A Treatise on Electricity and Magnetism/Part II/Chapter V

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A Treatise on Electricity and Magnetism by James Clerk Maxwell
Part II, Chapter V: Electrolytic Polarization



264.] When an electric current is passed through an electrolyte bounded by metal electrodes, the accumulation of the ions at the electrodes produces the phenomenon called Polarization, which consists in an electromotive force acting in the opposite direction to the current, and producing an apparent increase of the resistance.

When a continuous current is employed, the resistance appears to increase rapidly from the commencement of the current, and at last reaches a value nearly constant. If the form of the vessel in which the electrolyte is contained is changed, the resistance is altered in the same way as a similar change of form of a metallic conductor would alter its resistance, but an additional apparent resistance, depending on the nature of the electrodes, has always to be added to the true resistance of the electrolyte.

265.] These phenomena have led some to suppose that there is a finite electromotive force required for a current to pass through an electrolyte. It has been shewn, however, by the researches of Lenz, Neumann, Beetz, Wiedemann[1], Paalzow[2], and recently by those of MM. F. Kohlrausch and W. A. Nippoldt[3], that the conduction in the electrolyte itself obeys Ohm s Law with the same precision as in metallic conductors, and that the apparent resistance at the bounding surface of the electrolyte and the electrodes is entirely due to polarization.

266.] The phenomenon called polarization manifests itself in the case of a continuous current by a diminution in the current, indicating a force opposed to the current. Resistance is also perceived as a force opposed to the current, but we can distinguish between the two phenomena by instantaneously removing or reversing the electromotive force.

The resisting force is always opposite in direction to the current, and the external electromotive force required to overcome it is proportional to the strength of the current, and changes its direction when the direction of the current is changed. If the external electromotive force becomes zero the current simply stops.

The electromotive force due to polarization, on the other hand, is in a fixed direction, opposed to the current which produced it. If the electromotive force which produced the current is removed, the polarization produces a current in the opposite direction.

The difference between the two phenomena may be compared with the difference between forcing a current of water through a long capillary tube, and forcing water through a tube of moderate length up into a cistern. In the first case if we remove the pressure which produces the flow the current will simply stop. In the second case, if we remove the pressure the water will begin to flow down again from the cistern.

To make the mechanical illustration more complete, we have only to suppose that the cistern is of moderate depth, so that when a certain amount of water is raised into it, it begins to overflow. This will represent the fact that the total electromotive force due to polarization has a maximum limit.

267.] The cause of polarization appears to be the existence at the electrodes of the products of the electrolytic decomposition of the fluid between them. The surfaces of the electrodes are thus rendered electrically different, and an electromotive force between them is called into action, the direction of which is opposite to that of the current which caused the polarization.

The ions, which by their presence at the electrodes produce the phenomena of polarization, are not in a perfectly free state, but are in a condition in which they adhere to the surface of the electrodes with considerable force.

The electromotive force due to polarization depends upon the density with which the electrode is covered with the ion, but it is not proportional to this density, for the electromotive force does not increase so rapidly as this density.

This deposit of the ion is constantly tending to become free, and either to diffuse into the liquid, to escape as a gas, or to be precipitated as a solid.

The rate of this dissipation of the polarization is exceedingly small for slight degrees of polarization, and exceedingly rapid near the limiting value of polarization.

268.] We have seen, Art. 262, that the electromotive force acting in any electrolytic process is numerically equal to the mechanical equivalent of the result of that process on one electrochemical equivalent of the substance. If the process involves a diminution of the intrinsic energy of the substances which take part in it, as in the voltaic cell, then the electromotive force is in the direction of the current. If the process involves an increase of the intrinsic energy of the substances, as in the case of the electrolytic cell, the electromotive force is in the direction opposite to that of the current, and this electromotive force is called polarization.

In the case of a steady current in which electrolysis goes on continuously, and the ions are separated in a free state at the electrodes, we have only by a suitable process to measure the intrinsic energy of the separated ions, and compare it with that of the electrolyte in order to calculate the electromotive force required for the electrolysis. This will give the maximum polarization.

