In the case, of the substances investigated by Herr Lenard, PEz is always significantly greater than Rβν, since the potential difference, which the cathode rays must traverse in order to produce visible light, amounts in some cases to hundreds and in others to thousands of volts.aa It is therefore to be assumed that the kinetic energy of an electron goes into the production of many light energy quanta.
9. CONCERNING THE IONIZATION OF GASES BY ULTRAVIOLET LIGHT SOLID BODIES
We shall have to assume that, the ionization of a gas by ultraviolet light, an individual light energy quantum is used for the ionization of an individual gas molecule. From this is follows immediately that the work of ionization (i.e., the work theoretically needed for ionization) of a molecule cannot be greater than the energy of an absorbed light quantum capable of producing this effect. If one denotes by J the (theoretical) work of ionization per gram equivalent, then it follows that:Rβν ≥ J.
According to Lenard’s measurements, however, the largest effective wavelength for air is approximately 1.9 × 10−5 cm: therefore:Rβ ν = 6.4 · 1012 erg ≥ J.
An upper limit for the work of ionization can also be obtained from the ionization potentials of rarefied gases according to J. Starkab the smallest observed ionization potentials for air (at platinum anodes) is about 10 V.ac One therefore obtains 9.6 × 1012 as an upper limit for J, which is nearly equal to the value found above.
There is another consequence the experimental testing of which seems to me to be of great importance. If every absorbed light energy quantum ionizes a molecule, the following relation must obtain between the quantity of absorbed light L and the number of gram molecules of ionized gas j:j = L/Rβν.
If our conception is correct, this relationship must be valid for all gases which (at the relevant frequency) show no appreciable absorption without ionization.
Bern, 17 March 1905
Received 18 March 1905
“THE ATOMIC THEORY OF MATTER”
BY
MAX PLANCK
The problem with which we shall be occupied in the present lecture is that of a closer investigation of the atomic theory of matter. It is, however, not my intention to introduce this theory with nothing further, and to set it up as something apart and disconnected with other physical theories, but I intend above all to bring out the peculiar significance of the atomic theory as related to the present general system of theoretical physics; for in this way only will it be possible to regard the whole system as one containing within itself the essential compact unity, and thereby to realize the principal object of these lectures.
Consequently it is self evident that we must rely on that sort of treatment which we have recognized in last week’s lecture as fundamental. That is, the division of all physical processes into reversible and irreversible processes. Furthermore, we shall be convinced that the accomplishment of this division is only possible through the atomic theory of matter, or, in other words, that irreversibility leads of necessity to atomistics.
I have already referred at the close of the first lecture to the fact that in pure thermodynamics, which knows nothing of an atomic structure and which regards all substances as absolutely continuous, the difference between reversible and irreversible processes can only be defined in one way, which a priori carries a provisional character and does not withstand penetrating analysis. This appears immediately evident when one reflects that the purely thermodynamic definition of irreversibility which proceeds from the impossibility of the realization of certain changes in nature, as, e.g., the transformation of heat into work without compensation, has at the outset assumed a definite limit to man’s mental capacity, while, however, such a limit is not indicated in reality. On the contrary: mankind is making every endeavor to press beyond the present boundaries of its capacity, and we hope that later on many things will be attained which, perhaps, many regard at present as impossible of accomplishment. Can it not happen then that a process, which up to the present has been regarded as irreversible, may be proved, through a new discovery or invention, to be reversible? In this case the whole structure of the second law would undeniably collapse, for the irreversibility of a single process conditions that of all the others.
Published in Eight Lectures on Theoretical Physics (Mineola: Dover Publications 1998). First published in Eight Lectures on Theoretical Physics, Delivered at Columbia University in 1909, as Publication Number 3 of the Ernest Kempton Adams Fund For Physical Research.
It is evident then that the only means to assure to the second law real meaning consists in this, that the idea of irreversibility be made independent of any relationship to man and especially of all technical relations.
