Electrolytic Dissociation

Section 4

Professor Van t’Hoff acknowledged that many solutions formed very notable exceptions which were very irregular.

The analogy with gases did not seem to be maintained, for the osmotic pressure had a very different value from that indicated by the theory.

Everything, however, came right if one multiplied by a factor, determined according to each case, but greater than unity, the constant of the characteristic formula.

Similar divergences were manifested in the delays observed in congelation, and disappeared when subjected to an analogous correction.

Thus, the freezing-point of a normal solution, containing a molecule gramme (that is, the number of grammes equal to the figure representing the molecular mass) of alcohol or sugar in water, falls 1.85° C.

If the laws of solution were identically the same for a solution of sea-salt, the same depression should be noticed in a saline solution also containing 1 molecule per litre.

In fact, the fall reaches 3.26°, and the solution behaves as if it contained, not 1, but 1.75 normal molecules per litre. The consideration of the osmotic pressures would lead to similar observations, but we know that the experiment would be more difficult and less precise.

We may wonder whether anything really analogous to this can be met with in the case of a gas, and we are thus led to consider the phenomena of dissociation. [18]

If we heat a body which, in a gaseous state, is capable of dissociation—hydriodic acid, for example—at a given temperature, an equilibrium is established between three gaseous bodies, the acid, the iodine, and the hydrogen.

The total mass will follow with fair closeness Mariotte’s law, but the characteristic constant will no longer be the same as in the case of a non-dissociated gas. We here no longer have to do with a single molecule, since each molecule is in part dissociated.

The comparison of the two cases leads to the employment of a new image for representing the phenomenon which has been produced throughout the saline solution. We have introduced a single molecule of salt, and everything occurs as if there were 1.75 molecules.

May it not really be said that the number is 1.75, because the sea-salt is partly dissociated, and a molecule has become transformed into 0.75 molecule of sodium, 0.75 of chlorium, and 0.25 of salt?

This is a way of speaking which seems, at first sight, strangely contradicted by experiment.

Professor Van t’ Hoff, like other chemists, would certainly have rejected—in fact, he did so at first—such a conception, if, about the same time, an illustrious Swedish scholar, M. Arrhenius, had not been brought to the same idea by another road, and, had not by stating it precisely and modifying it, presented it in an acceptable form.

A brief examination will easily show that all the substances which are exceptions to the laws of Van t’Hoff are precisely those which are capable of conducting electricity when undergoing decomposition—that is to say, are electrolytes. The coincidence is absolute, and cannot be simply due to chance.

Now, the phenomena of electrolysis have, for a long time, forced upon us an almost necessary image. The saline molecule is always decomposed, as we know, in the primary phenomenon of electrolysis into two elements which Faraday termed ions. Secondary reactions, no doubt, often come to complicate the question, but these are chemical reactions belonging to the general order of things, and have nothing to do with the electric action working on the solution. The simple phenomenon is always the same—decomposition into two ions, followed by the appearance of one of these ions at the positive and of the other at the negative electrode. But as the very slightest expenditure of energy is sufficient to produce the commencement of electrolysis, it is necessary to suppose that these two ions are not united by any force. Thus the two ions are, in a way, dissociated. Clausius, who was the first to represent the phenomena by this symbol, supposed, in order not to shock the feelings of chemists too much, that this dissociation only affected an infinitesimal fraction of the total number of the molecules of the salt, and thereby escaped all check.

This concession was unfortunate, and the hypothesis thus lost the greater part of its usefulness. M. Arrhenius was bolder, and frankly recognized that dissociation occurs at once in the case of a great number of molecules, and tends to increase more and more as the solution becomes more dilute. It follows the comparison with a gas which, while partially dissociated in an enclosed space, becomes wholly so in an infinite one.

M. Arrhenius was led to adopt this hypothesis by the examination of experimental results relating to the conductivity of electrolytes. In order to interpret certain facts, it has to be recognized that a part only of the molecules in a saline solution can be considered as conductors of electricity, and that by adding water the number of molecular conductors is increased. This increase, too, though rapid at first, soon becomes slower, and approaches a certain limit which an infinite dilution would enable it to attain. If the conducting molecules are the dissociated molecules, then the dissociation (so long as it is a question of strong acids and salts) tends to become complete in the case of an unlimited dilution.

The opposition of a large number of chemists and physicists to the ideas of M. Arrhenius was at first very fierce. It must be noted with regret that, in France particularly, recourse was had to an arm which scholars often wield rather clumsily. They joked about these free ions in solution, and they asked to see this chlorine and this sodium which swam about the water in a state of liberty. But in science, as elsewhere, irony is not argument, and it soon had to be acknowledged that the hypothesis of M. Arrhenius showed itself singularly fertile and had to be regarded, at all events, as a very expressive image, if not, indeed, entirely in conformity with reality.