But during the first instants of the process of electrolysis the ions when deposited at the electrodes are not in a free state, and their intrinsic energy is less than their energy in a free state, though greater than their energy when combined in the electrolyte. In fact, the ion in contact with the electrode is in a state which when the deposit is very thin may be compared with that of chemical combination with the electrode, but as the deposit increases in density, the succeeding portions are no longer so intimately combined with the electrode, but simply adhere to it, and at last the deposit, if gaseous, escapes in bubbles, if liquid, diffuses through the electrolyte, and if solid, forms a precipitate.

In studying polarization we have therefore to consider

(1) The superficial density of the deposit, which we may call σ. This quantity σ represents the number of electrochemical equivalents of the ion deposited on unit of area. Since each electrochemical equivalent deposited corresponds to one unit of electricity transmitted by the current, we may consider σ as representing either a surface-density of matter or a surface-density of electricity.

(2) The electromotive force of polarization, which we may call p. This quantity p is the difference between the electric potentials of the two electrodes when the current through the electrolyte is so feeble that the proper resistance of the electrolyte makes no sensible difference between these potentials.

The electromotive force p at any instant is numerically equal to the mechanical equivalent of the electrolytic process going on at that instant which corresponds to one electrochemical equivalent of the electrolyte. This electrolytic process, it must be remembered, consists in the deposit of the ions on the electrodes, and the state in which they are deposited depends on the actual state of the surface of the electrodes, which may be modified by previous deposits.

Hence the electromotive force at any instant depends on the previous history of the electrode. It is, speaking very roughly, a function of σ, the density of the deposit, such that p = 0 when σ = 0, but p approaches a limiting value much sooner than σ does. The statement, however, that p is a function of σ cannot be considered accurate. It would be more correct to say that p is a function of the chemical state of the superficial layer of the deposit, and that this state depends on the density of the deposit according to some law involving the time.

269.] (3) The third thing we must take into account is the dissipation of the polarization. The polarization when left to itself diminishes at a rate depending partly on the intensity of the polarization or the density of the deposit, and partly on the nature of the surrounding medium, and the chemical, mechanical, or thermal action to which the surface of the electrode is exposed.

If we determine a time T such that at the rate at which the deposit is dissipated, the whole deposit would be removed in a time T, we may call T the modulus of the time of dissipation. When the density of the deposit is very small, T is very large, and may be reckoned by days or months. When the density of the deposit approaches its limiting value T diminishes very rapidly, and is probably a minute fraction of a second. In fact, the rate of dissipation increases so rapidly that when the strength of the current is maintained constant, the separated gas, instead of contributing to increase the density of the deposit, escapes in bubbles as fast as it is formed.

270.] There is therefore a great difference between the state of polarization of the electrodes of an electrolytic cell when the polarization is feeble, and when it is at its maximum value. For instance, if a number of electrolytic cells of dilute sulphuric acid with platinum electrodes are arranged in series, and if a small electromotive force, such as that of one Daniell's cell, be made to act on the circuit, the electromotive force will produce a current of exceedingly short duration, for after a very short time the electromotive force arising from the polarization of the cell will balance that of the Daniell's cell.

The dissipation will be very small in the case of so feeble a state of polarization, and it will take place by a very slow absorption of the gases and diffusion through the liquid. The rate of this dissipation is indicated by the exceedingly feeble current which still continues to flow without any visible separation of gases.

If we neglect this dissipation for the short time during which the state of polarization is set up, and if we call Q the total quantity of electricity which is transmitted by the current during this time, then if A is the area of one of the electrodes, and \sigma the density of the deposit, supposed uniform,

Q = A\sigma.

If we now disconnect the electrodes of the electrolytic apparatus from the Daniell's cell, and connect them with a galvanometer capable of measuring the whole discharge through it, a quantity of electricity nearly equal to Q will be discharged as the polarization disappears.

271.] Hence we may compare the action of this apparatus, which is a form of Ritter's Secondary Pile, with that of a Leyden jar.

