to M. P. E. Berthelot, " alchemy rested partly on the industrial processes of the ancient Egyptians, partly on the speculative theories of the Greek philosophers, and partly on the mystical reveries of the Gnostics and Alexandrians." The search for this essence subsequently resolved itself into the desire to effect the trans-mutation of metals, more especially the base metals, into silver and gold. It seems that this secondary principle became the dominant idea in alchemy, and in this sense the word is used in Byzantine literature of the 4th century; Suidas, writing in II the 1 rth century, defines chemistry as the " preparation of silver and gold " (see ALCHEMY). From the Alexandrians the science passed to the Arabs, who made discoveries and improved various methods of separating substances, and afterwards, from the 11th century, became seated in Europe, where the alchemical doctrines were assiduously studied until the 15th and 16th centuries. It is readily understood why men imbued with the authority of tradition should prosecute the search for a substance which would confer unlimited wealth upon the fortunate discoverer. Some alchemists honestly laboured to effect the transmutation and to discover the " philosopher's stone," and in many cases believed that they had achieved success, if we may rely upon writings assigned to them. The period, however, is one of literary forgeries; most of the MSS. are of uncertain date and authorship, and moreover are often so vague and mystical that they are of doubtful scientific value, beyond reflecting the tendencies of the age. The retaining of alchemists at various courts shows the high opinion which the doctrines had gained. It is really not extraordinary that Isaac Hollandus was able to indicate the method of the preparation of the " philosopher's stone " from " adamic " or " virgin " earth, and its action when medicinally employed; that in the writings assigned to Roger Bacon, Raimon Lull, Basil Valentine and others are to be found the exact quantities of it to be used in transmutation; and that George Ripley, in the 15th century, had grounds for regarding its action as similar to that of a ferment. In the view of some alchemists, the ultimate principles of matter were Aristotle's four elements; the proximate constituents were a " sulphur " and a " mercury," the father and mother of the metals; gold was supposed to have attained to the perfection of its nature by passing in succession through the forms of lead, brass and silver; gold and silver were held to contain very pure red sulphur and white quicksilver, whereas in the other metals these materials were coarser and of a different colour. From an analogy instituted between the healthy human being and gold, the most perfect of the metals, silver, mercury, copper, iron, lead and tin, were regarded in the light of lepers that required to be healed. Notwithstanding the false idea which prompted the researches of the alchemists, many advances were made in descriptive chemistry, the metals and their salts receiving much 'afro- chemistry. attention, and several of our important acids being chem discovered. Towards the 16th century the failure of the alchemists to achieve their cherished purpose, and the general increase of medical knowledge, caused attention to be given to the utilization of chemical preparations as medicines. As early as the 15th century the alchemist Basil Valentine had suggested this application, but the great exponent of this doctrine was Paracelsus, who set up a new definition: " The true use of chemistry is not to make gold but to prepare medicines." This relation of chemistry to medicine prevailed until the 17th century, and what in the history of chemistry is termed the iatrochemical period (see MEDICINE) was mainly fruitful in increasing the knowledge of compounds; the contributions to chemical theory are of little value, the most important controversies ranging over the nature of the " elements," which were generally akin to those of Aristotle, modified so as to be more in accord with current observations. At the same time, however, -there were many who, opposed to the Paracelsian definition of chemistry, still laboured at the problem of the alchemists, while others gave much attention to the chemical industries. Metallurgical operations, such as smelting, roasting and refining, were scientifically investigated, and in some degree explained, by Georg Agricola and Carlo Biringuiccio; ceramics was studied by Bernard Palissy, who is also to be remembered as an early worker in agricultural chemistry, having made experiments on the effect of manures on soils and crops; while general technical chemistry was enriched by Johann Rudolf Glauber.' ' The more notable chemists of this period were Turquet de Mayerne(1573-1665), a physician of Paris,who rejected the Galenian doctrines and accepted the exaggerations of Paracelsus; Andreas The second half of - the 17th century witnessed remarkable transitions and developments in all branches of natural science, and the facts accumulated by preceding generations Boyle. during their generally unordered researches were re- placed by a co-ordination of experiment and deduction. From the mazy and incoherent alchemical and iatrochemical doctrines, the former based on false conceptions of matter, the latter on erroneous views of life processes and physiology, a new science arose—the study of the composition of substances. The formulation of this definition of chemistry was due to Robert Boyle. In his Sceptical Chemist (1662) he freely criticized the prevailing scientific views and methods, with the object of showing that true knowledge could only be gained by the logical application of the principles of experiment and deduction. Boyle's masterly exposition of this method is his most important contribution to scientific progress. At the same time he clarified the conception of elements and compounds, rejecting the older notions, the four elements of the " vulgar Peripateticks " and the three principles of the vulgar Stagyrists," and defining an element as a substance incapable of decomposition, and a compound as composed of two or more elements. He explained chemical combination on the hypotheses that matter consisted of minute corpuscles, that by the coalescence of corpuscles of different sub-stances distinctly new corpuscles of a compound were formed, and that each corpuscle had a certain affinity for other corpuscles. Although Boyle practised the methods which he expounded, he was unable to gain general acceptance of his doctrine of elements; and, strangely enough, the theory which 1Ytogl next dominated chemical thought was an alchemical Ptheorystic invention, and lacked the lucidity and perspicuity of Boyle's views. This theory, named the phlogistic theory, was primarily based upon certain experiments on combustion and calcination, and in effect reduced the number of the alchemical principles, while setting up a new one, a principle of combustibility, named phlogiston (from 4,lwyurros, burnt). Much discussion had centred about fire or the "igneous principle." On the one hand, it had been held that when a substance was burned or calcined, it combined with an " air "; on the other hand, the operation was supposed to be attended by the destruction or loss of the igneous principle. Georg Ernst Stahl, following in some measure the views held by Johann Joachim Becher, as, for instance, that all combustibles contain a " sulphur " (which notion is itself of older date than Becher's terra pinguis), regarded all substances as capable of resolution into two components, the inflammable principle phlogiston, and another element—" water," " acid " or " earth." The violence or completeness of combustion was proportional to the amount of phlogiston present. Combustion meant the liberation of phlogiston. Metals on calcination gave calces from which the metals could be recovered by adding phlogiston, and experiment showed that this could generally be effected by the action of coal or carbon, which was therefore regarded as practically pure phlogiston; the other constituent being regarded as an acid. At the hands of Stahl and his school, the phlogistic theory, by exhibiting a fundamental similarity between all processes of combustion and by its remarkable flexibility, came to be a general theory of chemical action. The objections of the antiphlogistonists, such as the fact that calces weigh more than the original metals instead of less as the theory suggests, were answered by postulating that phlogiston was a principle of levity, or even completely ignored as an accident, the change of qualities being regarded as the only matter of importance. It is remarkable that this theory shouldhave gained the esteem of the notable chemists who flourished in the 18th century. Henry Cavendish, a careful and accurate experimenter, was a phlogistonist, as were J. Black, K. W. Scheele, A. S. Marggraf, J. Priestley and many others who might be mentioned. Libavius (d. 1616), chiefly famous for his Opera Omnia Medicochymica (1595) ; Jean Baptiste van Helmont (1577-1644), celebrated for his researches on gases ; F. de la Boe Sylvlus (1614-1672), who regarded' medicine as applied chemistry; and Otto Tachenius, who elucidated the nature of salts. Descriptive chemistry was now assuming considerable pro-portions; the experimental inquiries suggested by Boyle were Lavoisier. being assiduously developed; and a wealth of observa- tions was being accumulated, for the explanation of which the resources of the dominant theory were sorely taxed. To quote Antoine Laurent Lavoisier, " . . . chemists have turned phlogiston into a vague principle, . . . which consequently adapts itself to all the explanations for which it may be required. Sometimes this principle has weight, and sometimes it has not; sometimes it is free fire and sometimes it is fire combined with the earthy element; sometimes it passes through the pores of vessels, sometimes these are impervious to it; it explains both causticity and non-causticity, transparency and opacity, colours and their absence; it is a veritable Proteus changing in form at each instant." Lavoisier may be justly regarded as the founder of modern or quantitative chemistry. First and foremost, he demanded that the balance must be used in all investigations into chemical changes. He established as fundamental that combustion and calcination were attended by an increase of weight, and concluded, as .did Jean Rey and John Mayow in the 17th century, that the increase was due to the combination of the metal with the air. The problem could obviously be completely solved only when the composition of the air, and the parts played by its components, had been determined. At all times the air had received attention, especially since van Helmont made his far-reaching investigations on gases. Mayow had suggested the existence of two