Popular Science Monthly/Volume 19/June 1881/The Modern Development of Faraday's Conception of Electricity
|←Natural Production of Alcohol||Popular Science Monthly Volume 19 June 1881 (1881)
The Modern Development of Faraday's Conception of Electricity
By Hermann von Helmholtz
|Glucose and Grape-Sugar→|
By Professor H. HELMHOLTZ.
THE majority of Faraday's own researches were connected, directly or indirectly, with questions regarding the nature of electricity, and his most important and most renowned discoveries lay in this field. The facts which he has found are universally known. Nevertheless, the fundamental conceptions by which Faraday has been led to these much-admired discoveries have not been received with much consideration. His principal aim was to express, in his new conceptions, only facts, with the least possible use of hypothetical substances and forces. This was really a progress in general scientific method, destined to purify science from the last remnants of metaphysics. Now that the mathematical interpretation of Faraday's conceptions regarding the nature of electric and magnetic force has been given by Clerk Maxwell, we see how great a degree of exactness and precision was really hidden behind his words, which to his contemporaries appeared so vague or obscure; and it is astonishing in the highest degree to see what a large number of general theories, the methodical deduction of which requires the highest powers of mathematical analysis, he has found, by a kind of intuition, with the security of instinct, without the help of a single mathematical formula.
The electrical researches of Faraday, although embracing a great number of apparently minute and disconnected questions, all of which he has treated with the same careful attention and conscientiousness, are really always aiming at two fundamental problems of natural philosophy: the one more regarding the nature of physical forces, or of forces working at a distance; the other, in the same way, regarding chemical forces, or those which act from molecule to molecule, and the relation between these and the first.
The great fundamental problem which Faraday called up anew for discussion was the existence of forces working directly at a distance without any intervening medium. During the last and the beginning of the present century the model after the likeness of which nearly all physical theories had been formed was the force of gravitation acting between the sun, the planets, and their satellites. It is known how, with much caution and even reluctance. Sir Isaac Newton himself proposed his grand hypothesis, which was destined to become the first great and imposing example, illustrating the power of true scientific method.
But then came Oerstedt's discovery of the motions of magnets under the influence of electric currents. The force acting in these phenomena had a new and very singular character. It seemed as if it would drive a single isolated pole of a magnet in a circle around the wire conducting the current, on and on without end, never coming to rest. Faraday saw that a motion of this kind could not be produced by any force of attraction or repulsion, working from point to point. If the current is able to increase the velocity of the magnet, the magnet must react on the current. So he made the experiment, and discovered induced currents; he traced them out through all the various conditions under which they ought to appear. He concluded that somewhere in a part of the space traversed by magnetic force there exists a peculiar state of tension, and that every change of this tension produces electro-motive force. This unknown hypothetical state he called provisionally the electrotonic state, and he was occupied for years and years in finding out what was this electrotonic state. He discovered at first, in 1838, the dielectric polarization of electric insulators, subject to electric forces. Such bodies show, under the influence of electric forces, phenomena perfectly analogous to those exhibited by soft iron under the influence of the magnetic force. Eleven years later, in 1849, he was able to demonstrate that all ponderable matter is magnetized under the influence of sufficiently intense magnetic force, and at the same time he discovered the phenomena of diamagnetism, which indicated that even space, devoid of all ponderable matter, is magnetizable; and now, with quite a wonderful sagacity and intellectual precision, Faraday performed in his brain the work of a great mathematician without using a single mathematical formula. He saw with his mind's eye that, by these systems of tensions and pressures produced by the dielectric and magnetic polarization of space which surrounds electrified bodies, magnets or wires conducting electric currents, all the phenomena of electro-static, magnetic, electro-magnetic attraction, repulsion, and induction could be explained, without recurring at all to forces acting directly at a distance. This was the part of his path where so few could follow him; perhaps a Clerk Maxwell, a second man of the same power and independence of intellect, was necessary to reconstruct in the normal methods of science the great building, the plan of which Faraday had conceived in his mind and attempted to make visible to his contemporaries.
Nevertheless, the adherents of direct action at a distance have not yet ceased to search for solutions of the electro-magnetic problem. The present development of science, however, shows, as I think, a state of things very favorable to the hope that Faraday's fundamental conceptions may in the immediate future receive general assent. His theory, indeed, is the only existing one which is at the same time in perfect harmony with the facts observed, and which at least does not lead into any contradiction against the general axioms of dynamics.