Both the secondary pile and the Leyden jar are capable of being charged with a certain amount of electricity, and of being afterwards discharged. During the discharge a quantity of electricity nearly equal to the charge passes in the opposite direction. The difference between the charge and the discharge arises partly from dissipation, a process which in the case of small charges is very slow, but which, when the charge exceeds a certain limit, becomes exceedingly rapid. Another part of the difference between the charge and the discharge arises from the fact that after the electrodes have been connected for a time sufficient to produce an apparently complete discharge, so that the current has completely disappeared, if we separate the electrodes for a time, and afterwards connect them, we obtain a second discharge in the same direction as the original discharge. This is called the residual discharge, and is a phenomenon of the Leyden jar as well as of the secondary pile.

The secondary pile may therefore be compared in several respects to a Leyden jar. There are, however 3 certain important differences. The charge of a Leyden jar is very exactly proportional to the electromotive force of the charge, that is, to the difference of potentials of the two surfaces, and the charge corresponding to unit of electromotive force is called the capacity of the jar, a constant quantity. The corresponding quantity, which may be called the capacity of the secondary pile, increases when the electromotive force increases.

The capacity of the jar depends on the area of the opposed surfaces, on the distance between them, and on the nature of the substance between them, but not on the nature of the metallic surfaces themselves. The capacity of the secondary pile depends on the area of the surfaces of the electrodes, but not on the distance between them, and it depends on the nature of the surface of the electrodes, as well as on that of the fluid between them. The maximum difference of the potentials of the electrodes in each element of a secondary pile is very small compared with the maximum difference of the potentials of those of a charged Leyden jar, so that in order to obtain much electromotive force a pile of many elements must be used.

On the other hand, the superficial density of the charge in the secondary pile is immensely greater than the utmost superficial density of the charge which can be accumulated on the surfaces of a Leyden jar, insomuch that Mr. C. F. Varley[4], in describing the construction of a condenser of great capacity, recommends a series of gold or platinum plates immersed in dilute acid as preferable in point of cheapness to induction plates of tinfoil separated by insulating material.

The form in which the energy of a Leyden jar is stored up is the state of constraint of the dielectric between the conducting surfaces, a state which I have already described under the name of electric polarization, pointing out those phenomena attending this state which are at present known, and indicating the imperfect state of our knowledge of what really takes place. See Arts. 62, 111.

The form in which the energy of the secondary pile is stored up is the chemical condition of the material stratum at the surface of the electrodes, consisting of the ions of the electrolyte and the substance of the electrodes in a relation varying from chemical combination to superficial condensation, mechanical adherence, or simple juxtaposition.

The seat of this energy is close to the surfaces of the electrodes, and not throughout the substance of the electrolyte, and the form in which it exists may be called electrolytic polarization.

After studying the secondary pile in connexion with the Leyden jar, the student should again compare the voltaic battery with some form of the electrical machine, such as that described in Art. 211.

Mr. Varley has lately[5] found that the capacity of one square inch is from 175 to 542 microfarads and upwards for platinum plates in dilute sulphuric acid, and that the capacity increases with the electromotive force, being about 175 for 0.02 of a Daniell's cell, and 542 for 1.6 Daniell's cells.

But the comparison between the Leyden jar and the secondary pile may be carried still farther, as in the following experiment, due to Buff[6]. It is only when the glass of the jar is cold that it is capable of retaining a charge. At a temperature below 100°C the glass becomes a conductor. If a test-tube containing mercury is placed in a vessel of mercury, and if a pair of electrodes are connected, one with the inner and the other with the outer portion of mercury, the arrangement constitutes a Leyden jar which will hold a charge at ordinary temperatures. If the electrodes are connected with those of a voltaic battery, no current will pass as long as the glass is cold, but if the apparatus is gradually heated a current will begin to pass, and will increase rapidly in intensity as the temperature rises, though the glass remains apparently as hard as ever.

This current is manifestly electrolytic, for if the electrodes are disconnected from the battery, and connected with a galvanometer, a considerable reverse current passes, due to polarization of the surfaces of the glass.