components, a spiritus nitroaerus which supported combustion, and a spiritus nitri acidi which extinguished fire; J. Priestley and K. W. Scheele, although they isolated oxygen, were fogged by the phlogistic tenets; and H. Cavendish, who had isolated the nitrogen of the atmosphere, had failed to decide conclusively what had really happened to the air which disappeared during combustion. Lavoisier adequately recognized and acknowledged how much he owed to the researches of others; to himself is due the co-ordination of these researches, and the welding of his results into a doctrine to which the phlogistic theory ultimately succumbed. He burned phosphorus in air standing over mercury, and showed that (I) there was a limit to the amount of phosphorus which could be burned in the confined air, (2) that when no more phosphorus could be burned, one-fifth of the air had disappeared, (3) that the weight of the air lost was nearly equal to the difference in the weights of the white solid produced and the phosphorus burned, (4) that the density of the residual air was less than that of ordinary air. The same results were obtained with lead and tin; and a more elaborate repetition indubitably established their correctness. He also showed that on heating mercury calx alone an " air " was liberated which differed from other " airs," and was slightly heavier than ordinary air; moreover, the weight of the " air " set free from a given weight of the calx was equal to the weight taken up in forming the calx from mercury, and if the calx be heated with charcoal, the metal was recovered and a gas named " fixed air," the modern carbon dioxide, was formed. The former experiment had been performed by Scheele and Priestley, who had named the gas "phlogisticated air "; Lavoisier subsequently named it oxygen, regarding it as the " acid producer " (oEus, sour). The theory advocated by Lavoisier came to displace the phlogistic conception; but at first its acceptance was slow. Chemical literature was full of the phlogistic modes of expression—oxygen was " dephlogisticated air," nitrogen " phlogisticated air," &c.—and this tended to retard its promotion. Yet really the transition from the one theory to the other was simple, it being only necessary to change the " addition or loss of phlogiston " into the " loss or addition of oxygen." By his insistence upon the use of the balance as a quantitative check upon the masses involved in all chemical reactions, Lavoisier was enabled to establish by his own investigations and the results achieved by others the principle now known as the " conservation of mass." Matter can neither be created nor destroyed; however a chemical system be changed, the weights before and after areequal.l To him is also due a rigorous examination of the nature of elements and compounds; he held the same views that were laid down by Boyle, and with the same prophetic foresight predicted that some of the elements which he himself accepted might be eventually found to be compounds. It is unnecessary in this place to recapitulate the many results which had accumulated by the end of the 18th century, or to discuss the labours and theories of individual workers since these receive attention under biographical headings; in this article only the salient features in the history of our science can be treated. The beginning of the 19th century was attended by far-reaching discoveries in the nature of the composition of compounds. Investigations proceeded in two directions:—(1) the nature of chemical affinity, (2) the laws of chemical combination. The first question has not yet been solved, although it has been speculated upon cnem/ca/ a//m/ty. from the earliest times. The alchemists explained chemical action by means of such phrases as " like attracts like," substances being said to combine when one " loved " the other, and the reverse when it " hated " it. Boyle rejected this terminology, which was only strictly applicable to intelligent beings; and he used the word " affinity" as had been previously done by Stahl and others. The modern sense of the word, viz. the force which holds chemically dissimilar substances together (and also similar substances as is seen in di-, tri-, and poly-atomic molecules), was introduced by Hermann Boerhaave, and made more precise by Sir Isaac Newton. The laws of chemical combination were solved, in a measure, by John Dalton, and the solution expressed as Dalton's " atomic theory." Lavoisier appears to have assumed that the composition of every chemical compound was constant, and the same opinion was the basis of much experimental inquiry at the hands of Joseph Louis Proust during 1801 to 1809, who vigorously combated the doctrine of Claude Louis Berthollet (Essai de statique chimique, 1803), viz. that fixed proportions of elements and compounds combine only under exceptional conditions, the general rule being that the composition of a compound may vary continuously between certain limits .2 This controversy was unfinished when Dalton published the first part of his New System of Chemical Philosophy in 1808, although the per saltum theory was the most popular. Dalton. Led thereto by speculations on gases, Dalton assumed that matter was composed of atoms, that in the elements the atoms were simple, and in compounds complex, being composed of elementary atoms. Dalton furthermore perceived that the same two elements or substances may combine in different proportions, and showed that these proportions had always a simple ratio to one another. This is the " law of multiple proportions." He laid down the following arbitrary rules for determining the number of atoms in a compound: if only one compound of two elements exists, it is a binary compound and its atom is composed of one atom of each element; if two compounds exist one is binary (say A + B) and the other ternary (say A + 2B); if three, then one is binary and the others may be ternary (A + 2B, and 2A + B), and so on. More important is his deduction of equivalent weights, i.e. the relative weights of atoms. He took hydrogen, the lightest substance known, to be the standard. From analyses of water, which he regarded as composed of one atom of hydrogen and one of oxygen, he I This dictum was questioned by the researches of H. Landolt, A. Heydweiller and others. In a series of 75 reactions it was found that in 6i there was apparently a diminution in weight, but in 1908, after a most careful repetition and making allowance for all experimental errors, Landolt concluded that no change occurred (see ELEMENT). a The theory of Berthollet was essentially mechanical, and he attempted to prove that the course of a reaction depended not on affinities alone but also on the masses of the reacting components. In this respect his hypothesis has much in common with the " law of mass-action " developed at a much later date by the Swedish chemists Guldberg and Waage, and the American, Willard Gibbs (see CHEMICAL ACTION). In his classical thesis Berthollet vigorously attacked the results deduced by Bergman, who had followed in his table of elective attractions the path traversed by Stahl and S. F. Geoffroy. elements received symbols composed of circles, arcs of circles, and lines, while certain class symbols, such as 'tZ' for metals, +f or acids, for alkalies, c for salts,/ for calces, &c., were used. Compounds were represented by copulating simpler symbols, e.g. mercury calx was .3 Bergman's symbolism was obviously cumbrous, and the system used in 1782 by Lavoisier was equally abstruse, since the forms gave no clue as to composition; for instance water, oxygen, and nitric acid were 7 +i, and es.. deduced the relative weight of the oxygen atom to be 6.5; from marsh gas and olefiant gas he deduced carbon = 5, there being one atom of carbon and two of hydrogen in the former and one atom of hydrogen to one of carbon in the latter; nitrogen had an equivalent of 5, and so on.' The value of Dalton's generalizations can hardly be over-estimated, notwithstanding the fact that in several cases they needed correction. The first step in this direction was effected by the co-ordination of Gay Lussac's observations on the combining volumes of gases. He discovered that gases always combined in volumes having simple ratios, and that the volume of the product had a simple ratio to the volumes of the reacting gases. For example, one volume of oxygen combined with two of hydrogen to form two volumes of steam, three volumes of hydrogen combined with one of nitrogen to give two volumes of ammonia, one volume of hydrogen combined with one of chlorine to give two volumes of hydrochloric acid. An immediate inference was that the Daltonian " atom " must have parts which enter into combination with parts of other atoms; in other words, there must exist two orders of particles, viz. (i) particles derived by limiting mechanical subdivision, the modern molecule, and (2) particles derived from the first class by chemical subdivision, i.e. particles which are incapable of existing alone, but may exist in combination. Additional evidence as to the structure of the molecule was discussed by Avogadro in 1811, and by Ampere in 1814. From the gas-laws of Boyle and J. A. C. Charles—viz. equal changes in temperature and pressure occasion equal changes in equal volumes of all gases and vapours —Avogadro deduced the law: Under the same conditions of temperature and pressure, equal volumes of gases contain equal numbers of molecules; and he showed that the relative weights of the molecules are determined as the ratios of the weights of equal volumes, or densities. He established the existence of molecules and atoms as we have defined above, and stated that the number of atoms in the molecule is generally 2, but may be 4, 8, &c. We cannot tell whether his choice of the powers of 2 is accident or design. Notwithstanding Avogadro's perspicuous investigation, and a similar exposition of the atom and molecule by A. M. Ampere, Berzelius. the views therein expressed were ignored both by their own and the succeeding generation. In place of the relative molecular weights, attention was concentrated on relative atomic or equivalent weights. This may be due in some measure to the small number of gaseous and easily volatile substances then known, to the attention which the study of the organic compounds received, and especially to the energetic investigations of J. J. Berzelius, who, fired with enthusiasm by the original theory of Dalton and the law of multiple proportions, determined the equivalents of combining ratios of many elements in an enormous number of compounds.2 He prosecuted his labours in this field for thirty years; as proof of his industry it may be mentioned that as early as 1818 he had determined the combining ratios of about two thousand simple and compound substances. We may here notice the important chemical symbolism or notation introduced by Berzelius, which