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    "source_title": "Encyclopaedia Britannica (1911)",
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    "chunk_id": "1911:chemical action:eda0ed02eaf6",
    "title": "CHEMICAL ACTION",
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    "verified_text": "chemical action, the term given to any process in which change in chemical composition occurs. such processes may be set up by the application of some form of energy (heat, light, electricity, &c.) to a substance, or by the mixing of two or more substances together. if two or more substances be mixed one of three things may occur. first, the particles may be mechanically intermingled, the degree of association being dependent upon the fineness of the particles, &c. secondly, the substances may intermolecularly penetrate, as in the case of gas-mixtures and solutions. or thirdly they may react chemically. the question whether, in any given case, we have to deal with a physical mixture or a chemical compound is often decided by the occurrence of very striking phenomena. to take a simple example:--oxygen and hydrogen are two gases which may be mixed in all proportions at ordinary temperatures, and it is easy to show that the properties of the products are simply those of mixtures of the two free gases. if, however, an electric spark be passed through the mixtures, powerful chemical union ensues, with its concomitants, great evolution of heat and consequent rise of temperature, and a compound, water, is formed which presents physical and chemical properties entirely different from those of its constituents. in general, powerful chemical forces give rise to the evolution of large quantities of heat, and the properties of the resulting substance differ vastly more from those of its components than is the case with simple mixtures. this constitutes a valuable criterion as to whether mere mixture is involved on the one hand, or strong chemical union on the other. when, however, the chemical forces are weak and the reaction, being incomplete, leads to a state of chemical equilibrium, in which all the reacting substances are present side by side, this criterion vanishes. for example, the question whether a salt combines with water molecules when dissolved in water cannot be said even yet to be fully settled, and, although there can be no doubt that solution is, in many cases, attended by chemical processes, still we possess as yet no means of deciding, with certainty, how many molecules of water have bound themselves to a single molecule of the dissolved substance (_solute_). on the other hand, we possess exact methods of testing whether gases or solutes in dilute solution react one with another and of determining the equilibrium state which is attained. for if one solute react with another on adding the latter to its solution, then corresponding to the decrease of its concentration there must also be a decrease of vapour pressure, and of solubility in other solvents; further, in the case of a mixture of gases, the concentration of each single constituent follows from its solubility in some suitable solvent. we thus obtain the answer to the question: whether the concentration of a certain constituent has decreased during mixing, i.e. whether it has reacted chemically. when a compound can be obtained in a pure state, analysis affords us an important criterion of its chemical nature, for unlike mixtures, the compositions of which are always variable within wider or narrower limits, chemical compounds present definite and characteristic mass-relations, which find full expression in the atomic theory propounded by dalton (see atom). according to this theory a mixture is the result of the mutual interpenetration of the molecules of substances, which remain unchanged as such, whilst chemical union involves changes more deeply seated, inasmuch as new molecular species appear. these new substances, if well-defined chemical compounds, have a perfectly definite composition and contain a definite, generally small, number of elementary atoms, and therefore the law of constant proportions follows at once, and the fact that only an integral number of atoms of any element may enter into the composition of any molecule determines the law of multiple proportions. nature of chemical forces. these considerations bring us face to face with the task of more closely investigating the nature of chemical forces, in other words, of answering the question: what forces guide the atoms in the formation of a new molecular species? this problem is still far from being completely answered, so that a few general remarks must suffice here. it is remarkable that among the most stable chemical compounds, we find combinations of atoms of one and the same element. thus, the stability of the di-atomic molecule n2 is so great, that no trace of dissociation has yet been proved even at the highest temperatures, and as the constituent atoms of the molecule n2 must be regarded as absolutely identical, it is clear that \"polar\" forces cannot be the cause of all chemical action. on the other hand, especially powerful affinities are also at work when so-called electro-positive and electro-negative elements react. the forces which here come into play appear to be considerably greater than those just mentioned; for instance, potassium fluoride is perhaps the most stable of all known compounds. it is also to be noticed that the combinations of the electro-negative elements (metalloids) with one another exhibit a metalloid character, and also we find, in the mutual combinations of metals, all the characteristics of the metallic state; but in the formation of a _salt_ from a metal and a metalloid we have an entirely new substance, quite different from its components; and at the same time, the product is seen to be an electrolyte, i.e. to have the power of splitting up into a positively and a negatively charged constituent when dissolved in some solvent. these considerations lead to the conviction that forces of a \"polar\" origin play an important part here, and indeed we may make the general surmise that in the act of chemical combination forces of both a non-polar and polar nature play a part, and that the latter are in all probability identical with the electric forces. it now remains to be asked--what are the laws which govern the action of these forces? this question is of fundamental importance, since it leads directly to those laws which regulate the chemical process. besides the already mentioned fundamental law of chemical combination, that of constant and multiple proportions, there is the law of chemical mass-action, discovered by guldberg and waage in 1867, which we will now develop from a kinetic standpoint. _kinetic basis of the law of chemical mass-action._--we will assume that the molecular species a1, a2, ... a'1, a'2, ... are present in a homogeneous system, where they can react on each other only according to the scheme a1 + a2 + ... <--> a'1 + a'2 + ...; this is a special case of the general equation n1a1 + n2a2 + ... <--> n'1a'1 + n'2a'2 + ..., in which only one molecule of each substance takes part in the reaction. the reacting substances may be either gaseous or form a liquid mixture, or be dissolved in some selected solvent; but in each case we may state the following considerations regarding the course of the reaction. for a transformation to take place from left to right in the sense of the reaction equation, all the molecules a1, a2, ... must clearly collide at one point; otherwise no reaction is possible, since we shall not consider side-reactions. such a collision need not of course bring about that transposition of the atoms of the single molecules which constitutes the above reaction. much rather must it be of such a kind as is favourable to that loosening of the bonds that bind the atoms in the separate molecules, which must precede this transposition. of a large number of such collisions, therefore, only a certain smaller number will involve a transposition from left to right in the sense of the equation. but this number will be the same under the same external conditions, and the greater the more numerous the collisions; in fact a direct ratio must exist between the two. bearing in mind now, that the number of collisions must be proportional to each of the concentrations of the bodies a1, a2, ..., and therefore, on the whole, to the product of all these concentrations, we arrive at the conclusion that the velocity v of the transposition from left to right in the sense of the reaction equation is v = kc1c2 ..., in which c1, c2, ... represent the spatial concentrations, i.e. the number of gram-molecules of the substances a1,",
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