1911 Encyclopædia Britannica/Conduction, Electric/Liquids
Through liquid metals, such as mercury at ordinary temperatures and other metals at temperatures above their melting points, the electric current flows as in solid metals without changing the state of the conductor, except in so far as heat is developed by the electric resistance. But another class of liquid conductors exists, and in them the phenomena are quite different. The conductivity of fused salts, and of solutions of salts and acids, although less than that of metals, is very great compared with the traces of conductivity found in so-called non-conductors. In fused salts and conducting solutions the passage of the current is always accompanied by definite chemical changes; the substance of the conductor or electrolyte is decomposed, and the products of the decomposition appear at the electrodes, i.e. the metallic plates by means of which the current is led into and out of the solution. The chemical phenomena are considered in the article Electrolysis; we are here concerned solely with the mechanism of this electrolytic conduction of the current.
To explain the appearance of the products of decomposition at the electrodes only, while the intervening solution is unaltered, we suppose that, under the action of the electric forces, the opposite parts of the electrolyte move in opposite directions through the liquid. These opposite parts, named ions by Faraday, must therefore be associated with electric charges, and it is the convective movement of the opposite streams of ions carrying their charges with them that, on this view, constitutes the electric current.
In metallic conduction it is found that the current is proportional to the applied electromotive force—a relation known by the name of Ohm’s law. If we place in a circuit with a small electromotive force an electrolytic cell consisting of two platinum electrodes and a solution, the initial current soon dies away, and we shall find that a certain minimum electromotive force must be applied to the circuit before any considerable permanent current passes. The chemical changes which are initiated on the surfaces of the electrodes set up a reverse electromotive force of polarization, and, until this is overcome, only a minute current, probably due to the slow but steady removal of the products of decomposition from the electrodes by a process of diffusion, will pass through the cell. Thus it is evident that, considering the electrolytic cell as a whole, the passage of the current through it cannot conform to Ohm’s law. But the polarization is due to chemical changes, which are confined to the surfaces of the electrodes; and it is necessary to inquire whether, if the polarization at the electrodes be eliminated, the passage of the current through the bulk of the solution itself is proportional to the electromotive force actually applied to that solution. Rough experiment shows that the current is proportional to the excess of the electromotive force over a constant value, and thus verifies the law approximately, the constant electromotive force to be overcome being a measure of the polarization. A more satisfactory examination of the question was made by F. Kohlrausch in the years 1873 to 1876. Ohm’s law states that the current C is proportional to the electromotive force E, or C = kR, where k is a constant called the conductivity of the circuit. The equation may also be written as C = E/R, where R is a constant, the reciprocal of k, known as the resistance of the circuit. The essence of the law is the proportionality between C and E, which means that the ratio E/C is a constant. But E/C = R, and thus the law may be tested by examining the constancy of the measured resistance of a conductor when different currents are passing through it. In this way Ohm’s law has been confirmed in the case of metallic conduction to a very high degree of accuracy. A similar principle was applied by Kohlrausch to the case of electrolytes, and he was the first to show that an electrolyte possesses a definite resistance which has a constant value when measured with different currents and by different experimental methods.
Measurement of the Resistance of Electrolytes.—There are two effects of the passage of an electric current which prevent the possibility of measuring electrolytic resistance by the ordinary methods with the direct currents which are used in the case of metals. The products of the chemical decomposition of the electrolyte appear at the electrodes and set up the opposing electromotive force of polarization, and unequal dilution of the solution may occur in the neighbourhood of the two electrodes. The chemical and electrolytic aspects of these phenomena are treated in the article Electrolysis, but from our present point of view also it is evident that they are again of fundamental importance. The polarization at the surface of the electrodes will set up an opposing electromotive force, and the unequal dilution of the solution will turn the electrolyte into a concentration cell and produce a subsidiary electromotive force either in the same direction as that applied or in the reverse according as the anode or the cathode solution becomes the more dilute. Both effects thus involve internal electromotive forces, and prevent the application of Ohm’s law to the electrolytic cell as a whole. But the existence of a definite measurable resistance as a characteristic property of the system depends on the conformity of the system to Ohm’s law, and it is therefore necessary to eliminate both these effects before attempting to measure the resistance.