greatly contributed to the definite Chemical and convenient representation of chemical composition notation and the tracing of chemical reactions. The denotation of elements by symbols had been practised by the alchemists, and it is interesting to note that the symbols allotted to the well-known elements are identical with the astrological symbols of the sun and the other members of the solar system. Gold, the most perfect metal, had the symbol of the Sun, 0 ; silver, the semiperfect metal, had the symbol of the Moon, 3; copper, iron and antimony, the imperfect metals of the gold class, had the symbols of Venus ?, Mars ', and the Earth 6 ; tin and lead, the imperfect metals of the silver class, had the symbols of Jupiter 4, and Saturn I2 ; while mercury, the imperfect metal of both the gold and silver class, had the symbol of the planet, . Torbern Olof Bergman used an elaborate system in his Opuscula physica et chemica (1783) ; the 1 Dalton's atomic theory is treated in more detail in the article ATOM. 2 Berzelius, however, appreciated the necessity of differentiating the atom and the molecule, and even urged Dalton to amend his doctrine, but without success. A partial clarification was suggested in 1787 by J. H. Hassenfratz and Adet, who assigned to each element a symbol, and to each compound a sign which should record the elements present and their relative quantities. Straight lines and semicircles were utilized for the non-metallic elements, carbon, nitrogen, phosphorus and sulphur (the " simple acidifiable bases " of Lavoisier), and circles enclosing the initial letters of their names for the metals. The " compound acidifiable bases," i.e. the hypothetical radicals of acids, were denoted by squares enclosing the initial letter of the base; an alkali was denoted by a triangle, and the particular alkali by inserting the initial letter. Compounds were denoted by joining the symbols of the components, and by varying the manner of joining compounds of the same elements were distinguished. The symbol V was used to denote a liquid, and a vertical line to denote a gas. As an example of the complexity of this system we may note the five oxides of nitrogen, which were symbolized as the first three representing the gaseous oxides, and the last two the liquid oxides. A great advance was made by Dalton, who, besides introducing simpler symbols, regarded the symbol as representing not only the element or compound but also one atom of that element or compound; in other words, his symbol denoted equivalent weights.' This system, which permitted the correct representation of molecular composition, was adopted by Berzelius in 1814, who, having replaced the geometric signs of Dalton by the initial letter (or letters) of the Latin names of the elements, represented a compound by placing a plus sign between the symbols of its components, and the number of atoms of each component (except in the case of only one atom) by placing Arabic numerals before the symbols; for example, copper oxide was Cu +0, sulphur trioxide S+30. If two compounds combined, the + signs of the free compounds were discarded, and the number of atoms denoted by an Arabic index placed after the elements, and from these modified symbols the symbol of the new compound was derived in the same manner as simple compounds were built up from their elements. Thus copper sulphate was CuO+SO3, potassium sulphate 2S03+PoO2 (the symbol Po for potassium was subsequently discarded in favour of K from kalium). At a later date Berzelius denoted an oxide by dots, equal in number to the number of oxygen atoms present, placed over the element; this notation survived longest in mineralogy. He also introduced barred symbols, i.e. letters traversed by a horizontal bar, to denote the double atom (or molecule). Although the system of Berzelius has been modified and extended, its principles survive in the modern notation. In the development of the atomic theory and the deduction of the atomic weights of elements and the formulae of compounds, Dalton's arbitrary rules failed to find complete accept- Extension ante. Berzelius objected to the hypothesis that if of the two elements form only one compound, then the at"' atoms combine one and one; and although he agreed theory. with the adoption of simple rules as a first attempt at representing a compound, he availed himself of other data in order to gain further information as to the structure of compounds. For example, at first he represented ferrous and ferric oxides by the formulae FeO,, FeO,, and by the analogy of zinc and other basic oxides he regarded these substances as constituted similarly to FeO,, and the acidic oxides alumina and chromium oxide as similar to FeO,. He found, however, that chromic acid, which he had represented as CrOs, neutralized a base containing s the 3 The following symbols were also used by Bergman: b, Yf, °--°, V, , which represented zinc, manganese, cobalt, bismuth, nickel, arsenic, platinum, water, alcohol, phlogiston. 4 The following are the symbols employed by Dalton: O.0, 0.'®, ®, O, O, ®, ®, 0, 0, O which represent in order, hydrogen, nitrogen, carbon, oxygen, phosphorus, sulphur, magnesia, lime, soda, potash, strontia, baryta, mercury; iron, zinc, copper, lead, silver, platinum, and gold were represented by circles enclosing the initial letter of the element. ~+ 1 . V and V.-, quantity of oxygen. He inferred that chromic acid must contain only three atoms of oxygen, as did sulphuric acid SO3 ; consequently chromic oxide, which contains half the amount of oxygen, must be Cr203, and hence ferric oxide must be Fe203. The basic oxides must have the general formula MO. To these results he was aided by the law of isomorphism formulated by E. Mitscherlich in 182o; and he confirmed his conclusions by showing the agreement with the law of atomic heat formulated by Dulong and Petit in 1819. While successfully investigating the solid elements and their compounds gravimetrically, Berzelius. was guilty of several inconsistencies in his views on gases. He denied that gaseous atoms could have parts, although compound gases could. This attitude was due to his adherence to the " dualistic theory" of the structure of substances, which he deduced from electrochemical researches. From the behaviour of substances on electrolysis (q.v.) he assumed that all substances had two components, one bearing a negative charge, the other a positive charge. Combination was associated with the coalescence of these charges, and the nature of the resulting compound showed the nature of the residual electricity. For example, positive iron combined with negative oxygen to form positive ferrous oxide; positive sulphur combined with negative oxygen to form negative sulphuric acid; positive ferrous oxide combined with negative sulphuric acid to form neutral ferrous sulphate. Berzelius elevated this theory to an important position in the history of our science. He recognized that if an elementary atom had parts, his theory demanded that these parts should carry different electric charges when they entered into reaction, and the products of the reaction should vary according as a positive or negative atom entered into combination. For instance if the reaction 2H2+02=H2O+H20 be true, the molecules of water should be different, for a negative oxygen atom would combine in one case, and a positive oxygen atom in the other. Hence the gaseous atoms of hydrogen and oxygen could not have parts. A second inconsistency was presented when he was compelled by the researches of Dumas to admit Avogadro's hypothesis; but here he would only accept it for the elementary gases, and denied it for other substances. It is to be noticed that J. B. Dumas did not adopt the best methods for emphasizing his discoveries. His terminology was vague and provoked caustic criticism from Berzelius; he assumed that all molecules contained two atoms, and consequently the atomic weights deduced from vapour density determinations of sulphur, mercury, arsenic, and phosphorus were quite different from those established by gravimetric and other methods. Chemists gradually tired of the notion of atomic weights on account of the uncertainty which surrounded them; and the suggestion made by W. H. Wollaston as early as 1814 to deal only with " equivalents," i.e. the amount of an element which can combine with or replace unit weight of hydrogen, came into favour, being adopted by L. Gmelin in his famous text-book. Simultaneously with this discussion of the atom and molecule, great controversy was ranging over the constitution of corn-Atom/c pounds, more particularly over the carbon or organic and mole- compounds. This subject is discussed in section IV., cular Organic Chemistry. The gradual accumulation of data weights. referring to organic compounds brought in its train a revival of the discussion of atoms and molecules. A. Laurent and C. F. Gerhardt attempted a solution by investigating chemical reactions. They assumed the atom to be the smallest part of matter which can exist in combination, and the molecule to be the smallest part which can enter into a chemical reaction. Gerhardt found that reactions could be best followed if one assumed the molecular weight of an element or compound to be that weight which occupied the same volume as two unit weights of hydrogen, and this assumption led him to double the equivalents accepted by Gmelin, making 11=1, 0=16, and C=12, thereby agreeing with Berzelius, and also to halve the values given by Berzelius to many metals. Laurent generally agreed, except when the theory compelled the adoption of formulae containing fractions of atoms; in such cases he regarded the molecular weight as the weight occupying a volume equal to four unit weights of hydrogen. The bases upon which Gerhardt and Laurent founded their views were not sufficiently well grounded to lead to the acceptance of their results; Gerhardt himself returned to Gmelin's equivalents in his Lehrbuch der Chemie (1853) as they were in such general use. In r86o there prevailed such a confusion of hypotheses as to the atom and molecule that a conference was held at Karlsruhe to discuss the situation. At the conclusion of the sitting, Lothar Meyer obtained a paper written by Stanislas Cannizzaro in 1858 wherein was found the final link required for the determination of atomic weights. This link was the full extension of Avogadro's theory to all substances, Cannizzaro showing that chemical reactions in themselves would not suffice. He chose as his unit of reference the weight of an atom of hydrogen, i.e. the weight contained in a molecule of hydrochloric acid, thus differing from Avogadro who chose the weight of a hydrogen molecule. From a study of the free elements Cannizzaro showed that an element may have more than one molecular weight; for example, the molecular weight of sulphur varied with the temperature. And from the study