ENERGETICS. The most fundamental result attained by the progress of physical science in the 19th century was the definite enunciation and development of the doctrine of energy, which is now paramount both in mechanics and in thermodynamics. For a discussion of the elementary ideas underlying this conception see the separate heading Energy.
Ever since physical speculation began in the atomic theories of the Greeks, its main problem has been that of unravelling the nature of the underlying correlation which binds together the various natural agencies. But it is only in recent times that scientific investigation has definitely established that there is a quantitative relation of simple equivalence between them, whereby each is expressible in terms of heat or mechanical power; that there is a certain measurable quantity associated with each type of physical activity which is always numerically identical with a corresponding quantity belonging to the new type into which it is transformed, so that the energy, as it is called, is conserved in unaltered amount. The main obstacle in the way of an earlier recognition and development of this principle had been the doctrine of caloric, which was suggested by the principles and practice of calorimetry, and taught that heat is a substance that can be transferred from one body to another, but cannot be created or destroyed, though it may become latent. So long as this idea maintained itself, there was no possible compensation for the destruction of mechanical power by friction; it appeared that mechanical effect had there definitely been lost. The idea that heat is itself convertible into power, and is in fact energy of motion of the minute invisible parts of bodies, had been held by Newton and in a vaguer sense by Bacon, and indeed long before their time; but it dropped out of the ordinary creed of science in the following century. It held a place, like many other anticipations of subsequent discovery, in the system of Natural Philosophy of Thomas Young (1804); and the discrepancies attending current explanations on the caloric theory were insisted on, about the same time, by Count Rumford and Sir H. Davy. But it was not till the actual experiments of Joule verified the same exact equivalence between heat produced and mechanical energy destroyed, by whatever process that was accomplished, that the idea of caloric had to be definitely abandoned. Some time previously R. Mayer, physician, of Heilbronn, had founded a weighty theoretical argument on the production of mechanical power in the animal system from the food consumed; he had, moreover, even calculated the value of a unit of heat, in terms of its equivalent in power, from the data afforded by Regnault's determinations of the specific heats of air at constant pressure and at constant volume, the former being the greater on Mayer's hypothesis (of which his calculation in fact constituted the verification) solely on account of the power required for the work of expansion of the gas against the surrounding constant pressure. About the same time Helmholtz, in his early memoir on the Conservation of Energy, constructed a cumulative argument by tracing the ramifications of the principle of conservation of energy throughout the whole range of physical science.
Mechanical and Thermal Energy. - The amount of energy, defined in this sense by convertibility with mechanical work, which is contained in a material system, must be a function of its physical state and chemical constitution and of its temperature. The change in this amount, arising from a given transformation in the system, is usually measured by degrading the energy that leaves the system into heat; for it is always possible to do this, while the conversion of heat back again into other forms of energy is impossible without assistance, taking the form of compensating degradation elsewhere. We may adopt the provisional view which is the basis of abstract physics, that all these other forms of energy are in their essence mechanical, that is, arise from the motion or strain of material or ethereal media; then their distinction from heat will lie in the fact that these motions or strains are simply co-ordinated, so that they can be traced and controlled or manipulated in detail, while the thermal energy subsists in irregular motions of the molecules or smallest portions of matter, which we cannot trace on account of the bluntness of our sensual perceptions, but can only measure as regards total amount.
Historical: Abstract Dynamics. - Even in the case of a purely mechanical system, capable only of a finite number of definite types of disturbance, the principle of the conservation of energy is very far from giving a complete account of its motions; it forms only one among the equations that are required to determine their course. In its application to the kinetics of invariable systems, after the time of Newton, the principle was emphasized as fundamental by Leibnitz, was then improved and generalized by the Bernoullis and by Euler, and was ultimately expressed in its widest form by Lagrange. It is recorded by Helmholtz that it was largely his acquaintance in early years with the works of those mathematical physicists of the previous century, who had formulated and generalized the principle as a help towards the theoretical dynamics of complex systems of masses, that started him on the track of extending the principle throughout the whole range of natural phenomena. On the other hand, the ascertained validity of this extension to new types of phenomena, such as those of electrodynamics, now forms a main foundation of our belief in a mechanical basis for these sciences.
In the hands of Lagrange the mathematical expression for the manner in which the energy is connected with the geometrical constitution of the material system became a sufficient basis for a complete knowledge of its dynamical phenomena. So far as statics was concerned, this doctrine took its rise as far back as Galileo, who recognized in the simpler cases that the work expended in the steady driving of a frictionless mechanical system is equal to its output. The expression of this fact was generalized in a brief statement by Newton in the Principia, and more in detail by the Bernoullis, until, in the analytical guise of the so-called principle of "virtual velocities" or virtual work, it finally became the basis of Lagrange's general formulation of dynamics. In its application to kinetics a purely physical principle, also indicated by Newton, but developed long after with masterly applications by d'Alembert, that the reactions of the infinitesimal parts of the system against the accelerations of their motions statically equilibrate the forces applied to the system as a whole, was required in order to form a sufficient basis, and one which Lagrange soon afterwards condensed into the single relation of Least Action. As a matter of history, however, the complete formulation of the subject of abstract dynamics actually arose (in 1758) from Lagrange's precise demonstration of the principle of Least Action for a particle, and its immediate extension, on the basis of his new Calculus of Variations, to a system of connected particles such as might be taken as a representation of any material system; but here too the same physical as distinct from mechanical considerations come into play as in d'Alembert's principle. (See Dynamics: Analytical.)
It is in the cases of systems whose state is changing so slowly that reactions arising from changing motions can be neglected, that the conditions are by far the simplest. In such systems, whether stationary or in a state of steady motion, the energy depends on the configuration alone, and its mathematical expression can be determined from measurement of the work required for a sufficient number of simple transformations; once it is thus found, all the statical relations of the system are implicitly determined along with it, and the results of all other transformations can be predicted. The general development of such relations is conveniently classed as a separate branch of physics under the name Energetics, first invented by W.J.M. Rankine; but the essential limitations of this method have not always been observed. As regards statical change, the complete specification of a mechanical system is involved in its geometrical configuration and the function expressing its mechanical energy in terms thereof. Systems which have statical energy-functions of the same analytical form behave in corresponding ways, and can serve as models or representations of one another.
Extension to Thermal and Chemical Systems. - This dominant position of the principle of energy, in ordinary statical problems, has in recent times been extended to transformations involving change of physical state or chemical constitution as well as change of geometrical configuration. In this wider field we cannot assert that mechanical (or available) energy is never lost, for it may be degraded into thermal energy; but we can use the principle that on the other hand it can never spontaneously increase. If this were not so, cyclic processes might theoretically be arranged which would continue to supply mechanical power so long as energy of any kind remained in the system; whereas the irregular and uncontrollable character of the molecular motions and strains which constitute thermal energy, in combination with the vast number of the molecules, must place an effectual bar on their unlimited co-ordination. To establish a doctrine of energetics that shall form a sufficient foundation for a theory of the trend of chemical and physical change, we have, therefore, to impart precision to this motion of available energy.