The usual and most satisfactory method of measuring the resistance of electrolytes consists in eliminating the effects of polarization by the use of alternating currents, that is, currents that are reversed in direction many times a second.[1] The chemical action produced by the first current is thus reversed by the second current in the opposite direction, and the polarization caused by the first current on the surface of the electrodes is destroyed before it rises to an appreciable value. The polarization is also diminished in another way. The electromotive force of polarization is due to the deposition of films of the products of chemical decomposition on the surface of the electrodes, and only reaches its full value when a continuous film is formed. If the current be stopped before such a film is completed, the reverse electromotive force is less than its full value. A given current flowing for a given time deposits a definite amount of substance on the electrodes, and therefore the amount per unit area is inversely proportional to the area of the electrodes—to the area of contact, that is, between the electrode and the liquid. Thus, by increasing the area of the electrodes, the polarization due to a given current is decreased. Now the area of free surface of a platinum plate can be increased enormously by coating the plate with platinum black, which is metallic platinum in a spongy state, and with such a plate as electrode the effects of polarization are diminished to a very marked extent. The coating is effected by passing an electric current first one way and then the other between two platinum plates immersed in a 3% solution of platinum chloride to which a trace of lead acetate is sometimes added. The platinized plates thus obtained are quite satisfactory for the investigation of strong solutions. They have the power, however, of absorbing a certain amount of salt from the solutions and of giving it up again when water or more dilute solution is placed in contact with them. The measurement of very dilute solutions is thus made difficult, but, if the plates be heated to redness after being platinized, a grey surface is obtained which possesses sufficient area for use with dilute solutions and yet does not absorb an appreciable quantity of salt.
Any convenient source of alternating current may be used. The currents from the secondary circuit of a small induction coil are satisfactory, or the currents of an alternating electric light supply may be transformed down to an electromotive force of one or two volts. With such currents it is necessary to consider the effects of self-induction in the circuit and of electrostatic capacity. In balancing the resistance of the electrolyte, resistance coils may be used in which self-induction and the capacity are reduced to a minimum by winding the wire of the coil backwards and forwards in alternate layers.
 |
| Fig. 1. |
With these arrangements the usual method of measuring resistance by means of Wheatstone’s bridge may be adapted to the case of electrolytes. With alternating currents, however, it is impossible to use a galvanometer in the usual way. The galvanometer was therefore replaced by Kohlrausch by a telephone, which gives a sound when an alternating current passes through it. The most common plan of the apparatus is shown diagrammatically in fig. 1. The electrolytic cell and a resistance box form two arms of the bridge, and the sliding contact is moved along the metre wire which forms the other two arms till no sound is heard in the telephone. The resistance of the electrolyte is to that of the box as that of the right-hand end of the wire is to that of the left-hand end. A more accurate method of using alternating currents, and one more pleasant to use, gets rid of the telephone (Phil. Trans., 1900, 194, p. 321). The current from one or two voltaic cells is led to an ebonite drum turned by a motor or a hand-wheel and cord. On the drum are fixed brass strips with wire brushes touching them in such a manner that the current from the brushes is reversed several times in each revolution of the drum. The wires from the brushes are connected with the Wheatstone’s bridge. A moving coil galvanometer is used as indicator, its connexions being reversed in time with those of the battery by a slightly narrower set of brass strips fixed on the other end of the ebonite commutator. Thus any residual current through the galvanometer is direct and not alternating. The high moment of inertia of the coil makes the period of swing slow compared with the period of alternation of the current, and the slight periodic disturbances are thus prevented from affecting the galvanometer. When the measured resistance is not altered by increasing the speed of the commutator or changing the ratio of the arms of the bridge, the disturbing effects may be considered to be eliminated.
 | |
| Fig. 2. | Fig. 3. |
The form of vessel chosen to contain the electrolyte depends on the order of resistance to be measured. For dilute solutions the shape of cell shown in fig. 2 will be found convenient, while for more concentrated solutions, that indicated in fig. 3 is suitable. The absolute resistances of certain solutions have been determined by Kohlrausch by comparison with mercury, and, by using one of these solutions in any cell, the constant of that cell may be found once for all. From the observed resistance of any given solution in the cell the resistance of a centimetre cube—the so-called specific resistance—may be calculated. The reciprocal of this, or the conductivity, is a more generally useful constant; it is conveniently expressed in terms of a unit equal to the reciprocal of an ohm. Thus Kohlrausch found that a solution of potassium chloride, containing one-tenth of a gram equivalent (7.46 grams) per litre, has at 18° C. a specific resistance of 89.37 ohms per centimetre cube, or a conductivity of 1.119×10−2 mhos or 1.119×10−11 C.G.S. units. As the temperature variation of conductivity is large, usually about 2% per degree, it is necessary to place the resistance cell in a paraffin or water bath, and to observe its temperature with some accuracy.
