Chapter III: Principles (2)

But the most indisputable triumph of this thermodynamic statics is the discovery of the laws which regulate the changes of physical state or of chemical constitution. J.W. Gibbs was the author of this immense progress. His memoir, now celebrated, on "the equilibrium of heterogeneous substances," concealed in 1876 in a review at that time of limited circulation, and rather heavy to read, seemed only to contain algebraic theorems applicable with difficulty to reality. It is known that Helmholtz independently succeeded, a few years later, in introducing thermodynamics into the domain of chemistry by his conception of the division of energy into free and into bound energy: the first, capable of undergoing all transformations, and particularly of transforming itself into external action; the second, on the other hand, bound, and only manifesting itself by giving out heat. When we measure chemical energy, we ordinarily let it fall wholly into the calorific form; but, in reality, it itself includes both parts, and it is the variation of the free energy and not that of the total energy measured by the integral disengagement of heat, the sign of which determines the direction in which the reactions are effected.

But if the principle thus enunciated by Helmholtz as a consequence of the laws of thermodynamics is at bottom identical with that discovered by Gibbs, it is more difficult of application and is presented under a more mysterious aspect. It was not until M. Van der Waals exhumed the memoir of Gibbs, when numerous physicists or chemists, most of them Dutch--Professor Van t'Hoff, Bakhius Roozeboom, and others--utilized the rules set forth in this memoir for the discussion of the most complicated chemical reactions, that the extent of the new laws was fully understood.

The chief rule of Gibbs is the one so celebrated at the present day under the name of the Phase Law. We know that by phases are designated the homogeneous substances into which a system is divided; thus carbonate of lime, lime, and carbonic acid gas are the three phases of a system which comprises Iceland spar partially dissociated into lime and carbonic acid gas. The number of phases added to the number of independent components--that is to say, bodies whose mass is left arbitrary by the chemical formulas of the substances entering into the reaction--fixes the general form of the law of equilibrium of the system; that is to say, the number of quantities which, by their variations (temperature and pressure), would be of a nature to modify its equilibrium by modifying the constitution of the phases.

Several authors, M. Raveau in particular, have indeed given very simple demonstrations of this law which are not based on thermodynamics; but thermodynamics, which led to its discovery, continues to give it its true scope. Moreover, it would not suffice merely to determine quantitatively those laws of which it makes known the general form. We must, if we wish to penetrate deeper into details, particularize the hypothesis, and admit, for instance, with Gibbs that we are dealing with perfect gases; while, thanks to thermodynamics, we can constitute a complete theory of dissociation which leads to formulas in complete accord with the numerical results of the experiment. We can thus follow closely all questions concerning the displacements of the equilibrium, and find a relation of the first importance between the masses of the bodies which react in order to constitute a system in equilibrium.

The statics thus constructed constitutes at the present day an important edifice to be henceforth classed amongst historical monuments. Some theorists even wish to go a step beyond. They have attempted to begin by the same means a more complete study of those systems whose state changes from one moment to another. This is, moreover, a study which is necessary to complete satisfactorily the study of equilibrium itself; for without it grave doubts would exist as to the conditions of stability, and it alone can give their true meaning to questions relating to displacements of equilibrium.

The problems with which we are thus confronted are singularly difficult. M. Duhem has given us many excellent examples of the fecundity of the method; but if thermodynamic statics may be considered definitely founded, it cannot be said that the general dynamics of systems, considered as the study of thermal movements and variations, are yet as solidly established.

Sec. 5. ATOMISM

It may appear singularly paradoxical that, in a chapter devoted to general views on the principles of physics, a few words should be introduced on the atomic theories of matter.

Very often, in fact, what is called the physics of principles is set in opposition to the hypotheses on the constitution of matter, particularly to atomic theories. I have already said that, abandoning the investigation of the unfathomable mystery of the constitution of the Universe, some physicists think they may find, in certain general principles, sufficient guides to conduct them across the physical world. But I have also said, in examining the history of those principles, that if they are to-day considered experimental truths, independent of all theories relating to matter, they have, in fact, nearly all been discovered by scholars who relied on molecular hypotheses: and the question suggests itself whether this is mere chance, or whether this chance may not be ordained by higher reasons.