Carnot's Principle: Entropy. - The whole subject is involved in the new principle contributed to theoretical physics by Sadi Carnot in 1824, in which the far-reaching modern conception of cyclic processes was first scientifically developed. It was shown by Carnot, on the basis of certain axioms, whose theoretical foundations were subsequently corrected and strengthened by Clausius and Lord Kelvin, that a reversible mechanical process, working in a cycle by means of thermal transfers, which takes heat, say H1, into the material system at a given temperature T1, and delivers the part of it not utilized, say H2, at a lower given temperature T2, is more efficient, considered as a working engine, than any other such process, operating between the same two temperatures but not reversible, could be. This relation of inequality involves a definite law of equality, that the mechanical efficiencies of all reversible cyclic processes are the same, whatever be the nature of their operation or the material substances involved in them; that in fact the efficiency is a function solely of the two temperatures at which the cyclically working system takes in and gives out heat. These considerations constitute a fundamental general principle to which all possible slow reversible processes, so far as they concern matter in bulk, must conform in all their stages; its application is almost coextensive with the scope of general physics, the special kinetic theories in which inertia is involved, being excepted. (See Thermodynamics.) If the working system is an ideal gas-engine, in which a perfect gas (known from experience to be a possible state of matter) is passed through the cycle, and if temperature is measured from the absolute zero by the expansion of this gas, then simple direct calculation on the basis of the laws of ideal gases shows that H1/T1 = H2/T2; and as by the conservation of energy the work done is H1 − H2, it follows that the efficiency, measured as the ratio of the work done to the supply of heat, is 1 − T2/T1. If we change the sign of H1 and thus consider heat as positive when it is restored to the system as is H2, the fundamental equation becomes H1/T1 + H2/T2 = 0; and as any complex reversible working system may be considered as compounded in various ways of chains of elementary systems of this type, whose effects are additive, the general proposition follows, that in any reversible complete cyclic change which involves the taking in of heat by the system of which the amount is δH, when its temperature ranges between Tr and Tr + δT, the equation ΣδHr/Tr-0 holds good. Moreover, if the changes are not reversible, the proportion of the heat supply that is utilized for mechanical work will be smaller, so that more heat will be restored to the system, and ΣδHr/Tr or, as it may be expressed, ∫dH/T, must have a larger value, and must thus be positive. The first statement involves further, that for all reversible paths of change of the system from one state C to another state D, the value of ∫dH/T must be the same, because any one of these paths and any other one reversed would form a cycle; whereas for any irreversible path of change between the same states this integral must have a greater value (and so exceed the difference of entropies at the ends of the path). The definite quantity represented by this integral for a reversible path was introduced by Clausius in 1854 (also adumbrated by Kelvin's investigations about the same time), and was named afterwards by him the increase of the entropy of the system in passing from the state C to the state D. This increase, being thus the same for the unlimited number of possible reversible paths involving independent variation of all its finite co-ordinates, along which the system can pass, can depend only on the terminal states. The entropy belonging to a given state is therefore a function of that state alone, irrespective of the manner in which it has been reached; and this is the justification of the assignment to it of a special name, connoting a property of the system depending on its actual condition and not on its previous history. Every reversible change in an isolated system thus maintains the entropy of that system unaltered; no possible spontaneous change can involve decrease of the entropy; while any defect of reversibility, arising from diffusion of matter or motion in the system, necessarily leads to increase of entropy. For a physical or chemical system only those changes are spontaneously possible which would lead to increase of the entropy; if the entropy is already a maximum for the given total energy, and so incapable of further continuous increase under the conditions imposed upon the system, there must be stable equilibrium.
This definite quantity belonging to a material system, its entropy φ, is thus concomitant with its energy E, which is also a definite function of its actual state by the law of conservation of energy; these, along with its temperature T, and the various co-ordinates expressing its geometrical configuration and its physical and chemical constitution, are the quantities with which the thermodynamics of the system deals. That branch of science develops the consequences involved in just two principles: (i.) that the energy of every isolated system is constant, and (ii.) that its entropy can never diminish; any complication that may be involved arises from complexity in the systems to which these two laws have to be applied.
The General Thermodynamic Equation. - When any physical or chemical system undergoes an infinitesimal change of state, we have δE = δH + δU, where δH is the energy that has been acquired as heat from sources extraneous to the system during the change, and δU is the energy that has been imparted by reversible agencies such as mechanical or electric work. It is, however, not usually possible to discriminate permanently between heat acquired and work imparted, for (unless for isothermal transformations) neither δH nor δU is the exact differential of a function of the constitution of the system and so independent of its previous history, although their sum δE is such; but we can utilize the fact that δH is equal to Tδφ where δφ is such, as has just been seen. Thus E and φ represent properties of the system which, along with temperature, pressure and other independent data specifying its constitution, must form the variables of an analytical exposition. We have, therefore, to substitute Tδφ for δH; also the change of internal energy is determined by the change of constitution, involving a differential relation of type
δU = −pδv + δW + μ1δm1 + μ2δm2 + ... + μnδmn,
when the system consists of an intimate mixture (solution) of masses m1, m2, ... mn of given constituents, which differ physically or chemically but may be partially transformable into each other by chemical or physical action during the changes under consideration, the whole being of volume v and under extraneous pressure p, while W is potential energy arising from physical forces such as those of gravity, capillarity, etc. The variables m1, m2, ... mn may not be all independent; for example, if the system were chloride of ammonium gas existing along with its gaseous products of dissociation, hydrochloric acid and ammonia, only one of the three masses would be independently variable. The sufficient number of these variables (independent components) together with two other variables, which may be v and T, or v and φ, specifies and determines the state of the system, considered as matter in bulk, at each instant. It is usual to include δW in μ1δm1 + ...; in all cases where this is possible the single equation
δE = Tδφ − pδv + μ1δm1 + μ2δm2 + ... + μnδmn
thus expresses the complete variation of the energy-function E arising from change of state; and when the part involving the n constitutive differentials has been expressed in terms of the number of them that are really independent, this equation by itself becomes the unique expression of all the thermodynamic relations of the system. These are in fact the various relations ensuring that the right-hand side is an exact differential, and are of the type of reciprocal relations such as dμr/dφ = dT/dmr.
The condition that the state of the system be one of stable equilibrium is that δφ, the variation of entropy, be negative for all formally imaginable infinitesimal transformations which make δE vanish; for as δφ cannot actually be negative for any spontaneous variation, none of these transformations can then occur. From the form of the equation, this condition is the same as that δE − Tδφ must be positive for all possible variations of state of the system as above defined in terms of co-ordinates representing its constitution in bulk, without restriction.
We can change one of the independent variables expressing the state of the system from φ to T by subtracting δ(φT) from both sides of the equation of variation: then
δ(E − Tφ) = −φδT − pδv + μ1δm1 + ... + μnδmn.