Another way of eliminating the effects of polarization and of dilution has been used by W. Stroud and J. B. Henderson (Phil. Mag., 1897 [5], 43, p. 19). Two of the arms of a Wheatstone’s bridge are composed of narrow tubes filled with the solution, the tubes being of equal diameter but of different length. The other two arms are made of coils of wire of equal resistance, and metallic resistance is added to the shorter tube till the bridge is balanced. Direct currents of somewhat high electromotive force are used to work the bridge. Equal currents then flow through the two tubes; the effects of polarization and dilution must be the same in each, and the resistance added to the shorter tube must be equal to the resistance of a column of liquid the length of which is equal to the difference in length of the two tubes.
A somewhat different principle was adopted by E. Bouty in 1884. If a current be passed through two resistances in series by means of an applied electromotive force, the electric potential falls from one end of the resistances to the other, and, if we apply Ohm’s law to each resistance in succession, we see that, since for each of them E = CR, and C the current is the same through both, E the electromotive force or fall of potential between the ends of each resistance must be proportional to the resistance between them. Thus by measuring the potential difference between the ends of the two resistances successively, we may compare their resistances. If, on the other hand, we can measure the potential difference in some known units, and similarly measure the current flowing, we can determine the resistance of a single electrolyte. The details of the apparatus may vary, but its principle is illustrated in the following description. A narrow glass tube is fixed horizontally into side openings in two glass vessels, and an electric current passed through it by means of platinum electrodes and a battery of considerable electromotive force. In this way a steady fall of electric potential is set up along the length of the tube. To measure the potential difference between the ends of the tube, tapping electrodes are constructed, e.g. by placing zinc rods in vessels with zinc sulphate solution and connecting these vessels (by means of thin siphon tubes also filled with solution) with the vessels at the ends of the long tube which contains the electrolyte to be examined. Whatever be the contact potential difference between zinc and its solution, it is the same at both ends, and thus the potential difference between the zinc rods is equal to that between the liquid at the two ends of the tube. This potential difference may be measured without passing any appreciable current through the tapping electrodes, and thus the resistance of the liquid deduced.
Equivalent Conductivity of Solutions.—As is the case in the
other properties of solutions, the phenomena are much more
simple when the concentration is small than when it is great, and
a study of dilute solutions is therefore the best way of getting an
insight into the essential principles of the subject. The foundation
of our knowledge was laid by Kohlrausch when he had developed
the method of measuring electrolyte resistance described above.
He expressed his results in terms of “equivalent conductivity,”
that is, the conductivity (k) of the solution divided by the number
(m) of gram-equivalents of electrolyte per litre. He finds that, as
the concentration diminishes, the value of k/m approaches a
limit, and eventually becomes constant, that is to say, at great
dilution the conductivity is proportional to the concentration.
Kohlrausch first prepared very pure water by repeated distillation
and found that its resistance continually increased as the process
of purification proceeded. The conductivity of the water, and of
the slight impurities which must always remain, was subtracted
from that of the solution made with it, and the result, divided
by m, gave the equivalent conductivity of the substance dissolved.
This procedure appears justifiable, for as long as conductivity is
proportional to concentration it is evident that each part of the
dissolved matter produces its own independent effect, so that the
total conductivity is the sum of the conductivities of the parts; when this ceases to hold, the concentration of the solution has in
general become so great that the conductivity of the solvent may
be neglected. The general result of these experiments can be
represented graphically by plotting k/m as ordinates and 3√m
Fig. 4.
as abscissae, 3√m being a number proportional to the reciprocal
of the average distance between the molecules, to which it seems
likely that the molecular conductivity may be related. The
general types of curve for a simple neutral salt like potassium or
sodium chloride and for a caustic alkali or acid are shown in fig. 4.
