Yet up to now we hardly know of any other source for the excitation of electricity on metallic contact. According to Naumann (Allg. u. phys. Chemie [General and Physical Chemistry], Heidelberg, 1877, p. 675), "the contact-electromotive forces convert heat into electricity"; he finds "the assumption natural that the ability of these forces to produce electric motion depends on the quantity of heat present, or, in other words, that it is a function of the temperature," as has also been proved experimentally by Le Roux. Here too we find ourselves groping in the dark. The law of the voltaic series of metals forbids us to have recourse to the chemical processes that to a small extent are continually taking place at the contact surfaces, which are always covered by a thin layer of air and impure water, a layer as good as inseparable as far as we are concerned. An electrolyte should produce a constant current in the circuit, but the electricity of mere metallic contact, on the contrary, disappears on closing the circuit. And here we come to the real point: whether, and in what manner, the production of a constant current on the contact of chemically indifferent bodies is made possible by this "electric force of separation," which Wiedemann himself first of all restricted to metals, declaring it incapable of functioning without energy being supplied from outside, and then referred exclusively to a truly microscopical source of energy.
The voltaic series arranges the metals in such a sequence that each one behaves as electro-negative in relation to the preceding one and as electro-positive in relation to the one that follows it. Hence if we arrange a series of pieces of metal in this order, e.g. zinc, tin, iron, copper, platinum, we shall be able to obtain differences of electric potential at the two ends. If, however, we arrange the series of metals to form a circuit so that the zinc and platinum are in contact, the electric stress is at once neutralised and disappears. "Therefore the production of a constant current of electricity is not possible in a closed circuit of bodies belonging to the voltaic series." Wiedemann further supports this statement by the following theoretical consideration:
"In fact, if a constant electric current were to make its appearance in the circuit, it would produce heat in the metallic conductors themselves, and this heating could at the most be counterbalanced by cooling at the metallic junctions. In any case it would give rise to an uneven distribution of heat; moreover an electro-magnetic motor could be driven continuously by the current without any sort of supply from outside, and thus work would be performed, which is impossible, since on firmly joining the metals, for instance by soldering, no further changes to compensate for this work could take place even at the contact surfaces."
...For the time being, therefore, we put on record that Wiedemann's second explanation of the current gives us just as little assistance as his first one, and let us proceed further with the text:
"This process proves that the behaviour of the binary substance between the metals does not consist merely in a simple predominant attraction of its entire mass for one electricity or the other, as in the case of metals, but that in addition a special action of its constituents is exhibited. Since the constituent Cl is given off where the current of positive electricity enters the fluid, and the constituent H where the negative electricity enters, we assume that each equivalent of chlorine in the compound HCl is charged with a definite amount of negative electricity determining its attraction by the entering positive electricity. It is the electro-negative constituent of the compound. Similarly the equivalent H must be charged with positive electricity and so represent the electro-positive constituent of the compound. These charges could be produced on the combination of H and Cl in just the same way as on the contact of zinc and copper. Since the compound HCl as such is non-electric, we must assume accordingly that in it the atoms of the positive and negative constituents contain equal quantities of positive and negative electricity.
If now a zinc plate and a copper plate are dipped in dilute hydrochloric acid, we can suppose that the zinc has a stronger attraction towards the electro-negative constituent (Cl) than towards the electropositive one (H). Consequently, the molecules of hydrochloric acid in contact with the zinc would dispose themselves so that their electro- negative constituents are turned towards the zinc, and their electro-positive constituents towards the copper. Owing to the constituents when so arranged exerting their electrical attraction on the constituents of the next molecules of HCl, the whole series of molecules between the zinc and copper plates becomes arranged as in Fig. 10:
- Zinc Copper +
- + - + - + - + - +
Cl H Cl H Cl H Cl H Cl H
If the second metal acts on the positive hydrogen as the zinc does on the negative chlorine, it would help to promote the arrangement. If it acted in the opposite manner, only more weakly, at least the direction would remain unaltered.
By the influence exerted by the negative electricity of the electro-negative constituent Cl adjacent to the zinc, the electricity would be so distributed in the zinc that places on it which are close to the Cl of the immediately adjacent atom of acid would become charged positively, those farther away negatively.
