of more or less unstable intermediate products. Thus the unstable ozone is very often first formed on the evolution of oxygen, whilst in the reaction between oxygen and hydrogen water is often not at once formed, but first the unstable hydrogen peroxide as an intermediate product.
Let us now consider the chemical process in the light of the equation
reaction-velocity＝chemical force/chemical resistance.
Thermodynamics shows that at very low temperatures, i.e. in the immediate vicinity of the absolute zero, there is no equilibrium, but every chemical process advances to completion in the one or the other direction. The chemical forces therefore act in the one direction towards complete consumption of the reacting substance. But since the chemical resistance is now immensely great, they can produce practically no appreciable result.
At higher temperatures the reaction always proceeds, at least in homogeneous systems, to a certain equilibrium, and as the chemical resistance now has finite values this equilibrium will always finally be reached after a longer or shorter time. Finally, at very high temperatures the chemical resistance is in every case very small, and the equilibrium is almost instantaneously reached; at the same time, the affinity of the reaction, as in the case of the mutual affinity between oxygen and hydrogen, may very strongly diminish, and we have then chemical indifference again, not because, as at low temperatures, the denominator of the previous expression becomes very great, but because the numerator now assumes vanishingly small values. (W. N.)
CHEMISTRY formerly “chymistry”; Gr. χυμεία; 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 may 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 subdivisions 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.
I. History.—This 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.
III. Inorganic Chemistry.—Here is treated the history of descriptive inorganic chemistry; reference should be made to the articles on the separate elements for an account of their preparation, properties, &c.
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 compounds 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; Alloys; 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 accumulation 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 philosophy. matter is composed of minute discrete particles, prevailing in the Greek schools. These “elements,” 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 Alchemy. suggested for the word alchemy, and there seems to 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 transmutation 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