The curve for the neutral salt comes to a limiting value; that for
the acid attains a maximum at a certain very small concentration,
and falls again when the dilution
is carried farther. It has usually
been considered that this destruction
of conductivity is due to
chemical action between the acid
and the residual impurities in the
water. At such great dilution these
impurities are present in quantities
comparable with the amount of acid
which they convert into a less
highly conducting neutral salt. In
the case of acids, then, the maximum
must be taken as the limiting
value. The decrease in equivalent conductivity at great dilution
is, however, so constant that this explanation seems insufficient.
The true cause of the phenomenon may perhaps be connected
with the fact that the bodies in which it occurs, acids and
alkalis, contain the ions, hydrogen in the one case, hydroxyl in
the other, which are present in the solvent, water, and have,
perhaps because of this relation, velocities higher than those of any
other ions. The values of the molecular conductivities of all
neutral salts are, at great dilution, of the same order of magnitude,
while those of acids at their maxima are about three times as
large. The influence of increasing concentration is greater in the
case of salts containing divalent ions, and greatest of all in such
cases as solutions of ammonia and acetic acid, which are substances
of very low conductivity.
Theory of Moving Ions.—Kohlrausch found that, when the polarization at the electrodes was eliminated, the resistance of a solution was constant however determined, and thus established Ohm’s Law for electrolytes. The law was confirmed in the case of strong currents by G. F. Fitzgerald and F. T. Trouton (B.A. Report, 1886, p. 312). Now, Ohm’s Law implies that no work is done by the current in overcoming reversible electromotive forces such as those of polarization. Thus the molecular interchange of ions, which must occur in order that the products may be able to work their way through the liquid and appear at the electrodes, continues throughout the solution whether a current is flowing or not. The influence of the current on the ions is merely directive, and, when it flows, streams of electrified ions travel in opposite directions, and, if the applied electromotive force is enough to overcome the local polarization, give up their charges to the electrodes. We may therefore represent the facts by considering the process of electrolysis to be a kind of convection. Faraday’s classical experiments proved that when a current flows through an electrolyte the quantity of substance liberated at each electrode is proportional to its chemical equivalent weight, and to the total amount of electricity passed. Accurate determinations have since shown that the mass of an ion deposited by one electromagnetic unit of electricity, i.e. its electro-chemical equivalent, is 1.036×10−4× its chemical equivalent weight. Thus the amount of electricity associated with one gram-equivalent of any ion is 104/1.036 = 9653 units. Each monovalent ion must therefore be associated with a certain definite charge, which we may take to be a natural unit of electricity; a divalent ion carries two such units, and so on. A cation, i.e. an ion giving up its charge at the cathode, as the electrode at which the current leaves the solution is called, carries a positive charge of electricity; an anion, travelling in the opposite direction, carries a negative charge. It will now be seen that the quantity of electricity flowing per second, i.e. the current through the solution, depends on (1) the number of the ions concerned, (2) the charge on each ion, and (3) the velocity with which the ions travel past each other. Now, the number of ions is given by the concentration of the solution, for even if all the ions are not actively engaged in carrying the current at the same instant, they must, on any dynamical idea of chemical equilibrium, be all active in turn. The charge on each, as we have seen, can be expressed in absolute units, and therefore the velocity with which they move past each other can be calculated. This was first done by Kohlrausch (Göttingen Nachrichten, 1876, p. 213, and Das Leitvermögen der Elektrolyte, Leipzig, 1898) about 1879.