of compounds he showed that each element occurred in a definite weight or in some multiple of this weight. He called this proportion the " atom," since it invariably enters compounds without division, and the weight of this atom is the atomic weight. This generalization was of great value inasmuch as it permitted the deduction of the atomic weight of a non-gasifiable element from a study of the, densities of its gasifiable compounds. From the results obtained by Laurent and Gerhardt and their predecessors it immediately followed that, while an element could have but one atomic weight, it could have several equivalent weights. From a detailed study of organic compounds Gerhardt had promulgated a " theory of types " which represented a fusion of the older radical and type theories. This theory brought together, as it were, the most varied compounds, and stimulated inquiry into many fields. According to this theory, an element in a compound had a definite saturation capacity, an idea very old in itself, being framed in the law of multiple proportions. These saturation capacities were assidu- Valeacy. ously studied by Sir Edward Frankland, who from the investigation, not of simple inorganic compounds, but of the organo-metallic derivatives, determined the kernel of the theory of valency. Frankland showed that any particular element preferentially combined with a definite number (which might vary between certain limits) of other atoms; for example, some atoms always combined with one atom of oxygen, some with two, while with others two atoms entered into combination with one of oxygen. If an element or radical combined with one atom of hydrogen, it was termed monovalent; if with two (or with one atone of oxygen, which is equivalent to two atoms of hydrogen) it was divalent, and so on. The same views were expressed by Cannizzaro, and also by A. W. von Hofmann, who materially helped the acceptance of the doctrine by the lucid exposition in his Introduction to Modern Chemistry, 1865. The recognition of the quadrivalency of carbon by A. Kekule was the forerunner of his celebrated benzene theory in particular, and of the universal application of structural formulae to the representation of the most complex organic compounds equally lucidly as the representation of the simplest salts. Alexander Butlerow named the " structure theory," and contributed much to the development of the subject. He defined structure " as the manner of the mutual linking of the atoms in the molecule," but denied that any such structure could give information as to the orientation of the atoms in space. He regarded the chemical properties of a substance as due to (1) the chemical atoms composing it, and (2) the structure, and he asserted that while different compounds might have the same components (isomer-ism), yet only one compound could have a particular structure. Identity in properties necessitated identity in structure. While the principle of varying valency laid down by Frankland is still retained, Butlerow's view that structure had no spatial significance has been modified. The researches of L. Pasteur, J. A. Le Bel, J. Wislicenus, van't Hoff and others showed that substances having the same graphic formulae vary in properties and reactions, and consequently the formulae need modification in order to exhibit these differences. Such isomerism, named stereo-isomerism (q.v.) ,hasbeen assiduously developed duringrecentyears; it prevails among many different classes of organic compounds and many examples have been found in inorganic chemistry. The theory of valency as a means of showing similarity of properties and relative composition became a dominant feature of chemical theory, the older hypotheses of types, radicals, &c. being more or less discarded. We have seen how its Periodic utilization in the "structure theory " permitted great law. clarification, and attempts were not wanting for the deduction of analogies or a periodicity between elements. Frank-land had recognized the analogies existing between the chemical properties of nitrogen, phosphorus, arsenic and antimony, noting that they act as tri- or penta-valent. Carbon was joined with silicon, zirconium and titanium, while boron, being tri valent, was relegated to another group. A general classification of elements, however, was not realized by Frankland, nor even by Odling, who had also investigated the question from the valency standpoint. The solution came about by arranging the elements in the order of their atomic weights, tempering the arrangement with the results deduced from the theory of valencies and experimental observations. Many chemists contributed to the establishment of such a periodicity, the greatest advances being made by John Newlands in England, Lothar Meyer in Germany, and D. J. Mendeleeff in St Petersburg. For the development of this classification see ELEMENT. In the above sketch we have briefly treated the history of the main tendencies of our science from the earliest times to the summary. establishment of the modern laws and principles. We have seen that the science took its origin in the arts practised by the Egyptians, and, having come under the influence of philosophers, it chose for its purpose the isolation of the pinta essentia, and subsequently the " art of making gold and silver." This spirit gave way to the physicians, who regarded " chemistry as the art of preparing medicines," a denotation which in turn succumbed to the arguments of Boyle, who regarded it as the " science of the composition of substances," a definition which adequately fits the science to-day. We have seen how his classification of substances into elements and compounds, and the definitions which he assigned to these species, have similarly been retained; and how Lavoisier established the law of the "conservation of mass," overthrew the prevailing phlogistic theory, and became the founder of modern chemistry by the overwhelming importance which he gave to the use of the balance. The development of the atomic theory and its concomitants—the laws of chemical combination and the notion of atoms and equivalents—at the hands of Dalton and Berzelius, the extension to the modern theory of the atom and molecule, and to atomic and molecular weights by Avogadro, Ampere, Dumas, Laurent, Gerhardt, Cannizzaro and others, have been noted. The structure of the molecule, which mainly followed investigations in organic compounds, Frankland's conception of valency, and finally the periodic law, have also been shown in their chronological order. The principles outlined above constitute' the foundations of our science,' and although it may happen that experiments may be made with which they appear to be not in complete agreement, yet in general they constitute a body of working hypotheses of inestimable value. Chemical Education.—It is remarkable that systematic instruction in the theory and practice of chemistry only received earnest attention in our academic institutions during the opening decades of the 19th century. Although for a long time lecturers and professors had been attached to universities, generally their duties had also included the study of physics, mineralogy and other subjects, with the result that chemistry received scanty encouragement. Of practical instruction there was none other than that to be gained in a few private laboratories and in the shops of apothecaries. The necessity for experimental demonstration and practical instruction, in addition to academiclectures, appears to have been urged by the French chemists L. N. Vauquelin, Gay Lussac, Thenard, and more especially by A. F. Fourcroy and G. F. Rouelle, while in England Humphry. Davy expounded the same idea in the experimental demonstrations which gave his lectures their brilliant charm. But the real founder of systematic instruction in our science was Justus von Liebig, who, having accepted the professorship at Giessen in 1824, made his chemical laboratory and course of instruction the model of all others. He emphasized that the practical training should include (1) the qualitative and quantitative analysis of mixtures, (2) the preparation of substances according to established methods, (3) original research—a course which has been generally adopted. The pattern set by Liebig at Giessen was adopted by F. Wohler at Gottingen in 1836, by R. W. Bunsen at Marburg in 184o, and by O. L. Erdmann at Leipzig in 1843; and during the 'fifties and 'sixties, many other laboratories were founded. A new era followed the erection of the laboratories at Bonn and Berlin according to the plans of A. W. von Hofmann in 1867, and of that at Leipzig, designed by Kolbe in 1868. We may also mention the famous laboratory at Munich designed by A. von Baeyer in 1875. In Great Britain the first public laboratory appears to have been opened in 1817 by Thomas Thomson at Glasgow. But the first important step in providing means whereby students could systematically study chemistry was the foundation of the College of Chemistry in 1845. This institution was taken over by the Government in 1853, becoming the Royal College of Chemistry, and incorporated with the Royal School of Mines; in 1881 the names were changed to the Normal School of Science and Royal School of Mines, and again in 1890 to the Royal College of Science. In 1907 it was incorporated in the Imperial College of Science and Technology. Under A. W. von Hofmann, who designed the laboratories and accepted the professorship in 1845 at the instigation of Prince Albert, and under his successor (in 1864) Sir Edward Frankland, this institution became one of the most important centres of chemical instruction. Oxford and Cambridge sadly neglected the erection of convenient laboratories for many years, and consequently we find technical schools and other universities having a far better equipment and offering greater facilities. In the provinces Victoria University at Manchester exercised the greater impetus, numbering among its professors Sir W. H. Perkin and Sir Henry Roscoe. In America public laboratory instruction was first instituted at Yale College during the professorship of Benjamin Silliman. To the great progress made in recent years F. W. Clarke, W. Gibbs, E. W. Morley, Ira Remsen, and T. W. Richards have especially contributed. In France the subject was almost entirely neglected until late in the 19th century. The few laboratories existing in the opening decades were ill-fitted, and the exorbitant fees constituted a serious bar to general instruction, for these institutions received little government support. In 1869 A. Wurtz reported the existence of only one efficient laboratory in France, namely the Ecole Normale Superieure, under the direction of H. Sainte Claire Deville. During recent years chemistry has become one of the most important subjects in the curriculum of technical schools and universities, and at the present time no general educational institution is complete until it has its full equipment of laboratories and lecture theatres. Chemical Literature.