It is not at all necessary to accept any definite opinion about the ultimate nature of the agent which we call electricity.
Faraday himself avoided as much as he could giving any affirmative assertion regarding this problem, although he did not conceal his disinclination to believe in the existence of two opposite electric fluids.
For our own discussion of the electro-chemical phenomena, to which we shall turn now, I beg permission to use the language of the old dualistic theory, because we shall have to speak principally on relations of quantity.
I now turn to the second fundamental problem aimed at by Faraday, the connection between electric and chemical force. Already, before Faraday went to work, an elaborate electro-chemical theory had been established by the renowned Swedish chemist, Berzelius, which formed the connecting link of the great work of his life, the systematization of the chemical knowledge of his time. His starting-point was the series into which Volta had arranged the metals according to the electric tension which they exhibit after contact with each other. A fundamental point which Faraday's experiment contradicted was the supposition that the quantity of electricity collected in each atom was dependent on their mutual electro-chemical differences, which he considered as the cause of their apparently greater chemical affinity. But, although the fundamental conceptions of Berzelius's theory have been forsaken, chemists have not ceased to speak of positive and negative constituents of a compound body. Nobody can overlook that such a contrast of qualities, as was expressed in Berzelius's theory, really exists, well developed at the extremities, less evident in the middle terms of the series, playing an important part in all chemical actions, although often subordinated to other influences.
When Faraday began to study the phenomena of decomposition by the galvanic current, which of course were considered by Berzelius as one of the firmest supports of his theory, he put a very simple question; the first question, indeed, which every chemist speculating about electrolysis ought to have answered. He asked, What is the quantity of electrolytic decomposition if the same quantity of electricity is sent through several electrolytic cells? By this investigation he discovered that most important law, generally known under his name, but called by him the law of definite electrolytic action.
Faraday concluded from his experiments that a definite quantity of electricity can not pass a voltametric cell containing acidulated water between electrodes of platinum without setting free at the negative electrode a corresponding definite amount of hydrogen, and at the positive electrode the equivalent quantity of oxygen, one atom of oxygen for every pair of atoms of hydrogen. If, instead of hydrogen, any other element capable of substituting hydrogen is separated from the electrolyte, this is done also in a quantity exactly equivalent to the quantity of hydrogen which would have been evolved by the same electric current.
Since that time our experimental methods and our knowledge of the laws of electrical phenomena have made enormous progress, and a great many obstacles have now been removed which entangled every one of Faraday's steps, and obliged him to fight with the confused ideas and ill-applied theoretical conceptions of some of his contemporaries. We need not hesitate to say that, the more experimental methods were refined, the more the exactness and generality of Faraday's law was confirmed.
In the beginning, Berzelius and the adherents of Volta's original theory of galvanism, based on the effects of metallic contact, raised many objections against Faraday's law. By the combination of Nobili's astatic pairs of magnetic needles with Schweigger's multiplicator, a coil of copper wire with numerous circumvolutions, galvanometers became so delicate that the electro-chemical equivalent of the smaller currents they indicated was imperceptible for all chemical methods. With the newest galvanometers you can very well observe currents which would want to last a century before decomposing one milligramme of water, the smallest quantity which is usually weighed on chemical balances. You see that, if such a current lasts only some seconds or some minutes, there is not the slightest hope to discover its products of decomposition by chemical analysis. And, even if it should last a long time, the feeble quantities of hydrogen collected at the negative electrode can vanish, because they combine with the traces of atmospheric oxygen absorbed by the liquid. Under such conditions a feeble current may continue as long as you like without producing any visible trace of electrolysis, even not of galvanic polarization, the appearance of which can be used as an indication of previous electrolysis. Galvanic polarization, as you know, is an altered state of the metallic plates which have been used as electrodes during the decomposition of an electrolyte. Polarized electrodes, when connected by a galvanometer, give a current which they did not give before being polarized. By this current the plates are discharged again and returned to their original state of equality.
This depolarizing current is indeed a most delicate means of discovering previous decomposition. I have really ascertained that under favorable conditions one can observe the polarization produced during some seconds by a current which decomposes one milligramme of water in a century.
Products of decomposition can not appear at the electrodes without motions of the constituent molecules of the electrolyte throughout the whole length of the liquid. This subject has been studied very carefully, and for a great number of liquids, by Professor Hittorff, of Münster, and Professor G. Wiedemann, of Leipsic.