In order to develop Kohlrausch’s theory, let us take, as an example, the case of an aqueous solution of potassium chloride, of concentration n gram-equivalents per cubic centimetre. There will then be n gram-equivalents of potassium ions and the same number of chlorine ions in this volume. Let us suppose that on each gram-equivalent of potassium there reside +e units of electricity, and on each gram-equivalent of chlorine ions −e units. If u denotes the average velocity of the potassium ion, the positive charge carried per second across unit area normal to the flow is n e u. Similarly, if v be the average velocity of the chlorine ions, the negative charge carried in the opposite direction is n e v. But positive electricity moving in one direction is equivalent to negative electricity moving in the other, so that, before changes in concentration sensibly supervene, the total current, C, is ne(u + v). Now let us consider the amounts of potassium and chlorine liberated at the electrodes by this current. At the cathode, if the chlorine ions were at rest, the excess of potassium ions would be simply those arriving in one second, namely, nu. But since the chlorine ions move also, a further separation occurs, and nv potassium ions are left without partners. The total number of gram-equivalents liberated is therefore n(u + v). By Faradays law, the number of grams liberated is equal to the product of the current and the electro-chemical equivalent of the ion; the number of gram-equivalents therefore must be equal to ηC, where η denotes the electro-chemical equivalent of hydrogen in C.G.S. units. Thus we get
and it follows that the charge, e, on 1 gram-equivalent of each kind of ion is equal to 1/η. We know that Ohm’s Law holds good for electrolytes, so that the current C is also given by k·dP/dx, where k denotes the conductivity of the solution, and dP/dx the potential gradient, i.e. the change in potential per unit length along the lines of current flow. Thus
Now η is 1.036×10−4, and the concentration of a solution is usually expressed in terms of the number, m, of gram-equivalents per litre instead of per cubic centimetre. Therefore
| u + v = 1.036×10−1 | k | dP | . | |
| m | dx |
When the potential gradient is one volt (108 C.G.S. units) per centimetre this becomes
Thus by measuring the value of k/m, which is known as the equivalent conductivity of the solution, we can find u + v, the velocity of the ions relative to each other. For instance, the equivalent conductivity of a solution of potassium chloride containing one-tenth of a gram-equivalent per litre is 1119×10−13 C.G.S. units at 18° C. Therefore
In order to obtain the absolute velocities u and v, we must find some other relation between them. Let us resolve u into 12(u + v) in one direction, say to the right, and 12(u − v) to the left. Similarly v can be resolved into 12(v + u) to the left and 12(v − u) to the right. On pairing these velocities we have a combined movement of the ions to the right, with a speed of 12(u − v) and a drift right and left, past each other, each ion travelling with a speed of 12(u + v), constituting the electrolytic separation. If u is greater than v, the combined movement involves a concentration of salt at the cathode, and a corresponding dilution at the anode, and vice versa. The rate at which salt is electrolysed, and thus removed from the solution at each electrode, is 12(u + v). Thus the total loss of salt at the cathode is 12(u + v) − 12(u − v) or v, and at the anode, 12(v + u) − 12(v − u), or u. Therefore, as is explained in the article Electrolysis, by measuring the dilution of the liquid round the electrodes when a current passed, W. Hittorf (Pogg. Ann., 1853–1859, 89, p. 177; 98, p. 1; 103, p. 1; 106, pp. 337 and 513) was able to deduce the ratio of the two velocities, for simple salts when no complex ions are present, and many further experiments have been made on the subject (see Das Leitvermögen der Elektrolyte).
By combining the results thus obtained with the sum of the velocities, as determined from the conductivities, Kohlrausch calculated the absolute velocities of different ions under stated conditions. Thus, in the case of the solution of potassium chloride considered above, Hittorf’s experiments show us that the ratio of the velocity of the anion to that of the cation in this solution is .51 : .49. The absolute velocity of the potassium ion under unit potential gradient is therefore 0.000567 cm. per sec., and that of the chlorine ion 0.000592 cm. per sec. Similar calculations can be made for solutions of other concentrations, and of different substances.
Table IX. shows Kohlrausch’s values for the ionic velocities of three chlorides of alkali metals at 18° C, calculated for a potential gradient of 1 volt per cm.; the numbers are in terms of a unit equal to 10−6 cm. per sec.:—
Table IX.