It follows that for isothermal changes, i.e. those for which δT is maintained null by an environment at constant temperature, the condition of stable equilibrium is that the function E − Tφ shall be a minimum. If the system is subject to an external pressure p, which as well as the temperature is imposed constant from without and thus incapable of variation through internal changes, the condition of stable equilibrium is similarly that E − Tφ + pv shall be a minimum.
A chemical system maintained at constant temperature by communication of heat from its environment may thus have several states of stable equilibrium corresponding to different minima of the function here considered, just as there may be several minima of elevation on a landscape, one at the bottom of each depression; in fact, this analogy, when extended to space of n dimensions, exactly fits the case. If the system is sufficiently disturbed, for example, by electric shock, it may pass over (explosively) from a higher to a lower minimum, but never (without compensation from outside) in the opposite direction. The former passage, moreover, is often effected by introducing a new substance into the system; sometimes that substance is recovered unaltered at the end of the process, and then its action is said to be purely catalytic; its presence modifies the form of the function E − Tφ so as to obliterate the ridge between the two equilibrium states in the graphical representation.
There are systems in which the equilibrium states are but very slightly dependent on temperature and pressure within wide limits, outside which reaction takes place. Thus while there are cases in which a state of mobile dissociation exists in the system which changes continuously as a function of these variables, there are others in which change does not sensibly occur at all until a certain temperature of reaction is attained, after which it proceeds very rapidly owing to the heat developed, and the system soon becomes sensibly permanent in a transformed phase by completion of the reaction. In some cases of this latter type the cause of the delay in starting lies possibly in passive resistance to change, of the nature of viscosity or friction, which is competent to convert an unstable mechanical equilibrium into a moderately stable one; but in most such reactions there seems to be no exact equilibrium at any temperature, short of the ultimate state of dissipated energy in which the reaction is completed, although the velocity of reaction is found to diminish exponentially with change of temperature, and thus becomes insignificant at a small interval from the temperature of pronounced activity.
Free Energy. - The quantity E − Tφ thus plays the same fundamental part in the thermal statics of general chemical systems at uniform temperature that the potential energy plays in the statics of mechanical systems of unchanging constitution. It is a function of the geometrical co-ordinates, the physical and chemical constitution, and the temperature of the system, which determines the conditions of stable equilibrium at each temperature; it is, in fact, the potential energy generalized so as to include temperature, and thus be a single function relating to each temperature but at the same time affording a basis of connexion between the properties of the system at different temperatures. It has been called the free energy of the system by Helmholtz, for it is the part of the energy whose variation is connected with changes in the bodily structure of the system represented by the variables m1, m2, ... mn, and not with the irregular molecular motions represented by heat, so that it can take part freely in physical transformations. Yet this holds good only subject to the condition that the temperature is not varied; it has been seen above that for the more general variation neither δH nor δU is an exact differential, and no line of separation can be drawn between thermal and mechanical energies.
The study of the evolution of ideas in this, the most abstract branch of modern mathematical physics, is rendered difficult in the manner of most purely philosophical subjects by the variety of terminology, much of it only partially appropriate, that has been employed to express the fundamental principles by different investigators and at different stages of the development. Attentive examination will show, what is indeed hardly surprising, that the principles of the theory of free energy of Gibbs and Helmholtz had been already grasped and exemplified by Lord Kelvin in the very early days of the subject (see the paper "On the Thermoelastic and Thermomagnetic Properties of Matter, Part I." Quarterly Journal of Mathematics, No. 1, April 1855; reprinted in Phil. Mag., January 1878, and in Math. and Phys. Papers, vol. i. pp. 291, seq.). Thus the striking new advance contained in the more modern work of J. Willard Gibbs (1875-1877) and of Helmholtz (1882) was rather the sustained general application of these ideas to chemical systems, such as the galvanic cell and dissociating gaseous systems, and in general fashion to heterogeneous concomitant phases. The fundamental paper of Kelvin connecting the electromotive force of the cell with the energy of chemical transformation is of date 1851, some years before the distinction between free energy and total energy had definitely crystallized out; and, possibly satisfied with the approximate exactness of his imperfect formula when applied to a Daniell's cell (infra), and deterred by absence of experimental data, he did not return to the subject. In 1852 he briefly announced (Proc. Roy. Soc. Edin.) the principle of the dissipation of mechanical (or available) energy, including the necessity of compensation elsewhere when restoration occurs, in the form that "any restoration of mechanical energy, without more than an equivalent of dissipation, is impossible" - probably even in vital activity; but a sufficient specification of available energy (cf. infra) was not then developed. In the paper above referred to, where this was done, and illustrated by full application to solid elastic systems, the total energy is represented by c and is named "the intrinsic energy," the energy taken in during an isothermal transformation is represented by e, of which H is taken in as heat, while the remainder, the change of free (or mechanical or available) energy of the system is the unnamed quantity denoted by the symbol w, which is "the work done by the applied forces" at uniform temperature. It is pointed out that it is w and not e that is the potential energy-function for isothermal change, of which the form can be determined directly by dynamical and physical experiment, and from which alone the criteria of equilibrium and stress are to be derived - simply for the reason that for all reversible paths at constant temperature between the same terminal configurations, there must, by Carnot's principle, be the same gain or loss of heat. And a system of formulae are given (5) to (11) - Ex. gr. e = w − t dw/dt + J ∫ sdt for finding the total energy e for any temperature t when w and the thermal capacity s of the system, in a standard state, have thus been ascertained, and another for establishing connexion between the form of w for one temperature and its form for adjacent temperatures - which are identical with those developed by Helmholtz long afterwards, in 1882, except that the entropy appears only as an unnamed integral. The progress of physical science is formally identified with the exploration of this function w for physical systems, with continually increasing exactness and range - except where pure kinetic considerations prevail, in which cases the wider Hamiltonian dynamical formulation is fundamental. Another aspect of the matter will be developed below.
A somewhat different procedure, in terms of entropy as fundamental, has been adopted and developed by Planck. In an isolated system the trend of change must be in the direction which increases the entropy φ, by Clausius' form of the principle. But in experiment it is a system at constant temperature rather than an adiabatic one that usually is involved; this can be attained formally by including in the isolated system (cf. infra) a source of heat at that temperature and of unlimited capacity, when the energy of the original system increases by δE this source must give up heat of amount δE, and its entropy therefore diminishes δE/T. Thus for the original system maintained at constant temperature T it is δφ − δE/T that must always be positive in spontaneous change, which is the same criterion as was reached above. Reference may also be made to H.A. Lorentz's Collected Scientific Papers, part i.
A striking anticipation, almost contemporaneous, of Gibbs's thermodynamic potential theory (infra) was made by Clerk Maxwell in connexion with the discussion of Andrews's experiments on the critical temperature of mixed gases, in a letter published in Sir G.G. Stokes's Scientific Correspondence (vol. ii. p. 34).