Professor F. Kohlrausch, of Würzburg, has brought to light the very important fact that, in diluted solutions of salts, including hydrates of acids and hydrates of caustic alkalies, every atom under the influence of currents of the same density moves on with its own peculiar velocity, independently of other atoms moving at the same time in the same or in opposite directions. The total amount of chemical motion in every section of the fluid is represented by the sum of the equivalents of the cation gone forward and of the anion gone backward, in the same way as in the dualistic theory of electricity, and the total amount of electricity flowing through a section of the conductor corresponds to the sum of positive electricity going forward and negative electricity going backward.
This established, Faraday's law tells us that, through each section of an electrolytic conductor, we have always equivalent electrical and chemical motion. The same definite quantity of either positive or negative electricity moves always with each univalent ion, or with every unit of affinity of a multivalent ion, and accompanies it during all its motions through the interior of the electrolytic fluid. This we may call the electric charge of the atom.
Now, the most startling result, perhaps, of Faraday's law is this: If we accept the hypothesis that the elementary substances are composed of atoms, we can not avoid concluding that electricity also, positive as well as negative, is divided into definite elementary portions, which behave like atoms of electricity. As long as it moves about on the electrolytic liquid, each atom remains united with its electric equivalent or equivalents. At the surface of the electrodes decomposition can take place if there is sufficient electro-motive power, and then the atoms give off their electric charges and become electrically neutral.
Now arises the question, Are all these relations between electricity and chemical combination limited to that class of bodies which we know as electrolytes? In order to produce a current of sufficient strength to collect enough of the products of decomposition without producing too much heat in the electrolyte, the substance which we try to decompose ought not to have too much resistance against the current. But this resistance may be very great, and the motion of the ions may be very slow — so slow indeed that we should need to allow it to go on for hundreds of years before we should be able to collect even traces of the products of decomposition; nevertheless, all the essential attributes of the process of electrolysis could subsist. If you connect an electrified conductor with one of the electrodes of a cell filled with oil of turpentine, the other with the earth, you will find that the electricity of the conductor is discharged unmistakably more rapidly through the oil of turpentine than if you take it away and fill the cell only with air.
Also in this case we may observe polarization of the electrodes as a symptom of previous electrolysis. Another sign of electrolytic conduction is, that liquids brought between two different metals produce an electro-motive force. This is never done by metals of equal temperature, or other conductors which, like metals, let electricity pass without being decomposed.
The same effect is also observed even with a great many rigid bodies, although we have very few solid bodies which allow us to observe this electrolytic conduction with the galvanometer, and even these only at temperatures near to their melting-point. It is nearly impossible to shelter the quadrants of a delicate electrometer against being charged by the insulating bodies by which they are supported.
In all the cases which I have quoted one might suspect that traces of humidity absorbed by the substances or adhering to their surface were the electrolytes. I show you, therefore, this little Daniell's cell, in which the porous septum has been substituted by a thin stratum of glass. Externally, all is symmetrical at both poles; there is nothing in contact with the air but a closed surface of glass, through which two wires of platinum penetrate. The whole charges the electrometer exactly like a Daniell's cell of very great resistance, and this it would not do if the septum of glass did not behave like an electrolyte. All these facts show that electrolytic conduction is not at all limited to solutions of acids or salts.
Hitherto we have studied the motions of ponderable matter, as well as of electricity, going on in an electrolyte. Let us study now the forces which are able to produce these motions. It has always appeared somewhat startling to everybody who knows the mighty power of chemical forces, the enormous quantity of heat and of mechanical work which they are able to produce, and who compares with it the exceedingly small electric attraction which the poles of a battery of two Daniell's cells show. Nevertheless, this little apparatus is able to decompose water.
The quantity of electricity which can be conveyed by a very small quantity of hydrogen, when measured by its electrostatic forces, is exceedingly great. Faraday saw this, and has endeavored in various ways to give at least an approximate determination. The most powerful batteries of Leyden-jars, discharged through a voltameter, give scarcely any visible traces of gases. At present we can give definite numbers. The result is, that the electricity of one milligramme of water, separated and communicated to two balls one kilometre distant, would produce an attraction between them equal to the weight of twenty-five thousand kilos.