—The growth of chemical literature since the publication of Lavoisier's famous Traite de chimie in 1789, and of Berzelius' Lehrbuch der Chemie in 18o8-1818, has been enormous. These two works, and especially the latter, were the models followed by Thenard, Liebig, Strecker, Wohler and many others, including Thomas Graham, upon whose Elements of Chemistry was founded Otto's famous Lehrbuch der Chemie, to which H. Kopp contributed the general theoretical part, Kolbe the organic, and Buff and Zamminer the physico-chemical. Organic chemistry was especially developed by the publication of Gerhardt's Traite de chimie organique in 1853-1856, and of Kekule's Lehrbuch der organischen Chemie in 1861-1882. General theoretical and physical chemistry was treated with conspicuous acumen by Lothar Meyer in his Moderne Theorien, by W. Ostwald in his Lehrbuch der allgem. Chemie (1884-1887), and by Nernst in his Theoretische Chemie. In English, Roscoe and Schorlemmer's Treatise on Chemistry is a standard work ; it records a successful attempt to state the theories and facts of chemistry, not in condensed epitomes, but in an easily read form. The Tecate de chimie minerale, edited by H. Moissan, and the Handbuch der anorganischen Chemie, edited by Abegg, are of the same type. O. Dammer's Ilandbuch der anorganischen Chemie and F. Beilstein's Handbuch der organischen Chemie are invaluable works of reference. Of the earlier encyclopaedias we may notice the famous Handworterbuch der reinen and angewandten Chemie, edited by Liebig; Fremy's Encyclopedia de chimie, Wurtz's Dictionnaire de chimie pure et appliquee, Watts' Dictionary of Chemistry, and Ladenburg's Handworterbuch der Chemie. The number of periodicals devoted to chemistry has steadily increased since the early part of the 19th century. In England the most important is the Journal- of the Chemical Society of London, first published in 1848. Since 1871 abstracts of papers appearing in the other journals have been printed. In 1904 a new departure was made in issuing Annual Reports, containing resumes of the most important researches of the year. The Chemical News, founded by Sir W. Crookes in 186o, may also be noted. In America the chief periodical is the American Chemical Journal, founded in 1879. Germany is provided with a great number of magazines. The Berichte der deutschen chemischen Gesellschaft, published by the Berlin Chemical Society, the Chemisches Centralblatt, which is con-fined to abstracts of papers appearing in other journals, the Zeitschrift fur Chemie, and Liebig's Annalen der Chemie are the most important of the general magazines. Others devoted to special phases are the Journal fur praktische Chemie, founded by Erdmann in 1834, the Zeitschrift fur anorganische Chemie and the Zeitschrift fur physikalische Chemie. Mention may also be made of the invaluable Jahrssberichte and the Jahrbuch der Chemie. In France, the most important journals are the Annales de chimie et de physique, founded in 1789 with the title Annales de chimie, and the Comptes rendus, published weekly by the Academie francaise since 1835. II. GENERAL PRINCIPLES The substances with which the chemist has to deal admit of classification into elements and compounds. Of the former about eighty may be regarded as well characterized, although many more have been described. Elements.-The following table gives the names, symbols and atomic weights of the perfectly characterized elements:- International Atomic Weights, 1910. Name. Atomic Atomic Symbol. Weights. Name. Symbol. Weights. 0=16. 0=16. Aluminium Al 27.1 Mercury . . Hg 200.0 Antimony Sb I20.2 Molybdenum Mo 96.o Argon . A 39.9 Neodymium . Nd 144.3 Arsenic As 74'96 Neon . . . Ne 20 Barium .. Ba 137'37 Nickel . Ni 58.68 Beryllium or Be Nitrogen N Glucinum G1 9.1- . Os 14.01 Osmium . 190'9 Bismuth - Bi 208.0 Oxygen . O 16•oo Boron . B II.0 Palladium Pd 106.7 Bromine _ Br 79.92 Phosphorus P 31.0 Cadmium Cd 112.40 Platinum Pt 195.0 Caesium . Cs 132.81 Potassium . K 39.10 Calcium Ca 40.09 Praseodymium Pr 140.6 Carbon .0 I2.O Radium . Ra 226.4 Cerium Ce 140.25 Rhodium Rh 102.9 Chlorine . Cl 35.46 Rubidium . Rb 85.45 Chromium Cr 52.0 Ruthenium Ru I0I.7 Cobalt . . Co 58.97 Samarium . Sa 150.4 Columbium . Cb Scandium . Sc 44'1 or Niobium Nb 93'5 Selenium . Se 79.2 Copper . . Cu 63.57 Silicon . Si 28.3 Dysprosium . Dy 162.5 Silver . . Ag Io7.88 Erbium . Er 167.4 Sodium . Na 23.0 Europium . Eu 152.0 Strontium . Sr 87.62 Fluorine . F 19.0 Sulphur . S 32.07 Gadolinium Gd 157.3 Tantalum Ta 181.o Gallium . . Ga 69'9 Tellurium Te 127.5 Germanium Ge 72.5 Terbium . Tb 159.2 Gold . . Au 197.2 Thallium _ T1 204.0 Helium . He 4'0 Thorium . Th 232.42 Hydrogen H 1:008. Thulium . Tm 168.5 Indium In 114.8 Tin . Sn 119.0 Iodine 126..92 Titanium. Ti 48.1 Iridium Ir 193.1 Tungsten. W 184.0 Iron . Fe 55.85 Uranium . U 238.5 Krypton . Kr 83.o Vanadium . V 51.2 Lanthanum La 139.0 Xenon . . Xe 130.7 Lead . . Pb 207.10 Ytterbium (Neo- Lithium . Li 7•.00 ytterbium) . Yb 172 Lutecium Lu 174 Yttrium . . Y 89•o Magnesium Mg 24.32 Zinc . . Zn 65'37 Manganese Mn 54.93 Zirconium . Zr 90.6 The elements are usually divided into two classes, the metallic and the non-metallic elements; the following are classed as non-metals, and the remainder as metals: Hydrogen Oxygen Boron Neon Chlorine Sulphur Carbon Krypton Bromine Selenium Silicon Xenon Iodine Tellurium Phosphorus Helium Fluorine Nitrogen Argon Of these hydrogen, chlorine, fluorine, oxygen, nitrogen, argon, neon, krypton, xenon and helium are gases, bromine is a liquid, and the remainder are solids. All the metals are solids at ordinary temperatures with the exception of mercury, which is liquid. The metals are mostly bodies of high specific gravity; they exhibit, when polished, a peculiar brilliancy or metallic lustre, and they are good conductors of heat and electricity; the non-metals, on the other hand, are mostly bodies of low specific gravity, and bad conductors of heat and electricity, and do not exhibit metallic lustre. The non-metallic elements are also sometimes termed metalloids, but this appellation, which signifies metal-like substances (Gr. edoos, like), strictly belongs to certain elements which do not possess the properties of the true metals, although they more closely resemble them than the non-metals in many respects; thus, selenium and tellurium, which are closely allied to sulphur in their chemical properties, although bad conductors of heat and electricity, exhibit metallic lustre and have relatively high specific gravities. But when the properties of the elements are carefully contrasted together it is found that no strict line of demarcation can be drawn dividing them into two classes; and if they are arranged in a series, those which are most closely allied in properties being placed next to each other, it is observed that there is a more or less regular alteration in properties from term to term in the series. When binary compounds, or compounds of two elements, are decomposed by an electric current, the two elements make their appearance at opposite poles. Those elements which are disengaged at the negative pole are termed electro-positive, or positive, or basylous elements, whilst those disengaged at the positive pole are termed electro-negative, or negative, or chlorous elements. But the difference between these two classes of elements is one of degree only, and they gradually merge into each other; moreover the electric relations of elements are not absolute, but vary according to the state of combination in which they exist, so that it is just as impossible to divide the elements into two classes according to this property as it is to separate them into two distinct classes of metals and non-metals. The following, however, are negative towards the remaining elements which are more or less positive:: Fluorine, chlorine, bromine, iodine, oxygen, sulphur, selenium, tellurium. The metals may be arranged in a series according to their power of displacing one another in salt solutions, thus Cs, Rb, K,, Na,, Mg, Al, Mn, Zn, Cd, Tl, Fe, Co, Ni, Sn, Pb, (H), Sb, Bi, As, Cu, Hg, Ag, Pd, Pt, Au. Elements which readily enter into reaction with each other, and which develop a large amount of heat on combination, are said to have a powerful affinity for each other. The tendency of positive elements to unite with positive elements, or of negative elements to unite with negative elements, is much less than that of positive elements to unite with negative elements, and the greater the difference in properties between two elements the more powerful is their affinity for each other. Thus, the affinity of hydrogen and oxygen for each other is extremely powerful, much heat being developed by the combination of these two elements; when binary compounds of oxygen are decomposed by the electric current, the oxygen invariably appears at the positive pole, being negative to all other elements, but the hydrogen of hydrogen compounds is always disengaged at the negative pole. Hydrogen and oxygen are, therefore, of very opposite natures, and this is well illustrated by the circumstance that oxygen combines, with very few exceptions, with all the remaining elements, whilst compounds of only a limited number with hydrogen have been obtained. Compounds.-A chemical compound contains two or more elements; consequently it should be possible to analyse it, i.e. separate it into its components, or to synthesize it, i.e. build it up from its components. In general, a compound has properties markedly different from those of the elements of which it is composed. Laws of Chemical Combination.—A molecule may be defined as the smallest part of a substance which can exist alone; an atom as the smallest part of a substance which can exist in combination. The molecule of every compound must obviously contain at least two atoms, and generally the molecules of the elements are also polyatomic, the elements with monatomic molecules (at moderate temperate .es) being mercury and the gases of the argon group. The laws of chemical combination are as follows:- 1. Law of Definite Proportions.—The same compound always contains the same elements combined together in the same mass proportion. Silver chloride, for example, in whatever manner it may be prepared, invariably consists of chlorine and silver in the proportions by weight of 35'45 parts of the former and 107.93 of the latter. 2. Law of Multiple Proportions.