Available Energy. - The same quantity φ, which Clausius named the entropy, arose in various ways in the early development of the subject, in the train of ideas of Rankine and Kelvin relating to the expression of the available energy A of the material system. Suppose there were accessible an auxiliary system containing an unlimited quantity of heat at absolute temperature T0, forming a condenser into which heat can be discharged from the working system, or from which it may be recovered at that temperature: we proceed to find how much of the heat of our system is available for transformation into mechanical work, in a process which reduces the whole system to the temperature of this condenser. Provided the process of reduction is performed reversibly, it is immaterial, by Carnot's principle, in what manner it is effected: thus in following it out in detail we can consider each elementary quantity of heat δH removed from the system as set aside at its actual temperature between T and T + δT for the production of mechanical work δW and the residue of it δH0 as directly discharged into the condenser at T0. The principle of Carnot gives δH/T = δH0/T0, so that the portion of the heat δH that is not available for work is δH0, equal to T0δH/T. In the whole process the part not available in connexion with the condenser at T0 is therefore T0 ∫ δH/T. This quantity must be the same whatever reversible process is employed: thus, for example, we may first transform the system reversibly from the state C to the state D, and then from the state D to the final state of uniform temperature T0. It follows that the value of T0 ∫ dH/T, representing the heat degraded, is the same along all reversible paths of transformation from the state C to the state D; so that the function ∫ dH/T is the excess of a definite quantity φ connected with the system in the former state as compared with the latter.
It is usual to change the law of sign of δH so that gain of heat by the system is reckoned positive; then, relative to a condenser of unlimited capacity at T0, the state C contains more mechanically available energy than the state D by the amount EC − ED + T0 ∫ dH/T, that is, by EC − ED − T0(φC − φD). In this way the existence of an entropy function with a definite value for each state of the system is again seen to be the direct analytical equivalent of Carnot's axiom that no process can be more efficient than a reversible process between the same initial and final states. The name motivity of a system was proposed by Lord Kelvin in 1879 for this conception of available energy. It is here specified as relative to a condenser of unlimited capacity at an assigned temperature T0: some such specification is necessary to the definition; in fact, if T0 were the absolute zero, all the energy would be mechanically available.
But we can obtain an intrinsically different and self-contained comparison of the available energies in a system in two different states at different temperatures, by ascertaining how much energy would be dissipated in each in a reduction to the same standard state of the system itself, at a standard temperature T0. We have only to reverse the operation, and change back this standard state to each of the others in turn. This will involve abstractions of heat δH0 from the various portions of the system in the standard state, and returns of δH to the state at T0; if this return were δH0T/T0 instead of δH, there would be no loss of availability in the direct process; hence there is actual dissipation δH − δH0T/T0, that is T(δφ − δφ0). On passing from state 1 to state 2 through this standard state 0 the difference of these dissipations will represent the energy of the system that has become unavailable. Thus in this sense E − Tφ + Tφ0 + const. represents for each state the amount of energy that is available; but instead of implying an unlimited source of heat at the standard temperature T0, it implies that there is no extraneous source. The available energy thus defined differs from E − Tφ, the free energy of Helmholtz, or the work function of the applied forces of Kelvin, which involves no reference to any standard state, by a simple linear function of the temperature alone which is immaterial as regards its applications.
The determination of the available mechanical energy arising from differences of temperature between the parts of the same system is a more complex problem, because it involves a determination of the common temperature to which reversible processes will ultimately reduce them; for the simple case in which no changes of state occur the solution was given by Lord Kelvin in 1853, in connexion with the above train of ideas (cf. Tait's Thermodynamics, §179). In the present exposition the system is sensibly in equilibrium at each stage, so that its temperature T is always uniform throughout; isolated portions at different temperatures would be treated as different systems.
Thermodynamic Potentials. - We have now to develop the relations involved in the general equation (1) of thermodynamics. Suppose the material system includes two coexistent states or phases, with opportunity for free interchange of constituents - for example, a salt solution and the aqueous vapour in equilibrium with it. Then in equilibrium a slight transfer δm of the water-substance of mass mr constituting the vapour, into the water-substance of mass ms, existing in the solution, should not produce any alteration of the first order in δE − Tδφ; therefore μr must be equal to μs. The quantity μr is called by Willard Gibbs the potential of the corresponding substance of mass mr; it may be defined as its marginal available energy per unit mass at the given temperature. If then a system involves in this way coexistent phases which remain permanently separate, the potentials of any constituent must be the same in all of them in which that constituent exists, for otherwise it would tend to pass from the phases in which its potential is higher to those in which it is lower. If the constituent is non-existent in any phase, its potential when in that phase would have to be higher than in the others in which it is actually present; but as the potential increases logarithmically when the density of the constituent is indefinitely diminished, this condition is automatically satisfied - or, more strictly, the constitutent cannot be entirely absent, but the presence of the merest trace will suffice to satisfy the condition of equality of potential. When the action of the force of gravity is taken into account, the potential of each constituent must include the gravitational potential gh; in the equilibrium state the total potential of each constituent, including this part, must be the same throughout all parts of the system into which it is freely mobile. An example is Dalton's law of the independent distributions of the gases in the atmosphere, if it were in a state of rest. A similar statement applies to other forms of mechanical potential energy arising from actions at a distance.
When a slight constitutive change occurs in a galvanic element at given temperature, producing available energy of electric current, in a reversible manner and isothermally, at the expense of chemical energy, it is the free energy of the system E − Tφ, not its total intrinsic energy, whose value must be conserved during the process. Thus the electromotive force is equal to the change of this free energy per electrochemical equivalent of reaction in the cell. This proposition, developed by Gibbs and later by Helmholtz, modifies the earlier one of Kelvin - which tacitly assumed all the energy of reaction to be available - except in the cases such as that of a Daniell's cell, in which the magnitude of the electromotive force does not depend sensibly on the temperature.
The effects produced on electromotive forces by difference of concentrations in dilute solutions can thus be accounted for and traced out, from the knowledge of the form of the free energy for such cases; as also the effects of pressure in the case of gas batteries. The free energy does not sensibly depend on whether the substance is solid or fused - for the two states are in equilibrium at the temperature of fusion - though the total energy differs in these two cases by the heat of fusion; for this reason, as Gibbs pointed out, voltaic potential-differences are the same for the fused as for the solid state of the substances concerned.
Relations involving Constitution only. - The potential of a component in a given solution can depend only on the temperature and pressure of the solution, and the densities of the various components, including itself; as no distance-actions are usually involved in chemical physics, it will not depend on the aggregate masses present. The example above mentioned, of two coexistent phases liquid and vapour, indicates that there may thus be relations between the constitutions of the phases present in a chemical system which do not involve their total masses. These are developed in a very direct manner in Willard Gibbs's original procedure. In so far as attractions at a distance (a uniform force such as gravity being excepted) and capillary actions at the interfaces between the phases are inoperative, the fundamental equation (1) can be integrated. Increasing the volume k times, and all the masses to the same extent - in fact, placing alongside each other k identical systems at the same temperature and pressure - will increase φ and E in the same ratio k; thus E must be a homogeneous function of the first degree of the independent variables φ, v, m1, ..., mn, and therefore by Euler's theorem relating to such functions
E = Tφ − pv + μ1m1 + ... + μnmn.