Now the idea of irreversibility harks back to the idea of entropy; for a process is irreversible when it is connected with an increase of entropy. The problem is hereby referred back to a proper improvement of the definition of entropy. In accordance with the original definition of Clausius, the entropy is measured by means of a certain reversible process, and the weakness of this definition rests upon the fact that many such reversible processes, strictly speaking all, are not capable of being carried out in practice. With some reason it may be objected that we have here to do, not with an actual process and an actual physicist, but only with ideal processes, so-called thought experiments, and with an ideal physicist who operates with all the experimental methods with absolute accuracy. But at this point the difficulty is encountered: How far do the physicist’s ideal measurements of this sort suffice? It may be understood, by passing to the limit, that a gas is compressed by a pressure which is equal to the pressure of the gas, and is heated by a heat reservoir which possesses the same temperature as the gas, but, for example, that a saturated vapor shall be transformed through isothermal compression in a reversible manner to a liquid without at any time a part of the vapor being condensed, as in certain thermodynamic considerations is supposed, must certainly appear doubtful. Still more striking, however, is the liberty as regards thought experiments, which in physical chemistry is granted the theorist. With his semi-permeable membranes, which in reality are only realizable under certain special conditions and then only with a certain approximation, he separates in a reversible manner, not only all possible varieties of molecules, whether or not they are in stable or unstable conditions, but he also separates the oppositely charged ions from one another and from the undissociated molecules, and he is disturbed, neither by the enormous electrostatic forces which resist such a separation, nor by the circumstance that in reality, from the beginning of the separation, the molecules become in part dissociated while the ions in part again combine. But such ideal processes are necessary throughout in order to make possible the comparison of the entropy of the undissociated molecules with the entropy of the dissociated molecules; for the law of thermodynamic equilibrium does not permit in general of derivation in any other way, in case one wishes to retain pure thermodynamics as a basis. It must be considered remarkable that all these ingenious thought processes have so well found confirmation of their results in experience, as is shown by the examples considered by us in the last lecture.
If now, on the other hand, one reflects that in all these results every reference to the possibility of actually carrying out each ideal process has disappeared—there are certainly left relations between directly measurable quantities only, such as temperature, heat effect, concentration, etc.—the presumption forces itself upon one that perhaps the introduction as above of such ideal processes is at bottom a round-about method, and that the peculiar import of the principle of increase of entropy with all its consequences can be evolved from the original idea of irreversibility or, just as well, from the impossibility of perpetual motion of the second kind, just as the principle of conservation of energy has been evolved from the law of impossibility of perpetual motion of the first kind.
This step: to have completed the emancipation of the entropy idea from the experimental art of man and the elevation of the second law thereb
y to a real principle, was the scientific life’s work of Ludwig Boltzmann. Briefly stated, it consisted in general of referring back the idea of entropy to the idea of probability. Thereby is also explained, at the same time, the significance of the above (p. 17) auxiliary term used by me; “preference” of nature for a definite state. Nature prefers the more probable states to the less probable, because in nature processes take place in the direction of greater probability. Heat goes from a body at higher temperature to a body at lower temperature because the state of equal temperature distribution is more probable than a state of unequal temperature distribution.
Through this conception the second law of thermodynamics is removed at one stroke from its isolated position, the mystery concerning the preference of nature vanishes, and the entropy principle reduces to a well understood law of the calculus of probability.
The enormous fruitfulness of so “objective” a definition of entropy for all domains of physics I shall seek to demonstrate in the following lectures. But today we have principally to do with the proof of its admissibility; for on closer consideration we shall immediately perceive that the new conception of entropy at once introduces a great number of questions, new requirements and difficult problems. The first requirement is the introduction of the atomic hypothesis into the system of physics. For, if one wishes to speak of the probability of a physical state, i.e., if he wishes to introduce the probability for a given state as a definite quantity into the calculation, this can only be brought about, as in cases of all probability calculations, by referring the state back to a variety of possibilities; i.e., by considering a finite number of a priori equally likely configurations (complexions) through each of which the state considered may be realized. The greater the number of complexions, the greater is the probability of the state. Thus, e.g., the probability of throwing a total of four with two ordinary six-sided dice is found through counting the complexions by which the throw with a total of four may be realized. Of these there are three complexions:
with the first die, 1, with the second die, 3,
with the first die, 2, with the second die, 2,
with the first die, 3, with the second die, 1.
On the other hand, the throw of two is only realized through a single complexion. Therefore, the probability of throwing a total of four is three times as great as the probability of throwing a total of two.
Now, in connection with the physical state under consideration, in order to be able to differentiate completely from one another the complexions realizing it, and to associate it with a definite reckonable number, there is obviously no other means than to regard it as made up of numerous discrete homogeneous elements—for in perfectly continuous systems there exist no reckonable elements—and hereby the atomistic view is made a fundamental requirement. We have, therefore, to regard all bodies in nature, in so far as they possess an entropy, as constituted of atoms, and we therefore arrive in physics at the same conception of matter as that which obtained in chemistry for so long previously.