In a very profound work which appeared a few years ago, entitled _Essai critique sur l'hypothese des atomes_, M. Hannequin, a philosopher who is also an erudite scholar, examined the part taken by atomism in the history of science. He notes that atomism and science were born, in Greece, of the same problem, and that in modern times the revival of the one was closely connected with that of the other. He shows, too, by very close analysis, that the atomic hypothesis is essential to the optics of Fresnel and of Cauchy; that it penetrates into the study of heat; and that, in its general features, it presided at the birth of modern chemistry and is linked with all its progress. He concludes that it is, in a manner, the soul of our knowledge of Nature, and that contemporary theories are on this point in accord with history: for these theories consecrate the preponderance of this hypothesis in the domain of science.

If M. Hannequin had not been prematurely cut off in the full expansion of his vigorous talent, he might have added another chapter to his excellent book. He would have witnessed a prodigious budding of atomistic ideas, accompanied, it is true, by wide modifications in the manner in which the atom is to be regarded, since the most recent theories make material atoms into centres constituted of atoms of electricity. On the other hand, he would have found in the bursting forth of these new doctrines one more proof in support of his idea that science is indissolubly bound to atomism.

From the philosophical point of view, M. Hannequin, examining the reasons which may have called these links into being, arrives at the idea that they necessarily proceed from the constitution of our knowledge, or, perhaps, from that of Nature itself. Moreover, this origin, double in appearance, is single at bottom. Our minds could not, in fact, detach and come out of themselves to grasp reality and the absolute in Nature. According to the idea of Descartes, it is the destiny of our minds only to take hold of and to understand that which proceeds from them.

Thus atomism, which is, perhaps, only an appearance containing even some contradictions, is yet a well-founded appearance, since it conforms to the laws of our minds; and this hypothesis is, in a way, necessary.

We may dispute the conclusions of M. Hannequin, but no one will refuse to recognise, as he does, that atomic theories occupy a preponderating part in the doctrines of physics; and the position which they have thus conquered gives them, in a way, the right of saying that they rest on a real principle. It is in order to recognise this right that several physicists--M. Langevin, for example--ask that atoms be promoted from the rank of hypotheses to that of principles. By this they mean that the atomistic ideas forced upon us by an almost obligatory induction based on very exact experiments, enable us to co-ordinate a considerable amount of facts, to construct a very general synthesis, and to foresee a great number of phenomena.

It is of moment, moreover, to thoroughly understand that atomism does not necessarily set up the hypothesis of centres of attraction acting at a distance, and it must not be confused with molecular physics, which has, on the other hand, undergone very serious checks. The molecular physics greatly in favour some fifty years ago leads to such complex representations and to solutions often so undetermined, that the most courageous are wearied with upholding it and it has fallen into some discredit. It rested on the fundamental principles of mechanics applied to molecular actions; and that was, no doubt, an extension legitimate enough, since mechanics is itself only an experimental science, and its principles, established for the movements of matter taken as a whole, should not be applied outside the domain which belongs to them. Atomism, in fact, tends more and more, in modern theories, to imitate the principle of the conservation of energy or that of entropy, to disengage itself from the artificial bonds which attached it to mechanics, and to put itself forward as an independent principle.

Atomistic ideas also have undergone evolution, and this slow evolution has been considerably quickened under the influence of modern discoveries. These reach back to the most remote antiquity, and to follow their development we should have to write the history of human thought which they have always accompanied since the time of Leucippus, Democritus, Epicurus, and Lucretius. The first observers who noticed that the volume of a body could be diminished by compression or cold, or augmented by heat, and who saw a soluble solid body mix completely with the water which dissolved it, must have been compelled to suppose that matter was not dispersed continuously throughout the space it seemed to occupy. They were thus brought to consider it discontinuous, and to admit that a substance having the same composition and the same properties in all its parts--in a word, perfectly homogeneous--ceases to present this homogeneity when considered within a sufficiently small volume.