This integral equation merely expresses the additive character of the energies and entropies of adjacent portions of the system at uniform temperature, and thus depends only on the absence of sensible physical action directly across finite distances. If we form from it the expression for the complete differential δE, and subtract (1), there remains the relation
0 = φδT − vδp + m1δμ1 + ... + mnδμn.
This implies that in each phase the change of pressure depends on and is determined by the changes in T, μ1, ... μn alone; as we know beforehand that a physical property like pressure is an analytical function of the state of the system, it is therefore a function of these n + 1 quantities. When they are all independently variable, the densities of the various constituents and of the entropy in the phase are expressed by the partial fluxions of p with respect to them: thus
φ = dp , mr = dp .
v dT v dμr
But when, as in the case above referred to of chloride of ammonium gas existing partially dissociated along with its constituents, the masses are not independent, necessary linear relations, furnished by the laws of definite combining proportions, subsist between the partial fluxions, and the form of the function which expresses p is thus restricted, in a manner which is easily expressible in each special case.
This proposition that the pressure in any phase is a function of the temperature and of the potentials of the independent constituents, thus appears as a consequence of Carnot's axiom combined with the energy principle and the absence of effective actions at a distance. It shows that at a given temperature and pressure the potentials are not all independent, that there is a necessary relation connecting them. This is the equation of state or constitution of the phase, whose existence forms one mode of expression of Carnot's principle, and in which all the properties of the phase are involved and can thence be derived by simple differentiation.
The Phase Rule. - When the material system contains only a single phase, the number of independent variations, in addition to change of temperature and pressure, that can spontaneously occur in its constitution is thus one less than the number of its independent constituents. But where several phases coexist in contact in the same system, the number of possible independent variations may be much smaller. The present independent variables μ1, ..., μn are specially appropriate in this problem, because each of them has the same value in all the phases. Now each phase has its own characteristic equation, giving a relation between δp, δT, and δμ1, ... δμn, or such of the latter as are independent; if r phases coexist, there are r such relations; hence the number of possible independent variations, including those of v and T, is reduced to m − r + 2, where m is the number of independently variable chemical constituents which the system contains. This number of degrees of constitutive freedom cannot be negative; therefore the number of possible phases that can coexist alongside each other cannot exceed m + 2. If m + 2 phases actually coexist, there is no variable quantity in the system, thus the temperature and pressure and constitutions of the phases are all determined; such is the triple point at which ice, water and vapour exist in presence of each other. If there are m + 1 coexistent phases, the system can vary in one respect only; for example, at any temperature of water-substance different from the triple point two phases only, say liquid and vapour, or liquid and solid, coexist, and the pressure is definite, as also are the densities and potentials of the components. Finally, when but one phase, say water, is present, both pressure and temperature can vary independently. The first example illustrates the case of systems, physical or chemical, in which there is only one possible state of equilibrium, forming a point of transition between different constitutions; in the second type each temperature has its own completely determined state of equilibrium; in other cases the constitution in the equilibrium state is indeterminate as regards the corresponding number of degrees of freedom. By aid of this phase rule of Gibbs the number of different chemical substances actually interacting in a given complex system can be determined from observation of the degree of spontaneous variation which it exhibits; the rule thus lies at the foundation of the modern subject of chemical equilibrium and continuous chemical change in mixtures or alloys, and in this connexion it has been widely applied and developed in the experimental investigations of Roozeboom and van 't Hoff and other physical chemists, mainly of the Dutch school.
Extent to which the Theory can be practically developed. - It is only in systems in which the number of independent variables is small that the forms of the various potentials, - or the form of the fundamental characteristic equation expressing the energy of the system in terms of its entropy and constitution, or the pressure in terms of the temperature and the potentials, which includes them all, - can be readily approximated to by experimental determinations. Even in the case of the simple system water-vapour, which is fundamental for the theory of the steam-engine, this has not yet been completely accomplished. The general theory is thus largely confined, as above, to defining the restrictions on the degree of variability of a complex chemical system which the principle of Carnot imposes. The tracing out of these general relations of continuity of state is much facilitated by geometrical diagrams, such as James Thomson first introduced in order to exhibit and explain Andrews' results as to the range of coexistent phases in carbonic acid. Gibbs's earliest thermodynamic surface had for its co-ordinates volume, entropy and energy; it was constructed to scale by Maxwell for water-substance, and is fully explained in later editions of the Theory of Heat (1875); it forms a relief map which, by simple inspection, reveals the course of the transformations of water, with the corresponding mechanical and thermal changes, in its three coexistent states of solid, liquid and gas. In the general case, when the substance has more than one independently variable constituent, there are more than three variables to be represented; but Gibbs has shown the utility of surfaces representing, for instance, the entropy in terms of the constitutive variables when temperature and pressure are maintained constant. Such graphical methods are now of fundamental importance in connexion with the phase rule, for the experimental exploration of the trend of the changes of constitution of complex mixtures with interacting components, which arise as the physical conditions are altered, as, for example in modern metallurgy, in the theory of alloys. The study of the phenomena of condensation in a mixture of two gases or vapours, initiated by Andrews and developed in this manner by van der Waals and his pupils, forms a case in point (see Condensation of Gases).
Dilute Components: Perfect Gases and Dilute Solutions. - There are, however, two simple limiting cases, in which the theory can be completed by a determination of the functions involved in it, which throw much light on the phenomena of actual systems not far removed from these ideal limits. They are the cases of mixtures of perfect gases, and of very dilute solutions.
If, following Gibbs, we apply his equation (2) expressing the pressure in terms of the temperature and the potentials, to a very dilute solution of substances m2, m3, ... mn in a solvent substance m1, and vary the co-ordinate mr alone, p and T remaining unvaried, we have in the equilibrium state
mr dμr + m1 dμ1 + ... + mn dμn
dmr dmr dmr
in which every m except m1 is very small, while dμ1/dmr is presumably finite. As the second term is thus finite, this requires that the total potential of each component mr, which is mrdμr/dmr, shall be finite, say kr, in the limit when mr is null. Thus for very small concentrations the potential μr of a dilute component must be of the form krlog mr/v, being proportional to the logarithm of the density of that component; it thus tends logarithmically to an infinite value at evanescent concentrations, showing that removal of the last traces of any impurity would demand infinite proportionate expenditure of available energy, and is therefore practically impossible with finite intensities of force. It should be noted, however, that this argument applies only to fluid phases, for in the case of deposition of a solid mr is not uniformly distributed throughout the phase; thus it remains possible for the growth of a crystal at its surface in aqueous solution to extrude all the water except such as is in some form of chemical combination.