—When the same two elements combine together to form more than one compound, the different masses of one of the elements which unite with a constant mass of the other, bear a simple ratio to one another. Thus, r part by weight of hydrogen unites with 8 parts by weight of oxygen, forming water, and with 16 or 8 X 2 parts of oxygen, forming hydrogen peroxide. Again, in nitrous oxide we have a compound of 8 parts by weight of oxygen and 14 of nitrogen; in nitric oxide a compound of 16 or 8 X 2 parts of oxygen and 14 of nitrogen; in nitrous anhydride a compound of 24 or 8 X 3 parts of oxygen and 14 of nitrogen; in nitric peroxide a compound of 32 or 8 X 4 parts of oxygen and 14 of nitrogen; and lastly, in nitric anhydride a compound of 40 or 8 X 5 parts of oxygen and 14 of nitrogen. 3. Law of Reciprocal Proportions.—The masses of different elements which combine separately with one and the same mass of another element, are either the same as, or simple multiples of, the masses of these different elements which combine with each other. For instance, 35'45 ,parts of chlorine and 79.96 parts of bromine combine with 107.93 parts of silver; and when chlorine and bromine unite it is in the proportion of 35'45 parts of the former to 79.96 parts of the latter. Iodine unites with silver in the proportion of 126.97 parts to 107.93 parts of the latter, but it combines with chlorine in two proportions, viz. in the proportion of 126.97 parts either to 35'45 or to three times 35.45 parts of chlorine. There is a fourth law of chemical combination which only applies to gases. This law states that:—gases combine with one another in simple proportions by volume, and the volume of the product (if gaseous) has a simple ratio to the volumes of the original mixtures; in other words, the densities of gases are simply related to their combining weights. Nomenclature.—If a compound contains two atoms it is termed a binary compound, if three a ternary, if four a quaternary; and so on. Its systematic name is formed by replacing the last syllable of the electro-negative element by ide and prefixing the name of the other element. For example, compounds of oxygen are oxides, of chlorine, chlorides, and so on. If more than one compound be formed from the same two elements, ,the difference is shown by prefixing such words as mono-, di-, tri-, sesqui-, per-, sub-, &c., to the last part of the name, or the suffixes -ous and -ic may be appended to the name of the first element. For example take the oxides of nitrogen, N2O, NO, N2O3, NO2, N2O3; these are known respectively as nitrous oxide, nitric oxide, nitrogen trioxide, nitrogen peroxide and nitrogen pentoxide. The affixes -ous and sub- refer to the compounds containing more of the positive element, -ic and per- to those containing less. An acid (q.v.) is a compound of hydrogen, which element can be replaced by metals, the hydrogen being liberated, giving substances named salts. An alkali or base is a substance which neutralizes an acid with the production of salts but with noevolution of hydrogen. A base may be regarded as water in which part of the hydrogen is replaced by a metal, or by a radical which behaves as a metal. (The term radical is given to a group of atoms which persist in chemical changes, behaving as if the group were an element; the commonest is the ammonium group, NH4, which forms salts similar to the salts of sodium and potassium.) If the acid contains no oxygen it is a hydracid, and its systematic name is formed from the prefix hydro- and the name of the other element or radical, the last syllable of which has been replaced by the termination -ic. For example, the acid formed by hydrogen and chlorine is termed hydrochloric acid (and sometimes hydrogen chloride). If an acid contains oxygen it is termed an oxyacid. The nomenclature of acids follows the same general lines as that for binary compounds. If one acid be known its name is formed by the termination -ic, e.g. carbonic acid; if two, the one containing the less amount of oxygen takes the termination -ous and the other the termination -ic, e.g. nitrous acid, HNO2, nitric acid, HNO3. If more than two be known, the one inferior in oxygen content has the prefix hypo- and the termination -ous, and the one superior in oxygen content has the prefix per- and the termination -ic. This is illustrated in the four oxyacids of chlorine, HC1O, HC102, HC103, HC1O4, which have the names hypochlorous, chlorous, chloric and perchloric acids. An acid is said to be monobasic, dibasic, tribasic, &c., according to the number of replaceable hydrogen atoms; thus HNO3 is monobasic, sulphuric acid H2SO4 dibasic, phosphoric acid H3PO4 tribasic. An acid terminating in -ous forms a salt ending in -tile, and an oxyacid ending in -ic forms a salt ending in -ate. Thus the chlorine oxyacids enumerated above form salts named respectively hypochlorites, chlorites, chlorates and perchlorates. Salts formed from hydracids terminate in -ide, following the rule for ,binary compounds. An acid salt is one in which the whole amount of hydrogen has not been replaced by metal; a normal salt is one in which all the hydrogen has been replaced; and a basic salt is one in which part of the acid of the normal salt has been replaced by oxygen. Chemical Formulae.—Opposite the name of each element in the second column of the above table, the symbol is given which is always employed to represent it. This symbol, however, not. only represents the particular element, but a certain definite quantity of it. Thus, the letter H always stands for z. atom or x part by weight of hydrogen, the letter N for x atom or 14 parts of nitrogen, and the symbol Cl for r atom or 35'5 parts of chlorine.' Compounds are in like manner represented by writing the symbols of their constituent elements side by side, and if more than one atom of each element be present, the number is indicated by a numeral placed on the right of the symbol of the element either below or above the line. Thus, hydrochloric acid is represented by the formula HC1, that is to say, it is a compound of an atom of hydrogen with an atom of chlorine, or of r part by weight of hydrogen with 35'5 parts by weight of chlorine; again, sulphuric acid is represented by the formula H2SO4, which is a statement that it consists of 2 atoms of hydrogen, 1 of sulphur, and 4 of oxygen, and consequently of certain relative weights of these elements. A figure placed on the right of a symbol only affects the symbol to which it is attached, but when figures are placed in front of several symbols all are affected by it, thus 2H,SO4 means H2SO4 taken twice. The distribution of weight in chemical change is readily expressed in the form of equations by the aid of these symbols; the equation 2HC1+Zn = ZnCl2 for example, is to be read as meaning that from 73 parts of hydrochloric acid and 65 parts of zinc, 136 parts of zinc chloride and 2 parts of hydrogen are produced. The + sign is invariably employed in this way either to express combination or action upon, the mearring usu dly attached to the use of the sign = being that from such and such bodies such and such other bodies are formed. Approximate values of the atomic weights are empfoyed here. Usually, when the symbols of the elements are written or printed with a figure to the right, it is understood that this indicates a molecule of the element, the symbol alone representing an atom. Thus, the symbols H2 and P4 indicate that the molecules of hydrogen and phosphorus respectively contain 2 and 4 atoms. Since, according to the molecular theory, in all cases of chemical change the action is between molecules, such symbols as these ought always to be employed. Thus, the formation of hydrochloric acid from hydrogen and chlorine is correctly represented by the equation Hz+C12=2HCI; that is to say, a molecule of hydrogen and a molecule of chlorine give rise to two molecules of hydrochloric acid; whilst the following equation merely represents the r.elative weights of the elements which enter into reaction, and is not a complete expression of what is supposed to take place: H+Cl = HCI. In all cases it is usual to represent substances by formulae which to the best of our knowledge express their molecular composition in the state of gas, and not merely the relative number of atoms which they contain; thus, acetic acid consists of carbon, hydrogen and oxygen in the proportion of one atom of carbon, two of hydrogen, and one of oxygen, but its molecular weight corresponds to the formula C2H402, which therefore is always employed to represent acetic acid. When chemical change is expressed with the aid of molecular formulae not only is the distribution of weight represented, but by the mere inspection of the symbols it is possible to deduce from the law of gaseous combination mentioned above, the relative volumes which the agents and resultants occupy in the state of gas if measured at the same temperature and under the same pressure. Thus, the equation 2H2+02=2H20 not only represents that certain definite weights of hydrogen and oxygen furnish a certain definite weight of the compound which we term water, but that if the water in the state of gas, the hydrogen and the oxygen are all measured at the same temperature and pressure, the volume occupied by the oxygen is only half that occupied by the hydrogen, whilst the resulting water-gas will only occupy the same volume as the hydrogen. In other words, 2 volumes of oxygen and 4 volumes of hydrogen furnish 4 volumes of water-gas. A simple equation like this, therefore, when properly interpreted, affords a large amount of information. One other instance may be given; the equation 2NH3=N2+3H2 represents the decomposition of ammonia gas into nitrogen and hydrogen gases by the electric spark, and it not only conveys the information that a certain relative weight of ammonia, consisting of certain relative weights of hydrogen and nitrogen, is broken up into certain relative weights of hydrogen and nitrogen, but also that the nitrogen will be contained in half the space which contained the ammonia, and that the volume of the hydrogen will be one and a half times as great as that of the original ammonia, so that in the decomposition of ammonia the volume becomes doubled. Formulae which merely express the relative number of atoms of the different elements present in a compound are termed empirical formulae, and the formulae of all compounds whose molecular weights are undetermined are necessarily empirical. The molecular formula of a compound, however, is always a simple multiple of the empirical formula, if not identical with it; thus, the empirical formula of acetic acid is CH2O, and its molecular formula is C2H402, or twice CH2O. In addition to empirical and molecular formulae, chemists are in the habit of employing various kinds of rational formulae, called structural, constitutional or graphic formulae, &c., which not only express the molecular composition of the compounds to which they apply, but also embody certain assumptions as to the manner in which the constituent atoms are arranged, and convey more or less information with regard to the nature of the compound itself, viz. the class to which it belongs, the manner in whichit is formed, and the behaviour it will exhibit under various circumstances. Before explaining these formulae it will be necessary, however, to consider the differences in combining power exhibited by the various elements. Valency.