Modern experimenters have succeeded by direct experiments in placing in evidence this heterogeneous character of matter when taken in small mass. Thus, for example, the superficial tension, which is constant for the same liquid at a given temperature, no longer has the same value when the thickness of the layer of liquid becomes extremely small. Newton noticed even in his time that a dark zone is seen to form on a soap bubble at the moment when it becomes so thin that it must burst. Professor Reinold and Sir Arthur Ruecker have shown that this zone is no longer exactly spherical; and from this we must conclude that the superficial tension, constant for all thicknesses above a certain limit, commences to vary when the thickness falls below a critical value, which these authors estimate, on optical grounds, at about fifty millionths of a millimetre.

From experiments on capillarity, Prof. Quincke has obtained similar results with regard to layers of solids. But it is not only capillary properties which allow this characteristic to be revealed. All the properties of a body are modified when taken in small mass; M. Meslin proves this in a very ingenious way as regards optical properties, and Mr Vincent in respect of electric conductivity. M. Houllevigue, who, in a chapter of his excellent work, _Du Laboratoire a l'Usine_, has very clearly set forth the most interesting considerations on atomic hypotheses, has recently demonstrated that copper and silver cease to combine with iodine as soon as they are present in a thickness of less than thirty millionths of a millimetre. It is this same dimension likewise that is possessed, according to M. Wiener, by the smallest thicknesses it is possible to deposit on glass. These layers are so thin that they cannot be perceived, but their presence is revealed by a change in the properties of the light reflected by them.

Thus, below fifty to thirty millionths of a millimetre the properties of matter depend on its thickness. There are then, no doubt, only a few molecules to be met with, and it may be concluded, in consequence, that the discontinuous elements of bodies--that is, the molecules-- have linear dimensions of the order of magnitude of the millionth of a millimetre. Considerations regarding more complex phenomena, for instance the phenomena of electricity by contact, and also the kinetic theory of gases, bring us to the same conclusion.

The idea of the discontinuity of matter forces itself upon us for many other reasons. All modern chemistry is founded on this principle; and laws like the law of multiple proportions, introduce an evident discontinuity to which we find analogies in the law of electrolysis. The elements of bodies we are thus brought to regard might, as regards solids at all events, be considered as immobile; but this immobility could not explain the phenomena of heat, and, as it is entirely inadmissible for gases, it seems very improbable it can absolutely occur in any state. We are thus led to suppose that these elements are animated by very complicated movements, each one proceeding in closed trajectories in which the least variations of temperature or pressure cause modifications.

The atomistic hypothesis shows itself remarkably fecund in the study of phenomena produced in gases, and here the mutual independence of the particles renders the question relatively more simple and, perhaps, allows the principles of mechanics to be more certainly extended to the movements of molecules.

The kinetic theory of gases can point to unquestioned successes; and the idea of Daniel Bernouilli, who, as early as 1738, considered a gaseous mass to be formed of a considerable number of molecules animated by rapid movements of translation, has been put into a form precise enough for mathematical analysis, and we have thus found ourselves in a position to construct a really solid foundation. It will be at once conceived, on this hypothesis, that pressure is the resultant of the shocks of the molecules against the walls of the containing vessel, and we at once come to the demonstration that the law of Mariotte is a natural consequence of this origin of pressure; since, if the volume occupied by a certain number of molecules is doubled, the number of shocks per second on each square centimetre of the walls becomes half as much. But if we attempt to carry this further, we find ourselves in presence of a serious difficulty. It is impossible to mentally follow every one of the many individual molecules which compose even a very limited mass of gas. The path followed by this molecule may be every instant modified by the chance of running against another, or by a shock which may make it rebound in another direction.

The difficulty would be insoluble if chance had not laws of its own. It was Maxwell who first thought of introducing into the kinetic theory the calculation of probabilities. Willard Gibbs and Boltzmann later on developed this idea, and have founded a statistical method which does not, perhaps, give absolute certainty, but which is certainly most interesting and curious. Molecules are grouped in such a way that those belonging to the same group may be considered as having the same state of movement; then an examination is made of the number of molecules in each group, and what are the changes in this number from one moment to another. It is thus often possible to determine the part which the different groups have in the total properties of the system and in the phenomena which may occur.