The precise value of this logarithmic expression for the potential can be readily determined for the case of a perfect gas from its characteristic properties, and can be thence extended to other dilute forms of matter. We have pv = R/m·T for unit mass of the gas, where m is the molecular weight, being 2 for hydrogen, and R is a constant equal to 82 10  in C.G.S. dynamical units, or 2 calories approximately in thermal energy units, which is the same for all gases because they have all the same number of molecules per unit volume. The increment of heat received by the unit mass of the gas is δH = pδv + κδT, κ being thus the specific heat at constant volume, which can be a function only of the temperature. Thus
φ = ∫ dH/T = R/m · log v + ∫ κT−1dT;
and the available energy A per unit mass is E − Tφ + Tφ0 where E = ε + ∫ κdT, the integral being for a standard state, and ε being intrinsic energy of chemical constitution; so that
A = ε + φ0T + ∫ κdT − T ∫ κT−1dT − R/m · T log v.
If there are ν molecules in the unit mass, and N per unit volume, we have mν = Nmv, each being 2 ν', where ν' is the number of molecules per unit mass in hydrogen; thus the free energy per molecule is a' + R'T log bN, where b = m/2ν', R' = R/2ν', and a' is a function of T alone. It is customary to avoid introducing the unknown molecular constant ν' by working with the available energy per "gramme-molecule," that is, for a number of grammes expressed by the molecular weight of the substance; this is a constant multiple of the available energy per molecule, and is a + RT logρ, ρ being the density equal to bN where b = m/2ν'. This formula may now be extended by simple summation to a mixture of gases, on the ground of Dalton's experimental principle that each of the components behaves in presence of the others as it would do in a vacuum. The components are, in fact, actually separable wholly or partially in reversible ways which may be combined into cycles, for example, either (i.) by diffusion through a porous partition, taking account of the work of the pressures, or (ii.) by utilizing the modified constitution towards the top of a long column of the mixture arising from the action of gravity, or (iii.) by reversible absorption of a single component.
If we employ in place of available energy the form of characteristic equation which gives the pressure in terms of the temperature and potentials, the pressure of the mixture is expressed as the sum of those belonging to its components: this equation was made by Gibbs the basis of his analytical theory of gas mixtures, which he tested by its application to the only data then available, those of the equilibrium of dissociation of nitrogen peroxide (2NO2 ⇆ N2O4) vapour.
Van 't Hoff's Osmotic Principle: Theoretical Explanation. - We proceed to examine how far the same formulae as hold for gases apply to the available energy of matter in solution which is so dilute that each molecule of the dissolved substance, though possibly the centre of a complex of molecules of the solvent, is for nearly all the time beyond the Sphere of direct influence of the other molecules of the dissolved substance. The available energy is a function only of the co-ordinates of the matter in bulk and the temperature; its change on further dilution, with which alone we are concerned in the transformations of dilute solutions, can depend only on the further separation of these molecular complexes in space that is thereby produced, as no one of them is in itself altered. The change is therefore a function only of the number N of the dissolved molecules per unit volume, and of the temperature, and is, per molecule, expressible in a form entirely independent of their constitution and of that of the medium in which they are dissolved. This suggests that the expression for the change on dilution is the same as the known one for a gas, in which the same molecules would exist free and in the main outside each other's spheres of influence; which confirms and is verified by the experimental principle of van 't Hoff, that osmotic pressure obeys the laws of gaseous pressure with identically the same physical constants as those of gases. It can be held, in fact, that this suggestion does not fall short of a demonstration, on the basis of Carnot's principle, and independent of special molecular theory, that in all cases where the molecules of a component, whether it be of a gas or of a solution, are outside each other's spheres of influence, the available energy, so far as regards dilution, must have a common form, and the physical constants must therefore be the known gas-constants. The customary exposition derives this principle, by an argument involving cycles, from Henry's law of solution of gases; it is sensibly restricted to such solutes as appear concomitantly in the free gaseous state, but theoretically it becomes general when it is remembered that no solute can be absolutely non-volatile.
Source of the Idea of Temperature. - The single new element that thermodynamics introduces into the ordinary dynamical specification of a material system is temperature. This conception is akin to that of potential, except that it is given to us directly by our sense of heat. But if that were not so, we could still demonstrate, on the basis of Carnot's principle, that there is a definite function of the state of a body which must be the same for all of a series of connected bodies, when thermal equilibrium has become established so that there is no tendency for heat to flow from one to another. For we can by mere geometrical displacement change the order of the bodies so as to bring different ones into direct contact. If this disturbed the thermal equilibrium, we could construct cyclic processes to take advantage of the resulting flow of heat to do mechanical work, and such processes might be carried on without limit. Thus it is proved that if a body A is in temperature-equilibrium with B, and B with C, then A must be in equilibrium with C directly. This argument can be applied, by aid of adiabatic partitions, even when the bodies are in a field of force so that mechanical work is required to change their geometrical arrangement; it was in fact employed by Maxwell to extend from the case of a gas to that of any other system the proposition that the temperature is the same all along a vertical column in equilibrium under gravity.
It had been shown from the kinetic theory by Maxwell that in a gas-column the mean kinetic energy of the molecules is the same at all heights. If the only test of equality of temperature consisted in bringing the bodies into contact, this would be rather a proof that thermal temperature is of the same physical nature in all parts of the field of force; but temperature can also be equalized across a distance by radiation, so that this law for gases is itself already necessitated by Carnot's general principle, and merely confirmed or verified by the special gas-theory. But without introducing into the argument the existence of radiation, the uniformity of temperature throughout all phases in equilibrium is necessitated by the doctrine of energetics alone, as otherwise, for example, the raising of a quantity of gas to the top of the gravitational column in an adiabatic enclosure together with the lowering of an equal mass to the bottom would be a source of power, capable of unlimited repetition.
Laws of Chemical Equilibrium based on Available Energy. - The complete theory of chemical and physical equilibrium in gaseous mixtures and in very dilute solutions may readily be developed in terms of available energy (cf. Phil. Trans., 1897, A, pp. 266-280), which forms perhaps the most vivid and most direct procedure. The available energy per molecule of any kind, in a mixture of perfect gases in which there are N molecules of that kind per unit volume, has been found to be a' + R'T logbN where R' is the universal physical constant connected with R above. This expression represents the marginal increase of available energy due to the introduction of one more molecule of that kind into the system as actually constituted. The same formula also applies, by what has already been stated, to substances in dilute solution in any given solvent. In any isolated system in a mobile state of reaction or of internal dissociation, the condition of chemical equilibrium is that the available energy at constant temperature is a minimum, therefore that it is stationary, and slight change arising from fresh reaction would not sensibly alter it. Suppose that this reaction, per molecule affected by it, is equivalent to introducing n1 molecules of type N1, n2 of type N2, etc., into the system, n1, n2, ... being the numbers of molecules of the different types that take part in the reaction, as shown by its chemical equation, reckoned positive when they appear, negative when they disappear. Then in the state of equilibrium
n1 (a'1 + R'T log b1N1) + n2 (a'2 + R'T log b2N2) + ...
must vanish. Therefore N1n1N2n2 ... must be equal to K, a function of the temperature alone. This law, originally based by Guldberg and Waage on direct statistics of molecular interaction, expresses for each temperature the relation connecting the densities of the interacting substances, in dilution comparable as regards density with the perfect gaseous state, when the reaction has come to the state of mobile equilibrium.