If, while the battery is in action the apparatus is cooled, the current is stopped by the cold glass as before, but the polarization of the surfaces remains. The mercury may be removed, the surfaces may be washed with nitric acid and with water, and fresh mercury introduced. If the apparatus is then heated, the current of polarization appears as soon as the glass is sufficiently warm to conduct it.

We may therefore regard glass at 100°C, though apparently a solid body, as an electrolyte, and there is considerable reason to believe that in most instances in which a dielectric has a slight degree of conductivity the conduction is electrolytic. The existence of polarization may be regarded as conclusive evidence of electrolysis, and if the conductivity of a substance increases as the temperature rises, we have good grounds for suspecting that it is electrolytic.

On Constant Voltaic Elements.

272.] When a series of experiments is made with a voltaic battery in which polarization occurs, the polarization diminishes during the time that the current is not flowing, so that when it begins to flow again the current is stronger than after it has flowed for some time. If, on the other hand, the resistance of the circuit is diminished by allowing the current to flow through a short shunt, then, when the current is again made to flow through the ordinary circuit, it is at first weaker than its normal strength on account of the great polarization produced by the use of the short circuit.

To get rid of these irregularities in the current, which are exceedingly troublesome in experiments involving exact measurements, it is necessary to get rid of the polarization, or at least to reduce it as much as possible.

It does not appear that there is much polarization at the surface of the zinc plate when immersed in a solution of sulphate of zinc or in dilute sulphuric acid. The principal seat of polarization is at the surface of the negative metal. When the fluid in which the negative metal is immersed is dilute sulphuric acid, it is seen to become covered with bubbles of hydrogen gas, arising from the electrolytic decomposition of the fluid. Of course these bubbles, by preventing the fluid from touching the metal, diminish the surface of contact and increase the resistance of the circuit. But besides the visible bubbles it is certain that there is a thin coating of hydrogen, probably not in a free state, adhering to the metal, and as we have seen that this coating is able to produce an electromotive force in the reverse direction, it must necessarily diminish the electromotive force of the battery.

Various plans have been adopted to get rid of this coating of hydrogen. It may be diminished to some extent by mechanical means, such as stirring the liquid, or rubbing the surface of the negative plate. In Smee's battery the negative plates are vertical, and covered with finely divided platinum from which the bubbles of hydrogen easily escape, and in their ascent produce a current of liquid which helps to brush off other bubbles as they are formed.

A far more efficacious method, however, is to employ chemical means. These are of two kinds. In the batteries of Grove and Bunsen the negative plate is immersed in a fluid rich in oxygen, and the hydrogen, instead of forming a coating on the plate, combines with this substance. In Grove's battery the plate is of platinum immersed in strong nitric acid. In Bunsen's first battery it is of carbon in the same acid. Chromic acid is also used for the same purpose, and has the advantage of being free from the acid fumes produced by the reduction of nitric acid.

A different mode of getting rid of the hydrogen is by using copper as the negative metal, and covering the surface with a coat of oxide. This, however, rapidly disappears when it is used as the negative electrode. To renew it Joule has proposed to make the copper plates in the form of disks, half immersed in the liquid, and to rotate them slowly, so that the air may act on the parts exposed to it in turn.

The other method is by using as the liquid an electrolyte, the cation of which is a metal highly negative to zinc.

In Daniell's battery a copper plate is immersed in a saturated solution of sulphate of copper. When the current flows through the solution from the zinc to the copper no hydrogen appears on the copper plate, but copper is deposited on it. When the solution is saturated, and the current is not too strong, the copper appears to act as a true cation, the anion SO4 travelling towards the zinc.

When these conditions are not fulfilled hydrogen is evolved at the cathode, but immediately acts on the solution, throwing down copper, and uniting with SO4 to form oil of vitriol. When this is the case, the sulphate of copper next the copper plate is replaced by oil of vitriol, the liquid becomes colourless, and polarization by hydrogen gas again takes place. The copper deposited in this way is of a looser and more friable structure than that deposited by true electrolysis.

To ensure that the liquid in contact with the copper shall be saturated with sulphate of copper, crystals of this substance must be placed in the liquid close to the copper, so that when the solution is made weak by the deposition of the copper, more of the crystals may be dissolved.