The total force exerted by the attraction of an electrified body upon another charged with opposite electricity is always proportional to the quantity of electricity contained in the attracting as on the attracted body, and therefore even the feeble electric tension of two Daniell's elements, acting through an electrolytic cell upon the enormous quantities of electricity with which the constituent ions of water are charged, is mighty enough to separate these elements and to keep them separated.
We now turn to investigate what motions of the ponderable molecules require the action of these forces. Let us begin with the, case where the conducting liquid is surrounded everywhere by insulating bodies. Then no electricity can enter, none can go out through its surface, but positive electricity can be driven to one side, negative to the other, by the attracting and repelling forces of external electrified bodies. This process, going on as well in every metallic conductor, is called “electrostatic induction.” Liquid conductors behave quite like metals under these conditions. Professor Wüllner has proved that even our best insulators, exposed to electric forces for a long time, are charged at last quite in the same way as metals would be charged in an instant. There can be no doubt that even electro-motive forces going down to less than 1⁄100 Daniell produce perfect electrical equilibrium in the interior of an electrolytic liquid.
Another somewhat modified instance of the same effects is afforded by a voltametric cell containing two electrodes of platinum, which are connected with a Daniell's cell, the electro-motive force of which is insufficient to decompose the electrolyte. Under this condition the ions carried to the electrodes can not give off their electric charges. The whole apparatus behaves, as was first accentuated by Sir W. Thomson, like a condenser of enormous capacity.
Observing the polarizing and depolarizing currents in a cell containing two electrodes of platinum, hermetically sealed and freed of all air, Ave can observe these phenomena with the most feeble electro-motive forces of 1⁄1000 Daniell, and I found that down to this limit the capacity of the platinum surfaces proved to be constant. By taking greater surfaces of platinum I suppose it will be possible to reach a limit much lower than that. If any chemical force existed besides that of the electrical charges, which could bind all the pairs of opposite ions together, and require any amount of work to be vanquished, an inferior limit to the electro-motive forces ought to exist, which forces are able to attract the atoms to the electrodes and to charge these as condensers. No phenomenon indicating such a limit has as yet been discovered, and we must conclude, therefore, that no other force resists the motions of the ions through the interior of the liquid than the mutual attractions of their electric charges.
On the contrary, as soon as an ion is to be separated from its electrical charge we find that the electrical forces of the battery meet with a powerful resistance, the overpowering of which requires a good deal of work to be done. Usually the ions, losing their electric charges, are separated at the same time from the liquid; some of them are evolved as gases, others are deposited as rigid strata on the surface of the electrodes, like galvanoplastic copper. But the union of two constituents having powerful affinity to form a chemical compound, as you know very well, produces always a great amount of heat, and heat is equivalent to work. On the contrary, decomposition of the compound substances requires work, because it restores the energy of the chemical forces which has been spent by the act of combination.
Metals uniting with oxygen or halogens produce heat in the same way, some of them, like potassium, sodium, zinc, even more heat than an equivalent quantity of hydrogen; less oxidizable metals, like copper, silver, platinum, less. We find, therefore, that heat is generated when zinc drives copper out of its combination with the compound halogen of sulphuric acid, as is the case in a Daniell's cell.
If a galvanic current passes through any conductor, a metallic wire, or an electrolytic fluid, it evolves heat. Mr. Prescott Joule was the first who proved experimentally that, if no other work is done by the current, the total amount of heat evolved in a galvanic circuit during a certain time is exactly equal to that which ought to have been generated by the chemical actions which have been performed during that time. But this heat is not evolved at the surface of the electrodes, where these chemical actions take place, but is evolved in all the parts of the circuit, proportionally to the galvanic resistance of every part. From this it is evident that the heat evolved is an immediate effect, not of the chemical action, but of the galvanic current, and that the chemical work of the battery has been spent in producing only the electric action.
If we apply Faraday's law, a definite amount of electricity passing through the circuit corresponds to a definite amount of chemical decomposition going on in every electrolytic cell of the same circuit. According to the theory of electricity, the work done by such a definite quantity of electricity which passes, producing a current, is proportionate to the electro-motive force acting between both ends of the conductor. You see, therefore, that the electro-motive force of a galvanic circuit must be, and is, indeed, proportionate to the heat generated by the sum of all the chemical actions going on in all the electrolytic cells during the passage of the same quantity of electricity. In cells of the galvanic battery chemical forces are brought into action able to produce work; in cells in which decomposition is occurring work must be done against opposing chemical forces; the rest of the work done appears as heat evolved by the current, as far as it is not used up to produce motions of magnets or other equivalents of work.
