Eight Lectures on Theoretical Physics. Max PlanckЧитать онлайн книгу.
the technical problem of perpetual motion, so again a technical problem, namely, that of the steam engine, led to the differentiation between reversible and irreversible processes. Long ago Sadi Carnot recognized, although he utilized an incorrect conception of the nature of heat, that irreversible processes are less economical than reversible, or that in an irreversible process a certain opportunity to derive mechanical work from heat is lost. What then could have been simpler than the thought of making, quite in general, the measure of the irreversibility of a process the quantity of mechanical work which is unavoidably lost in the process. For a reversible process then, the unavoidably lost work is naturally to be set equal to zero. This view, in accordance with which the import of the second law consists in a dissipation of useful energy, has in fact, in certain special cases, e. g., in isothermal processes, proved itself useful. It has persisted, therefore, in certain of its aspects up to the present day; but for the general case, however, it has shown itself as fruitless and, in fact, misleading. The reason for this lies in the fact that the question concerning the lost work in a given irreversible process is by no means to be answered in a determinate manner, so long as nothing further is specified with regard to the source of energy from which the work considered shall be obtained.
An example will make this clear. Heat conduction is an irreversible process, or as Clausius expresses it: Heat cannot without compensation pass from a colder to a warmer body. What now is the work which in accordance with definition is lost when the quantity of heat passes through direct conduction from a warmer body at the temperature to a colder body, at the temperature ? In order to answer this question, we make use of the heat transfer involved in carrying out a reversible Carnot cyclical process between the two bodies employed as heat reservoirs. In this process a certain amount of work would be obtained, and it is just the amount sought, since it is that which would be lost in the direct passage by conduction; but this has no definite value so long as we do not know whence the work originates, whether, e. g., in the warmer body or in the colder body, or from somewhere else. Let one reflect that the heat given up by the warmer body in the reversible process is certainly not equal to the heat absorbed by the colder body, because a certain amount of heat is transformed into work, and that we can identify, with exactly the same right, the quantity of heat transferred by the direct process of conduction with that which in the cyclical process is given up by the warmer body, or with that absorbed by the colder body. As one does the former or the latter, he accordingly obtains for the quantity of lost work in the process of conduction:
We see, therefore, that the proposed method of expressing mathematically the irreversibility of a process does not in general effect its object, and at the same time we recognize the peculiar reason which prevents its doing so. The statement of the question is too anthropomorphic. It is primarily too much concerned with the needs of mankind, in that it refers directly to the acquirement of useful work. If one require from nature a determinate answer, he must take a more general point of view, more disinterested, less economic. We shall now seek to do this.
Let us consider any typical process occurring in nature. This will carry all bodies concerned in it from a determinate initial state, which I designate as state , into a determinate final state . The process is either reversible or irreversible. A third possibility is excluded. But whether it is reversible or irreversible depends solely upon the nature of the two states and , and not at all upon the way in which the process has been carried out; for we are only concerned with the answer to the question as to whether or not, when the state is once reached, a complete return to in any conceivable manner may be accomplished. If now, the complete return from to is not possible, and the process therefore irreversible, it is obvious that the state may be distinguished in nature through a certain property from state . Several years ago I ventured to express this as follows: that nature possesses a greater “preference” for state than for state . In accordance with this mode of expression, all those processes of nature are impossible for whose final state nature possesses a smaller preference than for the original state. Reversible processes constitute a limiting case; for such, nature possesses an equal preference for the initial and for the final state, and the passage between them takes place as well in one direction as the other.
We have now to seek a physical quantity whose magnitude shall serve as a general measure of the preference of nature for a given state. This quantity must be one which is directly determined by the state of the system considered, without reference to the previous history of the system, as is the case with the energy, with the volume, and with other properties of the system. It should possess the peculiarity of increasing in all irreversible processes and of remaining unchanged in all reversible processes, and the amount of change which it experiences in a process would furnish a general measure for the irreversibility of the process.
R. Clausius actually found this quantity and called it “entropy.” Every system of bodies possesses in each of its states a definite entropy, and this entropy expresses the preference of nature for the state in question. It can, in all the processes which take place within the system, only increase and never decrease. If it be desired to consider a process in which external actions upon the system are present, it is necessary to consider those bodies in which these actions originate as constituting part of the system; then the law as stated in the above form is valid. In accordance with it, the entropy of a system of bodies is simply equal to the sum of the entropies of the individual bodies, and the entropy of a single body is, in accordance with Clausius, found by the aid of a certain reversible process. Conduction of heat to a body increases its entropy, and, in fact, by an amount equal to the ratio of the quantity of heat given the body to its temperature. Simple compression, on the other hand, does not change the entropy.
Returning to the example mentioned above, in which the quantity of heat is conducted from a warmer body at the temperature to a colder body at the temperature , in accordance with what precedes, the entropy of the warmer body decreases in this process, while, on the other hand, that of the colder increases, and the sum of both changes, that is, the change of the total entropy of both bodies, is:
This positive quantity furnishes, in a manner free from all arbitrary assumptions, the measure of the irreversibility of the process of heat conduction. Such examples may be cited indefinitely. Every chemical process furnishes an increase of entropy.
We shall here consider only the most general case treated by Clausius: an arbitrary reversible or irreversible cyclical process, carried out with any physico-chemical arrangement, utilizing an arbitrary number of heat reservoirs. Since the arrangement at the conclusion of the cyclical process is the same as that at the beginning, the final state of the process is to be distinguished from the initial state solely through the different heat content of the heat reservoirs, and in that a certain amount of mechanical work has been furnished or consumed. Let be the heat given up in the course of the process by a heat reservoir at the temperature , and let be the total work yielded (consisting, e. g., in the raising of weights); then, in accordance with the first law of thermodynamics:
In accordance with the second law, the sum of the changes in entropy of all the heat reservoirs is positive, or zero. It follows, therefore, since the entropy of a reservoir is decreased by the amount through the loss of heat that:
This is the well-known inequality of Clausius.
In an isothermal cyclical process, is the same for all reservoirs. Therefore:
That is: in an isothermal cyclical process, heat is produced and work is consumed. In the limiting case, a reversible isothermal cyclical process, the sign of equality holds, and therefore the work consumed is zero, and also the heat produced. This law plays a leading rôle in the application of thermodynamics to physical chemistry.
The second law of thermodynamics including all of its consequences has thus led to the principle of increase of entropy. You will now readily understand, having regard to the questions mentioned above, why I express it as my opinion that in the theoretical physics of the future the first and most important differentiation of all physical processes will be into reversible and irreversible processes.
In fact, all reversible processes, whether they take place in material bodies, in the ether, or in both together, show a much greater similarity among themselves than to any irreversible process. In the differential equations of reversible processes the time differential enters only as an even