It would certainly be contrary to all experience, and even to common sense itself, to suppose that in dissolved chloride of sodium there is really free sodium, if we suppose these atoms of sodium to be absolutely identical with ordinary atoms. But there is a great difference. In the one case the atoms are electrified, and carry a relatively considerable positive charge, inseparable from their state as ions, while in the other they are in the neutral state. We may suppose that the presence of this charge brings about modifications as extensive as one pleases in the chemical properties of the atom. Thus the hypothesis will be removed from all discussion of a chemical order, since it will have been made plastic enough beforehand to adapt itself to all the known facts; and if we object that sodium cannot subsist in water because it instantaneously decomposes the latter, the answer is simply that the sodium ion does not decompose water as does ordinary sodium.

Still, other objections might be raised which could not be so easily refuted. One, to which chemists not unreasonably attached great importance, was this:—If a certain quantity of chloride of sodium is dissociated into chlorine and sodium, it should be possible, by diffusion, for example, which brings out plainly the phenomena of dissociation in gases, to extract from the solution a part either of the chlorine or of the sodium, while the corresponding part of the other compound would remain. This result would be in flagrant contradiction with the fact that, everywhere and always, a solution of salt contains strictly the same proportions of its component elements.

M. Arrhenius answers to this that the electrical forces in ordinary conditions prevent separation by diffusion or by any other process. Professor Nernst goes further, and has shown that the concentration currents which are produced when two electrodes of the same substance are plunged into two unequally concentrated solutions may be interpreted by the hypothesis that, in these particular conditions, the diffusion does bring about a separation of the ions. Thus the argument is turned round, and the proof supposed to be given of the incorrectness of the theory becomes a further reason in its favour.

It is possible, no doubt, to adduce a few other experiments which are not very favourable to M. Arrhenius’s point of view, but they are isolated cases; and, on the whole, his theory has enabled many isolated facts, till then scattered, to be co-ordinated, and has allowed very varied phenomena to be linked together. It has also suggested—and, moreover, still daily suggests—researches of the highest order.

In the first place, the theory of Arrhenius explains electrolysis very simply. The ions which, so to speak, wander about haphazard, and are uniformly distributed throughout the liquid, steer a regular course as soon as we dip in the trough containing the electrolyte the two electrodes connected with the poles of the dynamo or generator of electricity. Then the charged positive ions travel in the direction of the electromotive force and the negative ions in the opposite direction. On reaching the electrodes they yield up to them the charges they carry, and thus pass from the state of ion into that of ordinary atom. Moreover, for the solution to remain in equilibrium, the vanished ions must be immediately replaced by others, and thus the state of ionisation of the electrolyte remains constant and its conductivity persists.

All the peculiarities of electrolysis are capable of interpretation: the phenomena of the transport of ions, the fine experiments of M. Bouty, those of Professor Kohlrausch and of Professor Ostwald on various points in electrolytic conduction, all support the theory. The verifications of it can even be quantitative, and we can foresee numerical relations between conductivity and other phenomena. The measurement of the conductivity permits the number of molecules dissociated in a given solution to be calculated, and the number is thus found to be precisely the same as that arrived at if it is wished to remove the disagreement between reality and the anticipations which result from the theory of Professor Van t’ Hoff. The laws of cryoscopy, of tonometry, and of osmosis thus again become strict, and no exception to them remains.

If the dissociation of salts is a reality and is complete in a dilute solution, any of the properties of a saline solution whatever should be represented numerically as the sum of three values, of which one concerns the positive ion, a second the negative ion, and the third the solvent. The properties of the solutions would then be what are called additive properties. Numerous verifications may be attempted by very different roads. They generally succeed very well; and whether we measure the electric conductivity, the density, the specific heats, the index of refraction, the power of rotatory polarization, the colour, or the absorption spectrum, the additive property will everywhere be found in the solution.

The hypothesis, so contested at the outset by the chemists, is, moreover, assuring its triumph by important conquests in the domain of chemistry itself. It permits us to give a vivid explanation of chemical reaction, and for the old motto of the chemists, “Corpora non agunt, nisi soluta,” it substitutes a modern one, “It is especially the ions which react.” Thus, for example, all salts of iron, which contain iron in the state of ions, give similar reactions; but salts such as ferrocyanide of potassium, in which iron does not play the part of an ion, never give the characteristic reactions of iron.