Hitherto we have supposed that the ion with its electric charge is separated from the fluid. But the ponderable atoms can give off their electricity to the electrode and remain in the liquid, being now electrically neutral. This makes almost no difference in the value of the electro-motive force. For instance, if chlorine is separated at the anode it will remain at first absorbed by the liquid; if the solution becomes saturated, or if we make a vacuum over the liquid, the gas will rise in bubbles. The electro-motive force remains unaltered. The same may be observed with all the other gases. You see in this case that the change of electrically negative chlorine into neutral chlorine is the process which requires so great an amount of work, even if the ponderable matter of the atoms remains where it was.
The more the surface of the positive electrode is covered with negative atoms of the anion and the negative with the positive ones of the cation, the more the attracting force of the electrodes exerted upon the ions of the liquid is diminished by this second stratum of opposite electricity covering them. On the contrary, the force with which the positive electricity of an atom of hydrogen is attracted toward the negatively charged metal increases in proportion as more negative electricity collects before it on the metal and the more negative electricity collects behind it in the fluid.
Such is the mechanism by which electric force is concentrated and increased in its intensity to such a degree that it becomes able to overpower the mightiest chemical affinities we know of. If this can be done by a polarized surface, acting like a condenser, charged by a very moderate electro-motive force, can the attractions between the enormous electric charges of anions and cations play an unimportant and indifferent part in chemical affinity?
You see, therefore, if we use the language of the dualistic theory and treat positive and negative electricities as two substances, the phenomena are the same as if equivalents of positive and negative electricity were attracted by different atoms, and perhaps also by the different values of affinity belonging to the same atom, with different force. Potassium, sodium, zinc, must have strong attraction to a positive charge; oxygen, chlorine, bromine, to a negative charge.
Faraday very often recurs to this to express his conviction that the forces termed chemical affinity and electricity are one and the same. I have endeavored to give you a survey of the facts in their mutual connection, avoiding, as far as possible, introducing other hypotheses, except the atomic theory of modern chemistry. I think the facts leave no doubt that the very mightiest among the chemical forces are of electric origin. The atoms cling to their electric charges and the opposite electric charges cling to the atoms. But I don't suppose that other molecular forces are excluded, working directly from atom to atom. Several of our leading chemists have begun lately to distinguish two classes of compounds, molecular aggregates and typical compounds. The latter are united by atomic affinities, the former not. Electrolytes belong to the latter class.
If we conclude from the facts that every unit of affinity of every atom is charged always with one equivalent, either of positive or of negative electricity, they can form compounds, being electrically neutral, only if every unit charged positively unites under the influence of a mighty electric attraction with another unit charged negatively. You see that this ought to produce compounds in which every unit of affinity of every atom is connected with one and only with one other unit of another atom. This is, as you will see immediately, indeed, the modern chemical theory of quantivalence, comprising all the saturated compounds. The fact that even elementary substances, with few exceptions, have molecules composed of two atoms, makes it probable that even in these cases electric neutralization is produced by the combination of two atoms, each charged with its electric equivalent, not by neutralization of every single unit of affinity.
But I abstain from entering into mere specialties, as, for instance, the question of unsaturated compounds; perhaps I have gone already too far. I would not have dared to do it if I did not feel myself sheltered by the authority of that great man who was guided by a never-erring instinct of truth. I thought that the best I could do for his memory was to recall to the minds of the men, by the energy and intelligence of whom chemistry has undergone its modern astonishing development, what important treasures of knowledge lie still hidden in the works of that wonderful genius. I am not sufficiently acquainted with chemistry to be confident that I have given the right interpretation—that interpretation which Faraday himself would have given, perhaps, if he had known the law of chemical quantivalence, if he had had the experimental means of ascertaining how large the extent, how unexceptional the accuracy of his law really is; and if he had known the precise formulation of the law of energy applied to chemical work, and of the laws which determine the distribution of electric forces in space as well as in ponderable bodies, transmitting electric current or forming condensers. I shall consider my work of to-day well rewarded if I have succeeded in kindling anew the interest of chemists for the electro-chemical part of their science.
- The Faraday Lecture, delivered before the Fellows of the Chemical Society in the Theatre of the Royal Institution, London, on Tuesday, April 5, 1881, by Professor Helmholtz. Abstract revised by the author.