We have seen that it is necessary that the liquid next the copper should be saturated with sulphate of copper. It is still more necessary that the liquid in which the zinc is immersed should be free from sulphate of copper. If any of this salt makes its way to the surface of the zinc it is reduced, and copper is deposited on the zinc. The zinc, copper, and fluid then form a little circuit in which rapid electrolytic action goes on, and the zinc is eaten away by an action which contributes nothing to the useful effect of the battery.

To prevent this, the zinc is immersed either in dilute sulphuric acid or in a solution of sulphate of zinc, and to prevent the solution of sulphate of copper from mixing with this liquid, the two liquids are separated by a division consisting of bladder or porous earthenware, which allows electrolysis to take place through it, but effectually prevents mixture of the fluids by visible currents.

In some batteries sawdust is used to prevent currents. The experiments of Graham, however, shew that the process of diffusion goes on nearly as rapidly when two liquids are separated by a division of this kind as when they are in direct contact, provided there are no visible currents, and it is probable that if a septum is employed which diminishes the diffusion, it will increase in exactly the same ratio the resistance of the element, because electrolytic conduction is a process the mathematical laws of which have the same form as those of diffusion, and whatever interferes with one must interfere equally with the other. The only difference is that diffusion is always going on, while the current flows only when the battery is in action.

In all forms of Daniell's battery the final result is that the sulphate of copper finds its way to the zinc and spoils the battery. To retard this result indefinitely, Sir W. Thomson[7] has constructed Darnell's battery in the following form.

Fig. 21.

In each cell the copper plate is placed horizontally at the bottom and a saturated solution of sulphate of zinc is poured over it. The zinc is in the form of a grating and is placed horizontally near the surface of the solution. A glass tube is placed vertically in the solution with its lower end just above the surface of the copper plate. Crystals of sulphate of copper are dropped down this tube, and, dissolving in the liquid, form a solution of greater density than that of sulphate of zinc alone, so that it cannot get to the zinc except by diffusion. To retard this process of diffusion, a siphon, consisting of a glass tube stuffed with cotton wick, is placed with one extremity midway between the zinc and copper, and the other in a vessel outside the cell, so that the liquid is very slowly drawn off near the middle of its depth. To supply its place, water, or a weak solution of sulphate of zinc, is added above when required. In this way the greater part of the sulphate of copper rising through the liquid by diffusion is drawn off by the siphon before it reaches the zinc, and the zinc is surrounded by liquid nearly free from sulphate of copper, and having a very slow downward motion in the cell, which still further retards the upward motion of the sulphate of copper. During the action of the battery copper is deposited on the copper plate, and SO4 travels slowly through the liquid to the zinc with which it combines, forming sulphate of zinc. Thus the liquid at the bottom becomes less dense by the deposition of the copper, and the liquid at the top becomes more dense by the addition of the zinc. To prevent this action from changing the order of density of the strata, and so producing instability and visible currents in the vessel, care must be taken to keep the tube well supplied with crystals of sulphate of copper, and to feed the cell above with a solution of sulphate of zinc sufficiently dilute to be lighter than any other stratum of the liquid in the cell.

Daniell's battery is by no means the most powerful in common use. The electromotive force of Grove's cell is 192,000,000, of Daniell's 107,900,000 and that of Bunsen's 188,000,000.

The resistance of Daniell's cell is in general greater than that of Grove's or Bunsen's of the same size.

These defects, however, are more than counterbalanced in all cases where exact measurements are required, by the fact that Daniell's cell exceeds every other known arrangement in constancy of electromotive force. It has also the advantage of continuing in working order for a long time, and of emitting no gas.

  1. Galvanismus, bd. i.
  2. Berlin Monatsbericht, July, 1868.
  3. Pogg, Ann. bd. cxxxviii. s. 286 (October, 1869).
  4. Specification of C. F. Varley, 'Electric Telegraphs, &c.,' Jan. 1860.
  5. Proc. R. S., Jan. 12, 1871.
  6. Annalen der Chemie und Pharmacie, bd. xc. 257 (1854).
  7. Proc. R. S., Jan. 19, 1871.