Professor Ostwald and his pupils have drawn from the hypothesis of Arrhenius manifold consequences which have been the cause of considerable progress in physical chemistry. Professor Ostwald has shown, in particular, how this hypothesis permits the quantitative calculation of the conditions of equilibrium of electrolytes and solutions, and especially of the phenomena of neutralization. If a dissolved salt is partly dissociated into ions, this solution must be limited by an equilibrium between the non-dissociated molecule and the two ions resulting from the dissociation; and, assimilating the phenomenon to the case of gases, we may take for its study the laws of Gibbs and of Guldberg and Waage. The results are generally very satisfactory, and new researches daily furnish new checks.

Professor Nernst, who before gave, as has been said, a remarkable interpretation of the diffusion of electrolytes, has, in the direction pointed out by M. Arrhenius, developed a theory of the entire phenomena of electrolysis, which, in particular, furnishes a striking explanation of the mechanism of the production of electromotive force in galvanic batteries.

Extending the analogy, already so happily invoked, between the phenomena met with in solutions and those produced in gases, Professor Nernst supposes that metals tend, as it were, to vaporize when in presence of a liquid.

A piece of zinc introduced, for example, into pure water gives birth to a few metallic ions. These ions become positively charged, while the metal naturally takes an equal charge, but of contrary sign. Thus the solution and the metal are both electrified;

But this sort of vaporization is hindered by electrostatic attraction, and as the charges borne by the ions are considerable, an equilibrium will be established, although the number of ions which enter the solution will be very small.

If the liquid, instead of being a solvent like pure water, contains an electrolyte, it already contains metallic ions, the osmotic pressure of which will be opposite to that of the solution. Three cases may then present themselves—either there will be equilibrium, or the electrostatic attraction will oppose itself to the pressure of solution and the metal will be negatively charged, or, finally, the attraction will act in the same direction as the pressure, and the metal will become positively and the solution negatively charged.

developed this idea, Professor Nernst calculates, by means of the action of the osmotic pressures, the variations of energy brought into play and the value of the differences of potential by the contact of the electrodes and electrolytes. He deduces this from the electromotive force of a single battery cell which becomes thus connected with the values of the osmotic pressures, or, if you will, thanks to the relation discovered by Van t’ Hoff, with the concentrations. Some particularly interesting electrical phenomena thus become connected with an already very important group, and a new bridge is built which unites two regions long considered foreign to each other.

The recent discoveries on the phenomena produced in gases when rendered conductors of electricity almost force upon us, as we shall see, the idea that there exist in these gases electrified centres moving through the field, and this idea gives still greater probability to the analogous theory explaining the mechanism of the conductivity of liquids. It will also be useful, in order to avoid confusion, to restate with precision this notion of electrolytic ions, and to ascertain their magnitude, charge, and velocity.

The two classic laws of Faraday will supply us with important information. The first indicates that the quantity of electricity passing through the liquid is proportional to the quantity of matter deposited on the electrodes. This leads us at once to the consideration that, in any given solution, all the ions possess individual charges equal in absolute value.

The second law may be stated in these terms: an atom-gramme of metal carries with it into electrolysis a quantity of electricity proportionate to its valency. [19]

Numerous experiments have made known the total mass of hydrogen capable of carrying one coulomb, and it will therefore be possible to estimate the charge of an ion of hydrogen if the number of atoms of hydrogen in a given mass be known.

This last figure is already furnished by considerations derived from the kinetic theory, and agrees with the one which can be deduced from the study of various phenomena. The result is that an ion of hydrogen having a mass of 1.3 x 10^-20 grammes bears a charge of 1.3 X 10^-20 electromagnetic units; and the second law will immediately enable the charge of any other ion to be similarly estimated.

The measurements of conductivity, joined to certain considerations relating to the differences of concentration which appear round the electrode in electrolysis, allow the speed of the ions to be calculated.

Thus, in a liquid containing 1/10th of a hydrogen-ion per litre, the absolute speed of an ion would be 3/10ths of a millimetre per second in a field where the fall of potential would be 1 volt per centimetre. Sir Oliver Lodge, who has made direct experiments to measure this speed, has obtained a figure very approximate to this. This value is very small compared to that which we shall meet with in gases.

Another consequence of the laws of Faraday, to which, as early as 1881, Helmholtz drew attention, may be considered as the starting-point of certain new doctrines we shall come across later.

Helmholtz says:

“If we accept the hypothesis that simple bodies are composed of atoms, we are obliged to admit that, in the same way, electricity, whether positive or negative, is composed of elementary parts which behave like atoms of electricity.”

The second law seems, in fact, analogous to the law of multiple proportions in chemistry, and it shows us that the quantities of electricity carried vary from the simple to the double or treble, according as it is a question of a uni-, bi-, or trivalent metal; and as the chemical law leads up to the conception of the material atom, so does the electrolytic law suggest the idea of an electric atom.