| KCl | NaCl | LiCl | |||||||
| m | u + v | u | v | u + v | u | v | u + v | u | v |
| 0 | 1350 | 660 | 690 | 1140 | 450 | 690 | 1050 | 360 | 690 |
| 0.0001 | 1335 | 654 | 681 | 1129 | 448 | 681 | 1037 | 356 | 681 |
| .001 | 1313 | 643 | 670 | 1110 | 440 | 670 | 1013 | 343 | 670 |
| .01 | 1263 | 619 | 644 | 1059 | 415 | 644 | 962 | 318 | 644 |
| .03 | 1218 | 597 | 621 | 1013 | 390 | 623 | 917 | 298 | 619 |
| .1 | 1153 | 564 | 589 | 952 | 360 | 592 | 853 | 259 | 594 |
| .3 | 1088 | 531 | 557 | 876 | 324 | 552 | 774 | 217 | 557 |
| 1.0 | 1011 | 491 | 520 | 765 | 278 | 487 | 651 | 169 | 482 |
| 3.0 | 911 | 442 | 469 | 582 | 206 | 376 | 463 | 115 | 348 |
| 5.0 | 438 | 153 | 285 | 334 | 80 | 254 | |||
| 10.0 | 117 | 25 | 92 | ||||||
These numbers show clearly that there is an increase in ionic velocity as the dilution proceeds. Moreover, if we compare the values for the chlorine ion obtained from observations on these three different salts, we see that as the concentrations diminish the velocity of the chlorine ion becomes the same in all of them. A similar relation appears in other cases, and, in general, we may say that at great dilution the velocity of an ion is independent of the nature of the other ion present. This introduces the conception of specific ionic velocities, for which some values at 18° C. are given by Kohlrausch in Table X.:—
Table X.
| K | 66 | × 10−5 cms. | per sec. | Cl | 69 | × 10−5 cms. | per sec. |
| Na | 45 | ” | ” | I | 69 | ” | ” |
| Li | 36 | ” | ” | NO3 | 64 | ” | ” |
| NH4 | 66 | ” | ” | OH | 162 | ” | ” |
| H | 320 | ” | ” | C2H3O2 | 36 | ” | ” |
| Ag | 57 | ” | ” | C3H5O2 | 33 | ” | ” |
Having obtained these numbers we can deduce the conductivity of the dilute solution of any salt, and the comparison of the calculated with the observed values furnished the first confirmation of Kohlrausch’s theory. Some exceptions, however, are known. Thus acetic acid and ammonia give solutions of much lower conductivity than is indicated by the sum of the specific ionic velocities of their ions as determined from other compounds. An attempt to find in Kohlrausch’s theory some explanation of this discrepancy shows that it could be due to one of two causes. Either the velocities of the ions must be much less in these solutions than in others, or else only a fractional part of the number of molecules present can be actively concerned in conveying the current. We shall return to this point later.
Friction on the Ions.—It is interesting to calculate the magnitude of the forces required to drive the ions with a certain velocity. If we have a potential gradient of 1 volt per centimetre the electric force is 108 in C.G.S. units. The charge of electricity on 1 gram-equivalent of any ion is 1/.0001036 = 9653 units, hence the mechanical force acting on this mass is 9653×108 dynes. This, let us say, produces a velocity u; then the force required to produce unit velocity is PA = 9.653×1011u dynes = 9.84×105u kilograms-weight. If the ion have an equivalent weight A, the force producing unit velocity when acting on 1 gram is P1 = 9.84×105Au kilograms-weight. Thus the aggregate force required to drive 1 gram of potassium ions with a velocity of 1 centimetre per second through a very dilute solution must be equal to the weight of 38 million kilograms.
Table XI.
| Kilograms-weight. | Kilograms-weight. | ||||
| PA | P1 | PA | P1 | ||
| K | 15×108 | 38×106 | Cl | 14 108 | 40×106 |
| Na | 22 ” | 95 ” | I | 14 ” | 11 ” |
| Li | 27 ” | 390 ” | NO3 | 15 ” | 25 ” |
| NH4 | 15 ” | 83 ” | OH | 5.4 ” | 32 ” |
| H | 3.1 ” | 310 ” | C2H8O2 | 27 ” | 46 ” |
| Ag | 17 ” | 16 ” | C3H5O2 | 30 ” | 41 ” |
Since the ions move with uniform velocity, the frictional resistances brought into play must be equal and opposite to the driving forces, and therefore these numbers also represent the ionic friction coefficients in very dilute solutions at 18° C.
