"Negative catalysis," i.e. the retardation of a reaction by addition of some substance, which is occasionally observed, appears to depend upon the destruction of a "positive catalyte" by the body added.

A catalyte can have no influence, however, upon the affinity of a process, since that would be contrary to the second law of thermodynamics, according to which affinity of an isothermal process, which is measured by the maximum work, only depends upon the initial and final states. The effect of a catalyte is therefore limited to the resistances opposing the progress of a reaction, and does not influence its driving-force or affinity. Since the catalyte takes no part in the reaction its presence has no effect on the equilibrium-constant. This, in accordance with the law of mass-action, is the ratio of the separate reaction-velocities in the two contrary directions. A catalyte must therefore always accelerate the reverse-reaction. If the velocity of formation of a body be increased by addition of some substance then its velocity of decomposition must likewise increase. We have an example of this in the well-known fact that the formation, and no less the saponification, of esters, proceeds with increased velocity in the presence of acids, while the observation that in absence of water-vapour neither gaseous ammonium chloride dissociates nor dry ammonia combines with hydrogen chloride becomes clear on the same grounds.

A general theory of catalytic phenomena does not at present exist. The formation of intermediate products by the action of the reacting substance upon the catalyte has often been thought to be the cause of these. These intervening products, whose existence in many cases has been proved, then split up into the catalyte and the reaction-product. Thus chemists have sought to ascribe the influence of oxides of nitrogen on the formation of sulphuric acid to the initial formation of nitrosyl-sulphuric acid, SO2(OH)(NO2), from the mixture of sulphur dioxide, oxides of nitrogen and air, which then reacted with water to form sulphuric and nitrous acids. When the velocity of such intermediate reactions is greater than that of the total change, such an explanation may suffice, but a more certain proof of this theory of catalysis has only been reached in a few cases, though in many others it appears very plausible. Hence it is hardly possible to interpret all catalytic processes on these lines.

In regard to catalysis in heterogeneous systems, especially the hastening of gas-reactions by platinum, it is very probable that it is closely connected with the solution or absorption of the gases on the part of the metal. From the experiments of G. Bredig it seems that colloidal solutions of a metal act like the metal itself. The action of a colloidal-platinum solution on the decomposition of hydrogen peroxide is still sensible even at a dilution of 1/70,000,000 grm.-mol. per litre; indeed the activity of this colloidal-platinum solution calls to mind in many ways that of organic ferments, hence Bredig has called it an "inorganic ferment." This analogy is especially striking in the change of their activity with time and temperature, and in the possibility, by means of bodies like sulphuretted hydrogen, hydrocyanic acid, &c., which act as strong poisons upon the latter, of "poisoning" the former also, i.e. of rendering it inactive. In the case of the catalytic action of water-vapour upon many processes of combustion already mentioned, a part of the effect is probably due to the circumstance, disclosed by numerous experiments, that the union of hydrogen and oxygen proceeds, between certain temperature limits at least, after the equation H2 + O2 = H2O2, that is, with the preliminary formation of hydrogen peroxide, which then breaks down into water and oxygen, and further, above all, to the fact that this substance results from oxygen and water at high temperatures with great velocity, though indeed only in small quantities.

The view now suggests itself, that, for example, in the combustion of carbon monoxide at moderately high temperatures, the reaction

(I.) 2CO + O2 = 2CO2

advances with imperceptible speed, but that on the contrary the two stages

(II.) 2H2O + O2 = 2H2O2,

(III.) 2CO + 2H2O2 = 2CO2 + 2H2O,

which together result in (I.), proceed rapidly even at moderate temperatures.

Temperature and Reaction-Velocity.—There are few natural constants which undergo so marked a change with temperature as those of the velocities of chemical changes. As a rule a rise of temperature of 10 deg. causes a twofold or threefold rise of reaction-velocity.

If the reaction-coefficient k, in the sense of the equation derived above, viz. k = t^{-1} log [a/(a-x)], be determined for the inversion of cane-sugar by an acid of given concentration, the following values are obtained:—

Temperature = 25 deg. 40 deg. 45 deg. 50 deg. 55 deg. k = 9.7 73 139 268 491;

here a rise of temperature of only 30 deg. suffices to raise the speed of inversion fifty times.