But we can immediately go a step further yet. The conclusions reached hold, not only for thermodynamics of material bodies, but also possess complete validity for the processes of heat radiation, which are thus referred back to the second law of thermodynamics. That radiant heat also possesses an entropy follows from the fact that a body which emits radiation into a surrounding diathermanous medium experiences a loss of heat and, therefore, a decrease of entropy. Since the total entropy of a physical system can only increase, it follows that one part of the entropy of the whole system, consisting of the body and the diathermanous medium, must be contained in the radiated heat. If the entropy of the radiant heat is to be referred back to the notion of probability, we are forced, in a similar way as above, to the conclusion that for radiant heat the atomic conception possesses a definite meaning. But, since radiant heat is not directly connected with matter, it follows that this atomistic conception relates, not to matter, but only to energy, and hence, that in heat radiation certain energy elements play an essential rôle. Even though this conclusion appears so singular and even though in many circles today vigorous objection is strongly urged against it, in the long run physical research will not be able to withhold its sanction from it, and the less, since it is confirmed by experience in quite a satisfactory manner. We shall return to this point in the lectures on heat radiation. I desire here only to mention that the novelty involved by the introduction of atomistic conceptions into the theory of heat radiation is by no means so revolutionary as, perhaps, might appear at the first glance. For there is, in my opinion at least, nothing which makes necessary the consideration of the heat processes in a complete vacuum as atomic, and it suffices to seek the atomistic features at the source of radiation, i.e., in those processes which have their play in the centres of emission and absorption of radiation. Then the Maxwellian electrodynamic differential equations can retain completely their validity for the vacuum, and, besides, the discrete elements of heat radiation are relegated exclusively to a domain which is still very mysterious and where there is still present plenty of room for all sorts of hypotheses.
Returning to more general considerations, the most important question comes up as to whether, with the introduction of atomistic conceptions and with the reference of entropy to probability, the content of the principle of increase of entropy is exhaustively comprehended, or whether still further physical hypotheses are required in order to secure the full import of that principle. If this important question had been settled at the time of the introduction of the atomic theory into thermodynamics, then the atomistic views would surely have been spared a large number of conceivable misunderstandings and justifiable attacks. For it turns out, in fact—and our further considerations will confirm this conclusion—that there has as yet nothing been done with atomistics which in itself requires much more than an essential generalization, in order to guarantee the validity of the second law.
We must first reflect that, in accordance with the central idea laid down in the first lecture (p. 7), the second law must possess validity as an objective physical law, independently of the individuality of the physicist. There is nothing to hinder us from imagining a physicist—we shall designate him a “microscopic” observer—whose senses are so sharpened that he is able to recognize each individual atom and to follow it in its motion. For this observer each atom moves exactly in accordance with the elementary laws which general dynamics lays down for it, and these laws allow, so far as we know, of an inverse performance of every process. Accordingly, here again the question is neither one of probability nor of entropy and its increase. Let us imagine, on the other hand, another observer, designated a “macroscopic” observer, who regards an ensemble of atoms as a homogeneous gas, say, and consequently applies the laws of thermodynamics to the mechanical and thermal processes within it. Then, for such an observer, in accordance with the second law, the process in general is an irreversible process. Would not now the first observer be justified in saying: “The reference of the entropy to probability has its origin in the fact that irreversible processes ought to be explained through reversible processes. At any rate, this procedure appears to me in the highest degree dubious. In any case, I declare each change of state which takes place in the ensemble of atoms designated a gas, as reversible, in opposition to the macroscopic observer.” There is not the slightest thing, so far as I know, that one can urge against the validity of these statements. But do we not thereby place ourselves in the painful position of the judge who declared in a trial the correctness of the position of each separately of two contending parties and then, when a third contends that only one of the parties could emerge from the process victorious, was obliged to declare him also correct? Fortunately we find ourselves in a more favorable position. We can certainly mediate between the two parties without its being necessary for one or the other to give up his principal point of view. For closer consideration shows that the whole controversy rests upon a misunderstand
ing—a new proof of how necessary it is before one begins a controversy to come to an understanding with his opponent concerning the subject of the quarrel. Certainly, a given change of state cannot be both reversible and irreversible. But the one observer connects a wholly different idea with the phrase “change of state” than the other. What is then, in general, a change of state? The state of a physical system cannot well be otherwise defined than as the aggregate of all those physical quantities, through whose instantaneous values the time changes of the quantities, with given boundary conditions, are uniquely determined. If we inquire now, in accordance with the import of this definition, of the two observers as to what they understand by the state of the collection of atoms or the gas considered, they will give quite different answers. The microscopic observer will mention those quantities which determine the position and the velocities of all the individual atoms. There are present in the simplest case, namely, that in which the atoms may be considered as material points, six times as many quantities as atoms, namely, for each atom the three coordinates and the three velocity components, and in the case of combined molecules, still more quantities. For him the state and the progress of a process is then first determined when all these various quantities are individually given. We shall designate the state defined in this way the “micro-state.” The macroscopic observer, on the other hand, requires fewer data. He will say that the state of the homogeneous gas considered by him is determined by the density, the visible velocity and the temperature at each point of the gas, and he will expect that, when these quantities are given, their time variations and, therefore, the progress of the process, to be completely determined in accordance with the two laws of thermo-dynamics, and therefore accompanied by an increase in entropy. In this connection he can call upon all the experience at his disposal, which will fully confirm his expectation. If we call this state the “macro-state,” it is clear that the two laws: “the micro-changes of state are reversible” and “the macro-changes of state are irreversible,” lie in wholly different domains and, at any rate, are not contradictory.
The Dreams That Stuff is Made of Page 4