Direct Measurement of Ionic Velocities.—Sir Oliver Lodge was the first to directly measure the velocity of an ion (B.A. Report, 1886, p. 389). In a horizontal glass tube connecting two vessels filled with dilute sulphuric acid he placed a solution of sodium chloride in solid agar-agar jelly. This solid solution was made alkaline with a trace of caustic soda in order to bring out the red colour of a little phenol-phthalein added as indicator. An electric current was then passed from one vessel to the other. The hydrogen ions from the anode vessel of acid were thus carried along the tube, and, as they travelled, decolourized the phenol-phthalein. By this method the velocity of the hydrogen ion through a jelly solution under a known potential gradient was observed to about 0.0026 cm. per sec, a number of the same order as that required by Kohlrausch’s theory. Direct determinations of the velocities of a few other ions have been made by W. C. D. Whetham (Phil. Trans. vol. 184, A, p. 337; vol. 186, A, p. 507; Phil. Mag., October 1894). Two solutions having one ion in common, of equivalent concentrations, different densities, different colours, and nearly equal specific resistances, were placed one over the other in a vertical glass tube. In one case, for example, decinormal solutions of potassium carbonate and potassium bichromate were used. The colour of the latter is due to the presence of the bichromate group, Cr2O7. When a current was passed across the junction, the anions CO3 and Cr2O7 travelled in the direction opposite to that of the current, and their velocity could be determined by measuring the rate at which the colour boundary moved. Similar experiments were made with alcoholic solutions of cobalt salts, in which the velocities of the ions were found to be much less than in water. The behaviour of agar jelly was then investigated, and the velocity of an ion through a solid jelly was shown to be very little less than in an ordinary liquid solution. The velocities could therefore be measured by tracing the change in colour of an indicator or the formation of a precipitate. Thus decinormal jelly solutions of barium chloride and sodium chloride, the latter containing a trace of sodium sulphate, were placed in contact. Under the influence of an electromotive force the barium ions moved up the tube, disclosing their presence by the trace of insoluble barium sulphate formed. Again, a measurement of the velocity of the hydrogen ion, when travelling through the solution of an acetate, showed that its velocity was then only about the one-fortieth part of that found during its passage through chlorides. From this, as from the measurements on alcohol solutions, it is clear that where the equivalent conductivities are very low the effective velocities of the ions are reduced in the same proportion.
Another series of direct measurements has been made by Orme Masson (Phil. Trans. vol. 192, A, p. 331). He placed the gelatine solution of a salt, potassium chloride, for example, in a horizontal glass tube, and found the rate of migration of the potassium and chlorine ions by observing the speed at which they were replaced when a coloured anion, say, the Cr2O7 from a solution of potassium bichromate, entered the tube at one end, and a coloured cation, say, the Cu from copper sulphate, at the other. The coloured ions are specifically slower than the colourless ions which they follow, and in this case it follows that the coloured solution has a higher resistance than the colourless. For the same current, therefore, the potential gradient is higher in the coloured solution and lower in the colourless one. Thus a coloured ion which gets in front of the advancing boundary finds itself acted on by a smaller force and falls back into line, while a straggling colourless ion is pushed forward again. Hence a sharp boundary is preserved. B. D. Steele has shown that with these sharp boundaries the use of coloured ions is unnecessary, the junction line being visible owing to the difference in the optical refractive indices of two colourless solutions. Once the boundary is formed, too, no gelatine is necessary, and the motion can be watched through liquid aqueous solutions (see R. B. Denison and B. D. Steele, Phil. Trans., 1906).
All the direct measurements which have been made on simple binary electrolytes agree with Kohlrausch’s results within the limits of experimental error. His theory, therefore, probably holds good in such cases, whatever be the solvent, if the proper values are given to the ionic velocities, i.e. the values expressing the velocities with which the ions actually move in the solution of the strength taken, and under the conditions of the experiment. If we know the specific velocity of any one ion, we can deduce, from the conductivity of very dilute solutions, the velocity of any other ion with which it may be associated, a proceeding which does not involve the difficult task of determining the migration constant of the compound. Thus, taking the specific ionic velocity of hydrogen as 0.00032 cm. per second, we can find, by determining the conductivity of dilute solutions of any acid, the specific velocity of the acid radicle involved. Or again, since we know the specific velocity of silver, we can find the velocities of a series of acid radicles at great dilution by measuring the conductivity of their silver salts.