We possess no adequate explanation of this remarkable temperature influence; but some account of it is given by the molecular theory, according to which the energy of that motion of substances in homogeneous gaseous or liquid systems which constitutes heat increases with the temperature, and hence also the frequency of collision of the reacting substances. When we reflect that the velocity of motion of the molecules of gases, and in all probability those of liquids also, are proportional to the square root of the absolute temperature, and therefore rise by only 1/6% per degree at room-temperature, and that we must assume the number of collisions proportional to the velocity of the molecules, we cannot regard the actually observed increase of reaction-velocity, which often amounts to 10 or 12% per degree, as exclusively due to the quickening of the molecular motion by heat. It is more probable that the increase of the kinetic energy of the atomic motions within the molecule itself is of significance here, as the rise of the specific heat of gases with temperature seems to show. The change of the reaction-coefficient k with temperature may be represented by the empirical equation log k = -AT^{-1} + B + CT, where A, B, C are positive constants. For low temperatures the influence of the last term is as a rule negligible, whilst for high temperatures the first term on the right side plays a vanishingly small part.

Definition of Chemical Affinity.—We have still to discuss the question of what is to be regarded as the measure of chemical affinity. Since we are not in a position to measure directly the intensity of chemical forces, the idea suggests itself to determine the strength of chemical affinity from the amount of the work which the corresponding reaction is able to do. To a certain extent the evolution of heat accompanying the reaction is a measure of this work, and attempts have been made to measure chemical affinities thermo-chemically, though it may be easily shown that this definition was not well chosen. For when, as is clearly most convenient, affinity is so defined that it determines under all circumstances the direction of chemical change, the above definition fails in so far as chemical processes often take place with absorption of heat, that is, contrary to affinities so defined. But even in those cases in which the course of the reaction at first proceeds in the sense of the evolution of heat, it is often observed that the reaction advances not to completion but to a certain equilibrium, or, in other words, stops before the evolution of heat is complete.

A definition free from this objection is supplied by the second law of thermodynamics, in accordance with which all processes must take place in so far as they are able to do external work. When therefore we identify chemical affinity with the maximum work which can be gained from the process in question, we reach such a definition that the direction of the process is under all conditions determined by the affinity. Further, this definition has proved serviceable in so far as the maximum work in many cases may be experimentally measured, and moreover it stands in a simple relation to the equilibrium constant K. Thermodynamics teaches that the maximum work A may be expressed as A = RT log K, when R denotes the gas-constant, T the absolute temperature. In this it is further assumed that both the molecular species produced as well as those that disappear are present in unit concentration. The simplest experimental method of directly determining chemical affinity consists in the measurement of electromotive force. The latter at once gives us the work which can be gained when the corresponding galvanic element supplies the electricity, and, since the chemical exchange of one gram-equivalent from Faraday's law requires 96,540 coulombs, we obtain from the product of this number and the electromotive force the work per gram-equivalent in watt-seconds, and this quantity when multiplied by O.23872 is obtained in terms of the usual unit, the gram-calorie. Experience teaches that, especially when we have to deal with strong affinities, the affinity so determined is for the most part almost the same as the heat-evolution, whilst in the case in which only solid or liquid substances in the pure state take part in the reaction at low temperatures, heat-evolution and affinity appear to possess a practically identical value.

Hence it seems possible to calculate equilibria for low temperatures from heats of reaction, by the aid of the two equations

A = Q, A = RT log K;

and since the change of A with temperature, as required by the principles of thermodynamics, follows from the specific heats of the reacting substances, it seems further possible to calculate chemical equilibria from heats of reaction and specific heats. The circumstance that chemical affinity and heat-evolution so nearly coincide at low temperatures may be derived from the hypothesis that chemical processes are the result of forces of attraction between the atoms of the different elements. If we may disregard the kinetic energy of the atoms, and this is legitimate for low temperatures, it follows that both heat-evolution and chemical affinity are merely equal to the decrease of the potential energy of the above-mentioned forces, and it is at once clear that the evolution of heat during a reaction between only pure solid or pure liquid substances possesses special importance.

More complicated is the case in which gases or dissolved substances take part. This is simplified if we first consider the mixing of two mutually chemically indifferent gases. Thermodynamics teaches that external work may be gained by the mere mixing of two such gases (see DIFFUSION), and these amounts of work, which assume very considerable proportions at high temperatures, naturally affect the value of the maximum work and so also of the affinity, in that they always come into play when gases or solutions react. While therefore we regard as chemical affinity in the strictest sense the decrease of potential energy of the forces acting between the atoms, it is clear that the quantities here involved exhibit the simplest relations under the experimental conditions just given, for when only substances in a pure state take part in a reaction, all mixing of different kinds of molecules is excluded; moreover, the circumstance that the respective substances are considered at very low temperatures reduces the quantities of energy absorbed as kinetic energy by their molecules to the smallest possible amount.