Similarly, negative electricity would accumulate in the .copper next to the electro-positive constituent (H) of the adjacent atom of hydrochloric acid, and the positive electricity would be driven to the more remote parts.
Next, the positive electricity in the zinc would combine with the negative electricity of the immediately adjacent atom of Cl, and the latter itself with the zinc, to form non-electric ZnCl2. The electro-positive atom H, which was previously combined with this atom of Cl, would unite with the atom of Cl turned towards it belonging to the second atom of HCl, with simultaneous combination of the electricities contained in these atoms; similarly, the H of the second atom of HCl would combine with the Cl of the third atom, and so on, until finally an atom of H would be set free on the copper, the positive electricity of which would unite with the distributed negative electricity of the copper, so that it escapes in a non-electrified condition." This process would "repeat itself until the repulsive action of the electricities accumulated in the metal plates on the electricities of the hydrochloric acid constituents turned towards them balances the chemical attraction of the latter by the metals. If, however, the metal plates are joined by a conductor, the free electricities of the metal plates unite with one another and the above-mentioned processes can recommence. In this way a constant current of electricity comes into being. - It is evident that in the course of it a continual loss of vis viva occurs, owing to the constituents of the binary compound on their migration to the metals moving to the latter with a definite velocity and then coming to rest, either with formation of a compound (ZnCl2) or by escaping in the free state (H). (Note [by Wiedemann]: Since the gain in vis viva on separation of the constituents Cl and H ... is compensated by the vis viva lost on the union of these constituents with the constituents of the adjacent atoms, the influence of this process can be neglected.) This loss of vis viva is equivalent to the quantity of heat which is set free in the visibly occurring chemical process, essentially, therefore, that produced on the solution of an equivalent of zinc in the dilute acid. This value must be the same as that of the work expended on separating the electricities. If, therefore, the electricities unite to form a current, then, during the solution of an equivalent of zinc and the giving off of an equivalent of hydrogen from the liquid, there must make its appearance in the whole circuit, whether in the form of heat or in the form of external performance of work, an amount of work that is likewise equivalent to the development of heat corresponding to this chemical process."
"Let us assume - could - we must assume - we can suppose - would be distributed - would become charged," etc., etc. Sheer conjecture and subjunctives from which only three actual indicatives can be definitely extracted: firstly, that the combination of the zinc with the chlorine is now pronounced to be the condition for the liberation of hydrogen; secondly, as we now learn right at the end and as it were incidentally, that the energy herewith liberated is the source, and indeed the exclusive source, of all energy required for formation of the current; and thirdly, that this explanation of the current formation is as directly in contradiction to both those previously given as the latter are themselves mutually contradictory.
Further it is said:
"For the formation of a constant current, therefore, there is active wholly and solely the electric force of separation which is derived from the unequal attraction and polarisation of the atoms of the binary compound in the exciting liquid of the battery by the metal electrodes; at the place of contact of the metals, at which no further mechanical changes can occur, the electric force of separation must on the other hand be inactive. That this force, if by chance it counteracts the electromotive excitation of the metals by the liquid (as on immersion of zinc and lead in potassium cyanide solution), is not compensated by a definite share of the force of separation at the place of contact, is proved by the above-mentioned complete proportionality of the total electric force of separation (and electromotive force) in the circuit, with the abovementioned heat equivalent of the chemical process. Hence it must be neutralised in another way. This would most simply occur on the assumption that on contact of the exciting liquid with the metals the electromotive force is produced in a double manner; on the one hand by an unequally strong attraction of the mass of the liquid as a whole towards one or the other electricity, on the other hand by the unequal attraction of the metals towards the constituents of the liquid charged with opposite electricities. ... Owing to the former unequal (mass) attraction towards the electricities, the liquids would fully conform to the law of the voltaic series of metals, and in a closed circuit ... complete neutralisation to zero of the electric forces of separation (and electromotive forces) take place; the second (chemical) action ... on the other hand would be provided solely by the electric force of separation necessary for formation of the current and the corresponding electromotive force." (I, pp. 52-3.)
http://www.marxists.org/archive/marx/works/1883/don/ch06.htm
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