All properties of any system, including the heat of reaction, are expressible in terms of its available energy A, equal to E − Tφ + φ0T. Thus as the constitution of the system changes with the temperature, we have
dA = dE - T dφ − (φ
dT dT dT
δE = δH + δW, δH = Tδφ,
δH being heat and δW mechanical and chemical energy imparted to the system at constant temperature; hence
d(A − W) = −(φ − φ0), so that A = E + T
d(A − W) ,
which is equivalent to
E − W = −T d A −
This general formula, applied differentially, expresses the heat δE − δW absorbed by a reaction in terms of δA, the change produced by it in the available energy of the system, and of δW, the mechanical and electrical work done on the system during its progress.
In the problem of reaction in gaseous systems or in very dilute solution, the change of available energy per molecule of reaction has just been found to be
δA = δA0 + R'T log K', where K' = b1 [n1]b2n2 ... K;
thus, when the reaction is spontaneous without requiring external work, the heat absorbed per molecule of reaction is
−T d δA0 , or −R'T d log K.
dT T dT
This formula has been utilized by van 't Hoff to determine, in terms of the heat of reaction, the displacement of equilibrium in various systems arising from change of temperature; for K, equal to N1n1N2 [n2] ..., is the reaction-parameter through which alone the temperature affects the law of chemical equilibrium in dilute systems.
Interfacial Phenomena: Liquid Films. - The characteristic equation hitherto developed refers to the state of an element of mass in the interior of a homogeneous substance: it does not apply to matter in the neighbourhood of the transition between two adjacent phases. A remarkable analysis has been developed by J.W. Gibbs in which the present methods concerning matter in bulk are extended to the phenomena at such an interface, without the introduction of any molecular theory; it forms the thermodynamic completion of Gauss's mechanical theory of capillarity, based on the early form of the principle of total energy. The validity of the fundamental doctrine of available energy, so far as regards all mechanical actions in bulk such as surface tensions, is postulated, even when applied to interfacial layers so thin as to be beyond our means of measurement; the argument from perpetual motions being available here also, as soon as we have experimentally ascertained that the said tensions are definite physical properties of the state of the interface and not merely accidental phenomena. The procedure will then consist in assuming a definite excess of energy, of entropy, and of the masses of the various components, each per unit surface, at the interface, the potential of each component being of necessity, in equilibrium, the same as it is in the adjacent masses. The interfacial transition layer thus provides in a sense a new surface-phase coexistent with those on each side of it, and having its own characteristic equation. It is only the extent of the interface and not its curvatures that need enter into this relation, because any slight influence of the latter can be eliminated from the equation by slightly displacing the position of the surface which is taken to represent the interface geometrically. By an argument similar to one given above, it is shown that one of the forms of the characteristic equation is a relation expressing the surface tension as a function of the temperature and the potentials of the various components present on the two sides of the interface; and from the differentiation of this the surface densities of the superficial distributions of these components (as above defined) can be obtained. The conditions that a specified new phase may become developed when two other given ones are brought into contact, i.e. that a chemical reaction may start at the interface, are thence formally expressed in terms of the surface tensions of the three transition layers and the pressures in the three phases. In the case of a thin soap-film, sudden extension of any part reduces the interfacial density of each component at each surface of the film, and so alters the surface tension, which requires time to recover by the very slow diffusion of dissolved material from other parts of the thin film; the system being stable, this change must be an increase of tension, and constitutes a species of elasticity in the film. Thus in a vertical film the surface tension must be greater in the higher parts, as they have to sustain the weight of the lower parts; the upper parts, in fact, stretch until the superficial densities of the components there situated are reduced to the amounts that correspond to the tension required for this purpose. Such a film could not therefore consist of pure water. But there is a limit to these processes: if the film becomes so thin that there is no water in bulk between its surfaces, the tensions cannot adjust themselves in this slow way by migration of components from one part of the film to another; if the film can survive at all after it has become of molecular thickness, it must be as a definite molecular structure all across its thickness. Of such type are the black spots that break out in soap-films (suggested by Gibbs and proved by the measures of Reinold and Rücker): the spots increase in size because their tension is less than that of the surrounding film, but their indefinite increase is presumably stopped in practice by some clogging or viscous agency at their boundary.
Transition to Molecular Theory. - The subject of energetics, based on the doctrine of available energy, deals with matter in bulk and is not concerned with its molecular constitution, which it is expressly designed to eliminate from the problem. This analysis of the phenomena of surface tension shows how far the principle of negation of perpetual motions can carry us, into regions which at first sight might be classed as molecular. But, as in other cases, it is limited to pointing out the general scheme of relations within which the phenomena can have their play. There is now a considerable body of knowledge correlating surface tension with chemical constitution, especially to a certain extent with the numerical density of the distribution of molecules; thus R. Eötvös has shown that a law of proportionality exists for wide classes of substances between the temperature-gradient of the surface tension and the density of the molecules over the surface layer, which varies as the two-thirds power of the number per unit volume (see Chemistry: Physical). This takes us into the Sphere of molecular science, where at present we have only such indications largely derived from experiment, if we except the mere notion of inter-atomic forces of unknown character on which the older theories of capillarity, those of Laplace and Poisson, were constructed.