—It is found that the number of atoms of a given element, of chlorine, for example, which unite with an atom of each of the other elements is very variable. Thus, hydrogen unites with but a single atom of chlorine, zinc with two, boron with three, silicon with four, phosphorus with five and tungsten with six. Those elements which are equivalent in combining or displacing power to a single atom of hydrogen are said to be univalent or monad elements; whilst those which are equivalent to two atoms of hydrogen are termed bivalent or dyad elements; and those equivalent to three, four, five or six atoms of hydrogen triad, tetrad, pentad or hexad elements. But not only is the combining power orvalency (atomicity) of the elements different, it is also observed that one element may combine with another in several proportions, or that its valency may vary; for example, phosphorus forms two chlorides represented by the formulae PC13 and PC15, nitrogen the series of oxides represented by the formulae N20, NO, (N203), N2O4, N205, molybdenum forms the chlorides MoC12, MoC13, MoC14, MoC15, MoCl6(?), and tungsten the chlorides WC12, WC14, WC15, WC16. In explanation of these facts it is supposed that each element has a certain number of " units of affinity," which may be entirely, or only in part, engaged when it enters into combination with other elements; and in those cases in which the entire number of units of affinity are not engaged by other elements, it is supposed that those which are thus disengaged neutralize each other, as it were. For example, in phosphorus pentachloride the five units of affinity possessed by the phosphorus atom are satisfied by the five monad atoms of chlorine, but in the trichloride two are disengaged, and, it may be supposed, satisfy each other. Compounds in which all the units of affinity of the contained elements are engaged are said to be saturated, whilst those in which the affinities of the contained elements are not all engaged by other elements are said to be unsaturated. According to this view, it is necessary to assume that, in all unsaturated compounds, two, or some even number of affinities are disengaged; and also that all elements which combine with an even number of monad atoms cannot combine with an odd number, and vice versa,—in 'other words, that the number of units of affinity active in the case of any given element must be always either an even or an odd number, and that it cannot be at one time an even and at another an odd number. There are, however, a few remarkable exceptions to this " law." Thus, it must be supposed that in nitric oxide, NO, an odd number of affinities are disengaged, since a single atom of dyad oxygen is united with a single atom of nitrogen, which in all its compounds with other elements acts either as a triad or pentad. When nitric peroxide, N204, is converted into gas, it decomposes, and at about 1So° C. its vapour entirely consists of molecules of the composition NO2; while at temperatures between this and o° C. it consists of a mixture in different proportions of the two kinds of molecules, N2O4 and NO2. The oxide NO2 must be regarded as another instance of a compound in which an odd number of affinities of one of the contained elements are disengaged, since it contains two atoms of dyad oxygen united with a single atom of triad or pentad nitrogen. Again, when tungsten hexachloride is converted into vapour it is decomposed into chlorine and a pentachloride, having a normal vapour density, but as in the majority of its compounds tungsten acts as a hexad, we apparently must regard its pentachloride as a compound in which an odd number of free affinities are disengaged. Hither-to no explanation has been given of these exceptions to what appears to be a law of almost universal application, viz. that the sum of the units of affinity of all the atoms in a compound is an even number. The number of units of affinity active in the case of any particular element is largely dependent, however, upon the nature of the element or elements with which it is associated. Thus, an atom of iodine only combines with one of hydrogen, but may unite with three of chlorine, which never combines with more than a single atom of hydrogen; an atom of phosphorus unites with only three atoms of hydrogen, but with five of chlorine, or with four of hydrogen and one of iodine; and the chlorides corresponding to the higher oxides of lead, nickel, manganese and arsenic, PbO2, Ni203, MnO2 and As205 do not exist as stable compounds, but the lower chlorides, PbCl2, NiC12, MnCl2 and AsC13, are very stable. The valency of an element is usually expressed by dashes or Roman numerals placed on the right of its symbol, thus: H', 0", B", Mo''; but in constructing graphic formulae the symbols of the elements are written with as many lines attached to each symbol as the element which it represents has units of affinity. The periodic law (see ELEMENT) permits a grouping of the elements according to their valency as follows:—Group 0: helium, neon, argon, krypton and xenon appear to be devoid of valency. Group I.: the alkali metals Li, Na, K, Rb, Cs, and also Ag, monovalent; Cu, monovalent and divalent; Au, monovalent and trivalent. Group II.: the alkaline earth metals Ca, Sr, Ba, and also Be (Gl), Mg, Zn, Cd, divalent; Hg, monovalent and divalent. Group III.: B, trivalent; Al, trivalent, but possibly also tetra-or penta-valent; Ga, divalent and trivalent; In, mono-, di- and tri-valent; T1, monovalent and trivalent. Group IV.: C, Si, Ge, Zr, Th, tetravalent; Ti, tetravalent and hexavalent; Sn, Pb, divalent and tetravalent; Ce, trivalent and tetravalent. Group V.: N, trivalent and pentavalent, but divalent in nitric oxide; P, As, Sb, Bi, trivalent and pentavalent, the last being possibly divalent in BiO and BiC12. Group VI.: 0, usually divalent, but tetravalent and possibly hexavalent in oxonium and other salts; S, Se, Te, di-, tetra- and hexa-valent; Cr, di-, tri- and hexa-valent; Mo, W, di-, tri-, tetra-, penta- and hexa-valent. Group VII.: H (?), monovalent; the halogens F, Cl, Br, I, usually monovalent, but possibly also tri- and pentavalent; Mn, divalent and trivalent, and possibly heptavalent in permanganates. Group VIII.: Fe, Co, divalent and trivalent; Ni, divalent; Os, Ru, hexavalent and octavalent; Pd, Pt, divalent and tetravalent; Ir, tri-, tetra- and hexa-valent. (See also VALENCY.) Constitutional Formulae.—Graphic or constitutional formulae are employed to express the manner in which the constituent atoms of compounds are associated together; for example, the trioxide of sulphur is usually regarded as a compound of an atom of hexad sulphur with three atoms of dyad oxygen, and this hypothesis is illustrated by the graphic formula 0 =S0 When this oxide is brought into contact with water it combines with it forming sulphuric acid, H2SO4. In this compound only two of the oxygen atoms are wholly associated with the sulphur atom, each of the remaining oxygen atoms being united by one of its affinities to the sulphur atoms, and by the remaining affinity to an atom of hydrogen; thus H•0 S ,O H.O- O. The graphic formula of a sulphate is readily deduced by remembering that the hydrogen atoms are partially or entirely replaced. Thus acid sodium sulphate, normal sodium sulphate, and zinc sulphate have the formulae Na•O Na-0 ,O O ~O H.O>S 0, Na•O> O znS CH2, and .CH groups, which we have seen to characterize the different types of hydrocarbons. It may be noticed here that cyclic nuclei can only contain the groups > CH2. and >.CH, the first characterizing the polymethylene and reduced heterocyclic compounds, the second true aromatic compounds. Substituting one hydroxyl group into each of these residues, we obtain radicals of the type—CHz•OH, >CH•OH, and a C•OH; these compounds are known as alcohols (q.v.), and are termed primary, secondary, and tertiary respectively. Polymethylenes can give only secondary and tertiary alcohols, benzene only tertiary; these latter compounds are known as phenols. A second hydroxyl group may be introduced into the residues —CH2.OH and >CH•OH, with the production of radicals of the form —CH(OH)2 and >C(OH)z. Compounds containing these groupings are, however, rarely observed (see CHLORAL), and it is generally found that when compounds of these types are expected, the elements of water are split off, and the typical groupings are reduced to —CH: 0 and > C: 0. Compounds containing the group -CH:O are known as aldehydes (q.v.), while the group >C:0 (sometimes termed the carbonyl or keto group) characterizes the ketones (q.v.). A third hydroxyl group may be introduced into the—CH: 0 residue with the formation of the radical —C(OH):O; this is known as the carboxyl group, and characterizes the organic acids. Sulphur analogues of these oxygen compounds are known. Thus the thio-alcohols or mercaptans (q.v.) contain the group —CH2•SH; and the elimination of the elements of sulphuretted hydrogen between two molecules of a thio-alcohol results in the formation of a thio-ether or sulphide, R2S. Oxidation of thio-ethers results in the formation of sulphoxides, R2: S: 0, and sulphones, R2: SO2; oxidation of mercaptans yields sulphonic acids, R•S0,H, and of sodium mercaptides sulphinic acids, R.SO(OH). We may also notice that thio-ethers combine with alkyl iodides to form sulphine or sulphonium compounds, R, : SI. Thio-aldehydes, thio-ketones and thio-acids also exist. We proceed to consider various simple derivatives of the alcohols, which we may here regard as hydroxy hydrocarbons, R•OH, where R is an alkyl radical, either aliphatic or cyclic in nature. Of these, undoubtedly the simplest are the ethers (q.v.), formed by the elimination of the elements of water between two molecules of the same alcohol, " simple ethers," or of different alcohols, " mixed ethers." These compounds may be regarded as oxides in just the same way as the alcohols are regarded as hydroxides. In fact, the analogy between the alkyl groups and metallic elements forms a convenient basis from which to consider many derivatives. Thus from ethyl alcohol there can be prepared compounds, termed esters (q.v.), or ethereal salts, exactly comparable in structure with corresponding salts of, say, potassium; by the action of the phosphorus haloids, the hydroxyl group is replaced by a halogen atom with the formation of derivatives of the type R•Cl(Br,I); nitric acid forms nitrates, R•O•NO2; nitrous acid, nitrites, R•O•NO; sulphuric acid gives normal sulphates R2SO4, or acid sulphates, R•SO,H. Organic acids also condense with alcohols to form similar compounds: the fats, waxes, and essential oils are naturally occurring substances of this class. An important class of compounds, termed amines (q.v.), results from the condensation of alcohols with ammonia, water being eliminated between the alcoholic hydroxyl group and a hydrogen atom of the ammonia. Three types of amines are possible and have been prepared: primary, R•NH2; secondary, R2: NH; and tertiary, R3 i N ; the oxamines, R3N : O, are closely related to the tertiary ammonias, which also unite with a molecule of alkyl iodide to form salts of quaternary ammonium bases, e.g. R4N•I. It is worthy of note that phosphorus and arsenic bases analogous to the amines are known (see PHOSPHORUS and ARSENIC). From the primary amines are derived the diazo compounds (q.v.) and azo compounds (q.v.); closely related are the hydrazines (q.v.). Secondary amines yield nitrosamines, R2N•NO, with nitrous acid. By the action of hydroxylamine or phenylhydrazine on aldehydes or ketones, condensation occurs between the carbonyl oxygen of the aldehyde or ketone and the amino group of the hydroxylamine or hydrazine. Thus with hydroxylamine aldehydes yield aldoxirnes, R•CH : N.OH, and ketones, ketoximes, R2C:N•OH (see OXIMES), while phenyl hydrazine gives phenylhydrazones, R2C:N•NH•C6H, (see HYnRn-ZONES). Oxyaldehydes and oxyketones (viz. compounds containing an oxy in addition to an aldehydic or ketonic group) undergo both condensation and oxidation when treated with phenylhydrazine, forming compounds known as osozones; these are of great importance in characterizing the sugars (q.v.). The carboxyl group constitutes another convenient starting-point for the orientation of many types of organic compounds. This group may be considered as resulting from the fusion of a carbonyl (:CO) and a hydroxyl (HO.) group; and we may expect to meet with compounds bearing structural resemblances to the derivatives of alcohols and aldehydes (or ketones). Considering derivatives primarily concerned with transformations of the hydroxyl group, we may regard our typical acid as a fusion of a radical R.CO— (named acetyl, propionyl, butyl, &c., generally according to the name of the hydrocarbon containing the same number of carbon atoms) and a hydroxyl group. By replacing the hydroxyl group by a halogen, acid-haloids result; by the elimination of the elements of water between two molecules, acid-anhydrides, which may be oxidized to acid-peroxides; by replacing the hydroxyl group by the group •SH, thio-acids; by replacing it by the amino group, acid-amides (q.v.); by replacing it by the group —NH.NH2, acid-hydrazides. The structural relations of these compounds are here shown : R•CO.OH; R•CO•Cl; (R.CO)20; R•CO•SH; acid; acid-chloride; acid-anhydride; thin-acid; R•CO•NH2; R•CO•NH•NH2. acid-amide; acid-hydrazide. It is necessary clearly to distinguish such compounds as the amino- (or amido-) acids and acid-amides; in the first case the amino group is substituted in the hydrocarbon residue, in the second it is substituted in the carboxyl group. By transformations of the carbonyl group, and at the same time of the hydroxyl group, many interesting types of nitrogen compounds may be correlated. Thus from the acid-amides, which we have seen to be closely related to the acids themselves, we obtain, by replacing the carbonyl oxygen by chlorine, the acidamido-chlorides, R•CC12•NH2, from which are derived the imido-chlorides, R.CCI:NH, by loss of one molecule of hydrochloric acid. By replacing the chlorine in the imido-chloride by an oxyalkyl group we obtain the imido-ethers, R•C(OR'):NH; and by an amino group, the amidines, R•C(NH2) :NH. The carbonyl oxygen may also be replaced by the oxime group, : N•OH; thus the acids yield the hydroxamic acids, R•C(OH) : NOH, and the acid-amides the amidoximes, R•C(NH2): NOH. Closely related to the amidoximes are the nitrolic acids, R•C(NO2) : NOH. Cyclic Hydrocarbons and Nuclei. Having passed in rapid review the various types of compounds derived by substituting for hydrogen various atoms or groups of atoms in hydrocarbons (the separate articles on specific compounds should be consulted for more detailed accounts), we now proceed to consider the closed chain compounds. Here we meet with a great diversity of types: oxygen, nitrogen, sulphur and other elements may, in addition to carbon, combine together in a great number of arrangements to form cyclic nuclei, which exhibit characters closely resembling open-chain compounds in so far as they yield substitution derivatives, and behave as compound radicals. In classifying closed chain compounds, the first step consists in dividing them into: (1) carbocyclic, in which the ring is composed solely of carbon atoms—these are also known as homocyclic or isocyclic on account of the identity of the members of the ring—and (2) heterocyclic, in which different elements go to make up the ring. Two primary divisions of carbocyclic compounds may be conveniently made: (1) those in which the carbon atoms are completely saturated—these are known by the generic term polymethylenes, their general formula being (CH2),,: it will be noticed that they are isomeric with ethylene and its homologues; they differ, however, from this series in not containing a double linkage, but have a ringed structure; and (2) those containing fewer hydrogen atoms than suffice to saturate the carbon valencies—these are known as the aromatic compounds proper, or as benzene compounds, from the predominant part which benzene plays in their constitution. It was long supposed that the simplest ring obtainable contained six atoms of carbon, and the discovery of trimethylene in 1882 by August Freund by the action of sodium on trimethylene bromide, Br(CH2)3Br, came somewhat as a surprise, especially in view of its behaviour with bromine and hydrogen bromide. In comparison with the isomeric propylene, CH3•HC:CH2, it is remarkably inert, being only very slowly attacked by bromine, which readily combines with propylene. But on the other hand, it is readily converted by hydrobromic acid into normal propyl bromide, CH3•CH2•CH2Br. The separation of carbon atoms united by single affinities in this manner at the time the observation was made was altogether without precedent. A similar behaviour has since been noticed in other trimethylene derivatives, but the fact that bromine, which usually acts so much more readily than hydrobromic acid on unsaturated compounds, should be so inert when hydrobromic acid acts readily is one still needing a satisfactory explanation. A great impetus was given to the study of polymethylene derivatives by the important and unexpected observation made by W. H. Perkin, junr., in 1883, that ethylene and trimethylene bromides are capable of acting in such a way on sodium acetoacetic ester as to form tri- and tetra-methylene rings. Perkin has himself contributed largely to our knowledge of such compounds; penta- and hexa-methylene derivatives have also received considerable attention (see P OLYMETHYLENES) . A. von Baeyer has sought to explain the variations in stability manifest in the various polymethylene rings by a purely mechanical hypothesis, the " strain " or Spannungs theory (Ber., 1885, p. 2277). Assuming the four valencies of the carbon atom to be directed from the centre of a regular tetra. hedron towards its four corners, the angle at which they meet is 109° 28'. Baeyer supposes that in the formation of carbon " rings " the valencies become deflected from their positions, and that the tension thus introduced may be deduced from a comparison of this angle with the angles at which the strained valencies would meet. He regards the amount of deflection as a measure .of the stability of the " ring." The readiness with which ethylene is acted on in comparison with other types of hydrocarbon, for example, is in harmony, he considers, with the circumstance that the greatest distortion must be involved in its formation, as if deflected into parallelism each valency will be drawn out of its. position through 2.109° 28'. The values in other cases are calculable from the formula 1(1o9° 28'—a), where a is the internal angle of the regular polygon contained by sides equal in number to the number of the carbon atoms composing the ring. These values are: Trimethylene. Tetramethylene. ;(Io9° 28'—60°) =24° 44'. 1(109° 28'—90 ) =9° 44'. Pentamethylene. Hexamethylene. 1(109° 28'—toe) =0° 44'. i(109° 28'—I2O°)= -5° 16'. The general behaviour of the several types of hydrocarbons is certainly in accordance with this conception, and it is a remark-able fact that when benzene is reduced with hydriodic acid, it is converted into a mixture of hexamethylene and methylpentamethylene (cf. W. Markownikov, Ann., 1898, 302, p. 1); and many other cases of the conversion of six-carbon rings into five-carbon rings have been recorded (see below, Decompositions of the Benzene Ring). Similar considerations will apply to rings containing other elements besides carbon. As an illustration it may be pointed out that in the case of the two known types of lactones—the 'y-lactones, which contain four carbon atoms and one oxygen atom in the ring, are more readily formed and more stable (less readily hydrolysed) than the E-lactones, which contain one oxygen and five carbon atoms in the ring. That the number of atoms which can be associated in a ring by single affinities is limited there can be no doubt, but there is not yet sufficient evidence to show where the limit must be placed. Baeyer has suggested that his hypothesis may also be applied to explain the instability of acetylene and its derivatives, and the still greater instability of the polyacetylene compounds. Benzene. The ringed structure of benzene, C6H6, was first suggested in 1865 by August Kekule, who represented the molecule by six CH groups placed at the six angles of a regular hexagon, the sides of which denoted the valencies saturated by adjacent carbon atoms, the fourth valencies of each carbon atom being represented as saturated along alternate sides. This formula, notwithstanding many attempts at both disproving and modifying it, has well stood the test of time; the subject has been the basis of constant discussion, many variations have been proposed, but the original conception of Kekule remains quite as convenient as any of the newer forms, especially when considering the syntheses and decompositions of the benzene complex. It will be seen, however, that the absolute disposition of the fourth valency may be ignored in a great many cases, and consequently the complex may be adequately represented as a hexagon. This symbol is in general use; it is assumed that at each corner there is a CH group which, however, is not always written in; if a hydrogen atom be substituted by another group, then this group is attached to the corner previously occupied by the displaced hydrogen. The following diagrams illustrate these statements oil C•OH OH
End of Article: CHEMISTRY (formerly "chymistry"; Gr. xvµela; for derivation see ALCHEMY)
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