Such a method, analogous to the one employed by statisticians for following the social phenomena in a population, is all the more legitimate the greater the number of individuals counted in the averages; now, the number of molecules contained in a limited space-- for example, in a centimetre cube taken in normal conditions--is such that no population could ever attain so high a figure. All considerations, those we have indicated as well as others which might be invoked (for example, the recent researches of M. Spring on the limit of visibility of fluorescence), give this result:--that there are, in this space, some twenty thousand millions of molecules. Each of these must receive in the space of a millimetre about ten thousand shocks, and be ten thousand times thrust out of its course. The free path of a molecule is then very small, but it can be singularly augmented by diminishing the number of them. Tait and Dewar have calculated that, in a good modern vacuum, the length of the free path of the remaining molecules not taken away by the air-pump easily reaches a few centimetres.

By developing this theory, we come to consider that, for a given temperature, every molecule (and even every individual particle, atom, or ion) which takes part in the movement has, on the average, the same kinetic energy in every body, and that this energy is proportional to the absolute temperature; so that it is represented by this temperature multiplied by a constant quantity which is a universal constant.

This result is not an hypothesis but a very great probability. This probability increases when it is noted that the same value for the constant is met with in the study of very varied phenomena; for example, in certain theories on radiation. Knowing the mass and energy of a molecule, it is easy to calculate its speed; and we find that the average speed is about 400 metres per second for carbonic anhydride, 500 for nitrogen, and 1850 for hydrogen at 0 deg. C. and at ordinary pressure. I shall have occasion, later on, to speak of much more considerable speeds than these as animating other particles.

The kinetic theory has permitted the diffusion of gases to be explained, and the divers circumstances of the phenomenon to be calculated. It has allowed us to show, as M. Brillouin has done, that the coefficient of diffusion of two gases does not depend on the proportion of the gases in the mixture; it gives a very striking image of the phenomena of viscosity and conductivity; and it leads us to think that the coefficients of friction and of conductivity are independent of the density; while all these previsions have been verified by experiment. It has also invaded optics; and by relying on the principle of Doppler, Professor Michelson has succeeded in obtaining from it an explanation of the length presented by the spectral rays of even the most rarefied gases.

But however interesting are these results, they would not have sufficed to overcome the repugnance of certain physicists for speculations which, an imposing mathematical baggage notwithstanding, seemed to them too hypothetical. The theory, moreover, stopped at the molecule, and appeared to suggest no idea which could lead to the discovery of the key to the phenomena where molecules exercise a mutual influence on each other. The kinetic hypothesis, therefore, remained in some disfavour with a great number of persons, particularly in France, until the last few years, when all the recent discoveries of the conductivity of gases and of the new radiations came to procure for it a new and luxuriant efflorescence. It may be said that the atomistic synthesis, but yesterday so decried, is to-day triumphant.

The elements which enter into the earlier kinetic theory, and which, to avoid confusion, should be always designated by the name of molecules, were not, truth to say, in the eyes of the chemists, the final term of the divisibility of matter. It is well known that, to them, except in certain particular bodies like the vapour of mercury and argon, the molecule comprises several atoms, and that, in compound bodies, the number of these atoms may even be fairly considerable. But physicists rarely needed to have recourse to the consideration of these atoms. They spoke of them to explain certain particularities of the propagation of sound, and to enunciate laws relating to specific heats; but, in general, they stopped at the consideration of the molecule.

The present theories carry the division much further. I shall not dwell now on these theories, since, in order to thoroughly understand them, many other facts must be examined. But to avoid all confusion, it remains understood that, contrary, no doubt, to etymology, but in conformity with present custom, I shall continue in what follows to call atoms those particles of matter which have till now been spoken of; these atoms being themselves, according to modern views, singularly complex edifices formed of elements, of which we shall have occasion to indicate the nature later.