In other topics the same restrictions on the scope of the simple statical theory of energy appear. From the ascertained behaviour in certain respects of gaseous media we are able to construct their characteristic equation, and correlate their remaining relations by means of its consequences. Part of the experimental knowledge required for this purpose is the values of the gas-constants, which prove to be the same for all nearly perfect gases. The doctrine of energetics by itself can give no clue as to why this should be so; it can only construct a scheme for each simple or complex medium on the basis of its own experimentally determined characteristic equation. The explanation of uniformities in the intrinsic constitutions of various media belongs to molecular theory, which is a distinct and in the main more complex and more speculative department of knowledge. When we proceed further and find, with van 't Hoff, that these same universal gas-constants reappear in the relations of very dilute solutions, our demand for an explanation such as can only be provided by molecular theory (as supra) is intensely stimulated. But except in respects such as these the doctrine of energetics gives a complete synthesis of the course and relations of the chemical reactions of matter in bulk, from which we can eliminate atomism altogether by restating the merely numerical atomic theory of Dalton as a principle of equivalent combining proportions. Of recent years there has been a considerable school of chemists who insist on this procedure as a purification of their science from the hypothetical ideas as to atoms and molecules, in terms of which its experimental facts have come to be expressed. A complete system of doctrine can be developed in this manner, but its scope will be limited. It makes use of one principle of correlation, the doctrine of available energy, and discards another such principle, the atomic theory. Nor can it be said that the one principle is really more certain and definite than the other. This may be illustrated by what has sometimes by German writers been called Gibbs's paradox: the energy that is available for mechanical effect in the inter-diffusion of given volumes of two gases depends only on these volumes and their pressures, and is independent of what the gases are; if the gases differed only infinitesimally in constitution it would still be the same, and the question arises where we are to stop, for we cannot suppose the inter-diffusion of two identical gases to be a source of power. This then looks like a real failure, or rather limitation, of the principle; and there are other such, that can only be satisfactorily explained by aid of the complementary doctrine of molecular theory. That theory, in fact, shows that the more nearly identical the gases are, the slower will be the process of inter-diffusion, so that the mechanical energy will indeed be available, but only after a time that becomes indefinitely prolonged. It is a case in which the simple doctrine of energetics becomes inadequate before the limit is reached. The phenomena of highly rarefied gases provide other cases. And in fact the only reason hitherto thought of for the invariable tendency of available energy to diminish, is that it represents the general principle that in the kinetic play of a vast assemblage of independent molecules individually beyond our control, the normal tendency is for the regularities to diminish and the motions to become less correlated: short of some such reason, it is an unexplained empirical principle. In the special departments of dynamical physics on the other hand, the molecular theory, there dynamical and therefore much more difficult and less definite, is an indispensable part of the framework of science; and even experimental chemistry now leans more and more on new physical methods and instruments. Without molecular theory the clue which has developed into spectrum analysis, bringing with it stellar chemistry and a new physical astronomy, would not have been available; nor would the laws of diffusion and conduction in gases have attained more than an empirical form; nor would it have been possible to weave the phenomena of electrodynamics and radiation into an entirely rational theory.
The doctrine of available energy, as the expression of thermodynamic theory, is directly implied in Carnot's Essai of 1824, and constitutes, in fact, its main theme; it took a fresh start, in the light of fuller experimental knowledge regarding the nature of heat, in the early memoirs of Rankine and Lord Kelvin, which may be found in their Collected Scientific Papers; a subsequent exposition occurs in Maxwell's Theory of Heat; its most familiar form of statement is Lord Kelvin's principle of the dissipation of available energy. Its principles were very early applied by James Thomson to a physico-chemical problem, that of the influence of stress on the growth of crystals in their mother liquor. The "thermodynamic function" introduced by Rankine into its development is the same as the "entropy" of the material system, independently defined by Clausius about the same time. Clausius's form of the principle, that in an adiabatic system the entropy tends continually to increase, has been placed by Professor Willard Gibbs, of Yale University, at the foundation of his magnificent but complex and difficult development of the theory. His monumental memoir "On the Equilibrium of Heterogeneous Substances," first published in Trans. Connecticut Academy (1876-1878), made a clean sweep of the subject; and workers in the modern experimental science of physical chemistry have returned to it again and again to find their empirical principles forecasted in the light of pure theory, and to derive fresh inspiration for new departures. As specially preparatory to Gibbs's general discussion may be mentioned Lord Rayleigh's memoir on the thermodynamics of gaseous diffusion (Phil. Mag., 1876), which was expounded by Maxwell in the 9th edition of the Ency. Brit. (art. Diffusion). The fundamental importance of the doctrine of dissipation of energy for the theory of chemical reaction had already been insisted on in general terms by Rayleigh; subsequent to, but independently of, Gibbs's work it had been elaborated by von Helmholtz (Gesamm. Abhandl. ii. and iii.) in connexion with the thermodynamics of voltaic cells, and more particularly in the calculation of the free or available energy of solutions from data of vapour-pressure, with a view to the application to the theory of concentration cells, therein also coming close to the doctrine of osmotic pressure. This form of the general theory has here been traced back substantially to Lord Kelvin under date 1855. Expositions and developments on various lines will be found in papers by Riecke and by Planck in Annalen der Physik between 1890 and 1900, in the course of a memoir by Larmor, Phil. Trans., 1897, A, in Voigt's Compendium der Physik and his more recent Thermodynamik, in Planck's Vorlesungen über Thermodynamik, in Duhem's elaborate Traité de mécanique chimique and Le Potential thermodynamique, in Whetham's Theory of Solution and in Bryan's Thermodynamics. Numerous applications to special problems are expounded in van't Hoff's Lectures on Theoretical and Physical Chemistry.
The theory of energetics, which puts a diminishing limit on the amount of energy available for mechanical purposes, is closely implicated in the discovery of natural radioactive substances by H. Becquerel, and their isolation in the very potent form of radium salts by M. and Mme Curie. The slow degradation of radium has been found by the latter to be concomitant with an evolution of heat, in amount enormous compared with other chemical changes. This heat has been shown by E. Rutherford to be about what must be due to the stoppage of the α and β particles, which are emitted from the substance with velocities almost of the same scale as that of light. If they struck an ideal rigid target, their lost kinetic energy must all be sent away as radiation; but when they become entangled among the molecules of actual matter, it will, to a large extent, be shared among them as heat, with availability reduced accordingly. In any case the particles that escape into the surrounding space are so few and their velocity so uniform that we can, to some extent, treat their energy as directly available mechanically, in contradistinction to the energy of individual molecules of a gas (cf. Maxwell's "demons"), e.g. for driving a vane, as in Crookes's experiment with the cathode rays. Indeed, on account of the high velocity of projection of the particles from a radium salt, the actions concerned would find their equilibrium at such enormously high temperatures that any influence of actually available differences of temperature is not sensibly a feature of the phenomena. Such actions, however, like explosive actions in general, are beyond our powers of actual direct measurement as regards the degradation of availability of the energy. It has been pointed out by Rutherford, R.J. Strutt and others, that the energy of degradation of even a very minute admixture of active radium would entirely dominate and mask all other cosmical modes of transformation of energy; for example, it far outweighs that arising from the exhaustion of gravitational energy, which has been shown by Helmholtz and Kelvin to be an ample source for all the activities of our cosmical system, and to be itself far greater than the energy of any ordinary chemical rearrangements consequent on a fall of temperature: a circumstance that makes the existence and properties of this substance under settled cosmic conditions still more anomalous (see Radioactivity). Theoretically it is possible to obtain unlimited concentration of availability of energy at the expense of an equivalent amount of degradation spread over a wider field; the potency of electric furnaces, which have recently opened up a new department of chemistry, and are limited only by the refractoriness of the materials of which they are constituted, forms a case in point. In radium we have the very remarkable phenomenon of far higher concentration occurring naturally in very minute permanent amounts, so that merely chemical sifting is needed to produce its aggregation. Even in pitchblende only one molecule in 10  seems to be of radium, renewable, however, when lost, by internal transformation.
The energetics of Radiation is treated under that heading. See also Thermodynamics.
Note - this article incorporates content from Encyclopaedia Britannica, Eleventh Edition, (1910-1911)