Chemical Resistance.—When we know the chemical affinity of a reaction, we are in a position to decide in which direction the process must advance, but, unless we know the reaction-velocity also, we can in many cases say nothing as to whether or not the reaction in question will progress with a practically inappreciable velocity so that apparent chemical indifference is the result. This question may be stated in the light of the law of mass-action briefly as follows:—From a knowledge of the chemical affinity we can calculate the equilibrium, i.e. the numerical value of the constant K = k/k'; but to be completely informed of the process we must know not only the ratio of the two velocity-constants k and k', but also the separate absolute values of the same.

In many respects the following view is more comprehensive, though naturally in harmony with the one just expressed. Since the chemical equilibrium is periodically attained, it follows that, as in the case of the motion of a body or of the diffusion of a dissolved substance, it must be opposed by very great friction. In all these cases the velocity of the process at every instant is directly proportional to the driving-force and inversely proportional to the frictional resistance. We hence arrive at the result that an equation of the form

reaction-velocity = chemical force/chemical resistance

must also hold for chemical change; here we have an analogy with Ohm's law. The "chemical force" at every instant may be calculated from the maximum work (affinity); as yet little is known about "chemical resistance," but it is not improbable that it may be directly measured or theoretically deduced. The problem of the calculation of chemical reaction-velocity in absolute measure would then be solved; so far we possess indeed only a few general facts concerning the magnitude of chemical resistance. It is immeasurably small at ordinary temperatures for ion-reactions, and, on the other hand, fairly large for nearly all reactions in which carbon-bonds must be loosened (so-called "inertia of the carbon-bond") and possesses very high values for most gas-reactions also. With rising temperature it always strongly diminishes; on the other hand, at very low temperatures its values are always enormous, and at the absolute zero of temperature may be infinitely great. Therefore at that temperature all reactions cease, since the denominator in the above expression assumes enormous values.

It is a very remarkable phenomenon that the chemical resistance is often small in the case of precisely those reactions in which the affinity is also small; to this circumstance is to be traced the fact that in many chemical changes the most stable condition is not at once reached, but is preceded by the formation 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. [Greek: chymeia]; 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.

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.—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

Greek philosophy.

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 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).

Alchemy.

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 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 the 11th 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.

Iatrochemistry.

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 attention, and several of our important acids being 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.[1]

Boyle.

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 during their generally unordered researches were replaced 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 substances distinctly new corpuscles of a compound were formed, and that each corpuscle had a certain affinity for other corpuscles.

Phlogistic theory.

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 next dominated chemical thought was an alchemical 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 [Greek: phlogistos], 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 should have 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.

Lavoisier.

Descriptive chemistry was now assuming considerable proportions; the experimental inquiries suggested by Boyle were being assiduously developed; and a wealth of observations 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 (1) 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" ([Greek: oxys], 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 are equal.[2] 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.

Chemical Affinity.

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 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.[3]

Dalton.

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. 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 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.[4]

The value of Dalton's generalizations can hardly be overestimated, 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. (1) 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.

Berzelius.

Notwithstanding Avogadro's perspicuous investigation, and a similar exposition of the atom and molecule by A. M. Ampere, 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.[5] 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.

Chemical notation.

We may here notice the important chemical symbolism or notation introduced by Berzelius, which greatly contributed to the definite and convenient representation of chemical composition 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, [*]; silver, the semiperfect metal, had the symbol of the Moon, [*]; copper, iron and antimony, the imperfect metals of the gold class, had the symbols of Venus [*], Mars [*], and the Earth [*]; tin and lead, the imperfect metals of the silver class, had the symbols of Jupiter [*], and Saturn [*]; 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 elements received symbols composed of circles, arcs of circles, and lines, while certain class symbols, such as [*] for metals, [*] for acids, [*] for alkalies, [*] for salts, [*] for calces, &c., were used. Compounds were represented by copulating simpler symbols, e.g. mercury calx was [*][*].[6] 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 [*], [*], and [*].

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 / 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

[*], [*], [*], [*], and [*],

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.[7] 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+O, sulphur trioxide S+3O. 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 + SO^3, potassium sulphate 2SO^3 + PoO^2 (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.

Extension of the atomic theory.