By such methods W. Ostwald, G. Bredig and other observers have found the specific velocities of many ions both of inorganic and organic compounds, and examined the relation between constitution and ionic velocity. The velocity of elementary ions is found to be a periodic function of the atomic weight, similar elements lying on corresponding portions of a curve drawn to express the relation between these two properties. Such a curve much resembles that giving the relation between atomic weight and viscosity in solution. For complex ions the velocity is largely an additive property; to a continuous additive change in the composition of the ion corresponds a continuous but decreasing change in the velocity. The following table gives Ostwald’s results for the formic acid series:—
Table XII.
| Velocity. | Difference for CH2. | ||
| Formic acid | HCO2 | 51.2 | .. |
| Acetic acid | H3C2O2 | 38.3 | −12.9 |
| Propionic acid | H5C3O2 | 34.3 | − 4.0 |
| Butyric acid | H7C4O2 | 30.8 | − 3.5 |
| Valeric acid | H9C5O2 | 28.8 | − 2.0 |
| Caprionic acid | H11C6O2 | 27.4 | − 1.4 |
Nature of Electrolytes.—We have as yet said nothing about the fundamental cause of electrolytic activity, nor considered why, for example, a solution of potassium chloride is a good conductor, while a solution of sugar allows practically no current to pass.
All the preceding account of the subject is, then, independent of any view we may take of the nature of electrolytes, and stands on the basis of direct experiment. Nevertheless, the facts considered point to a very definite conclusion. The specific velocity of an ion is independent of the nature of the opposite ion present, and this suggests that the ions themselves, while travelling through the liquid, are dissociated from each other. Further evidence, pointing in the same direction, is furnished by the fact that since the conductivity is proportional to the concentration at great dilution, the equivalent-conductivity, and therefore the ionic velocity, is independent of it. The importance of this relation will be seen by considering the alternative to the dissociation hypothesis. If the ions are not permanently free from each other their mobility as parts of the dissolved molecules must be secured by continual interchanges. The velocity with which they work their way through the liquid must then increase as such molecular rearrangements become more frequent, and will therefore depend on the number of solute molecules, i.e. on the concentration. On this supposition the observed constancy of velocity would be impossible. We shall therefore adopt as a wording hypothesis the theory, confirmed by other phenomena (see Electrolysis), that an electrolyte consists of dissociated ions.
It will be noticed that neither the evidence in favour of the dissociation theory which is here considered, nor that described in the article Electrolysis, requires more than the effective dissociation of the ions from each other. They may well be connected in some way with solvent molecules, and there are several indications that an ion consists of an electrified part of the molecule of the dissolved salt with an attendant atmosphere of solvent round it. The conductivity of a salt solution depends on two factors—(1) the fraction of the salt ionized; (2) the velocity with which the ions, when free from each other, move under the electric forces.[2] When a solution is heated, both these factors may change. The coefficient of ionization usually, though not always, decreases; the specific ionic velocities increase. Now the rate of increase with temperature of these ionic velocities is very nearly identical with the rate of decrease of the viscosity of the liquid. If the curves obtained by observations at ordinary temperatures be carried on they indicate a zero of fluidity and a zero of ionic velocity about the same point, 38.5° C. below the freezing point of water (Kohlrausch, Sitz. preuss. Akad. Wiss., 1901, 42, p. 1026). Such relations suggest that the frictional resistance to the motion of an ion is due to the ordinary viscosity of the liquid, and that the ion is analogous to a body of some size urged through a viscous medium rather than to a particle of molecular dimensions finding its way through a crowd of molecules of similar magnitude. From this point of view W. K. Bousfield has calculated the sizes of ions on the assumption that Stokes’s theory of the motion of a small sphere through a viscous medium might be applied (Zeits. phys. Chem., 1905, 53, p. 257; Phil. Trans. A, 1906, 206, p. 101). The radius of the potassium or chlorine ion with its envelope of water appears to be about 1.2×10−8 centimetres.
For the bibliography of electrolytic conduction see Electrolysis. The books which deal more especially with the particular subject of the present article are Das Leitvermögen der Elektrolyte, by F. Kohlrausch and L. Holborn (Leipzig, 1898), and The Theory of Solution and Electrolysis, by W. C. D. Whetham (Cambridge, 1902). (W. C. D. W.)
- ↑ F. Kohlrausch and L. Holborn, Das Leitvermögen der Elektrolyte (Leipzig, 1898).
- ↑ It should be noticed that the velocities calculated in Kohlrausch’s theory and observed experimentally are the average velocities, and involve both the factors mentioned above; they include the time wasted by the ions in combination with each other, and, except at great dilution, are less than the velocity with which the ions move when free from each other.