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 acceptance. Berzelius objected to the hypothesis that if two elements form only one compound, then the atoms combine one and one; and although he agreed 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 FeO2, FeO3, and by the analogy of zinc and other basic oxides he regarded these substances as constituted similarly to FeO2, and the acidic oxides alumina and chromium oxide as similar to FeO3. He found, however, that chromic acid, which he had represented as CrO6, neutralized a base containing 1/3 the 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 Cr2O3, and hence ferric oxide must be Fe2O3. 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 1820; 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 + O2 = H2O + H2O 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.

Atomic and molecular weights.

Simultaneously with this discussion of the atom and molecule, great controversy was ranging over the constitution of compounds, more particularly over the carbon or organic compounds. This subject is discussed in section IV., Organic Chemistry.The gradual accumulation of data 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 H = 1, O = 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 1860 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.

Valency.

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 assiduously 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 atom 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 (isomerism), 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 stereoisomerism (q.v.), has been assiduously developed during recent years; it prevails among many different classes of organic compounds and many examples have been found in inorganic chemistry.

Periodic law.

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 utilization in the "structure theory" permitted great clarification, and attempts were not wanting for the deduction of analogies or a periodicity between elements. Frankland 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 trivalent, 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.

Summary.

In the above sketch we have briefly treated the history of the main tendencies of our science from the earliest times to the 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 quinta 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 academic lectures, 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 1840, 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 1808-1818, 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 Traite de chimie minerale, edited by H. Moissan, and the Handbuch der anorganischen Chemie, edited by Abegg, are of the same type. O. Dammer's Handbuch 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 und angewandten Chemie, edited by Liebig; Fremy's Encyclopedie 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 1860, 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 confined 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 Jahresberichte 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.

Atomic Atomic Name. Symbol. Weights. Name. Symbol. Weights. O=16. O=16. Aluminium Al 27.1 Mercury Hg 200.0 Antimony Sb 120.2 Molybdenum Mo 96.0 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} 9.1 Nitrogen N 14.01 Glucinum Gl} Osmium Os 190.9 Bismuth Bi 208.0 Oxygen O 16.00 Boron B 11.0 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 C 12.0 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 101.7 Cobalt Co 58.97 Samarium Sa 150.4 Columbium Cb} 93.5 Scandium Sc 44.1 or Niobium Nb} Selenium Se 79.2 Copper Cu 63.57 Silicon Si 28.3 Dysprosium Dy 162.5 Silver Ag 107.88 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 181.0 Gallium Ga 69.9 Tellurium Te 127.5 Germanium Ge 72.5 Terbium Tb 159.2 Gold Au 197.2 Thallium Tl 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 I 126.92 Titanium Ti 48.1 Iridium Ir 193.1 Tungsten W 184.0 Iron Fe 55.85 Uranium U 238.5 Krypton Kr 83.0 Vanadium V 51.2 Lanthanum La 139.0 Xenon Xe 130.7 Lead Pb 207.10 Ytterbium Yb 172 Lithium Li 7.00 (Neoytterbium) Lutecium Lu 174 Yttrium Y 89.0 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. [Greek: eidos], 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 temperatures) 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, 1 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, N2O5; 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 no evolution 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, HClO, HClO2, HClO3, HClO4, 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 -ite, 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 1 atom or 1 part by weight of hydrogen, the letter N for 1 atom or 14 parts of nitrogen, and the symbol Cl for 1 atom or 35.5 parts of chlorine.[8] 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 HCl, that is to say, it is a compound of an atom of hydrogen with an atom of chlorine, or of 1 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 2H2SO4 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

2HCl + Zn = ZnCl2 + H2,

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 meaning usually attached to the use of the sign = being that from such and such bodies such and such other bodies are formed.

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

H2 + Cl2 = 2HCl;

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 relative weights of the elements which enter into reaction, and is not a complete expression of what is supposed to take place:—

H + Cl = HCl.

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 C2H4O2, 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 + O2= 2H2O

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 C2H4O2, 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 which it 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 or valency (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 PCl3 and PCl5, nitrogen the series of oxides represented by the formulae N2O, NO, (N2O3), N2O4, N2O5, molybdenum forms the chlorides MoCl2, MoCl3, MoCl4, MoCl5, MoCl6(?), and tungsten the chlorides WCl2, WCl4, WCl5, WCl6.

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, N2O4, is converted into gas, it decomposes, and at about 180 deg. C. its vapour entirely consists of molecules of the composition NO2; while at temperatures between this and 0 deg. 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. Hitherto 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.