to the electrode where there is no ionization. A plate of metal will
be as effectual as one made of a non-conductor, and thus we get the
remarkable result that by interposing a plate of an excellent conductor
like copper or silver between the electrode, we can entirely
stop the current. This experiment can easily be tried by using a
hot plate as the electrode at which the ionization takes place: then
if the other electrode is cold the current which passes when the hot
plate is cathode can be entirely stopped by interposing a cold metal
plate between the electrodes.
Methods of counting the Number of Ions.—The detection of the ions and the estimation of their number in a given volume is much facilitated by the property they possess of promoting the condensation of water-drops in dust-free air supersaturated with water vapour. If such air contains no ions, then it requires about an eightfold supersaturation before any water-drops are formed; if, however, ions are present C. T. R. Wilson (Phil. Trans. 189, p. 265) has shown that a sixfold supersaturation is sufficient to cause the water vapour to condense round the ions and to fall down as raindrops. The absence of the drops when no ions are present is due to the curvature of the drop combined with the surface tension causing, as Lord Kelvin showed, the evaporation from a small drop to be exceeding rapid, so that even if a drop of water were formed the evaporation would be so great in its early stages that it would rapidly evaporate and disappear. It has been shown, however (J. J. Thomson, Application of Dynamics to Physics and Chemistry, p. 164; Conduction of Electricity through Gases, 2nd ed. p. 179), that if a drop of water is charged with electricity the effect of the charge is to diminish the evaporation; if the drop is below a certain size the effect the charge has in promoting condensation more than counterbalances the effect of the surface tension in promoting evaporation. Thus the electric charge protects the drop in the most critical period of its growth. The effect is easily shown experimentally by taking a bulb connected with a piston arranged so as to move with great rapidity. When the piston moves so as to increase the volume of the air contained in the bulb the air is cooled by expansion, and if it was saturated with water vapour before it is supersaturated after the expansion. By altering the throw of the piston the amount of supersaturation can be adjusted within very wide limits. Let it be adjusted so that the expansion produces about a sixfold supersaturation; then if the gas is not exposed to any ionizing agents very few drops (and these probably due to the small amount of ionization which we have seen is always present in gases) are formed. If, however, the bulb is exposed to strong Röntgen rays expansion produces a dense cloud which gradually falls down and disappears. If the gas in the bulb at the time of its exposure to the Röntgen rays is subject to a strong electric field hardly any cloud is formed when the gas is suddenly expanded. The electric field removes the charged ions from the gas as soon as they are formed so that the number of ions present is greatly reduced. This experiment furnishes a very direct proof that the drops of water which form the cloud are only formed round the ions.
This method gives us an exceedingly delicate test for the presence of ions, for there is no difficulty in detecting ten or so raindrops per cubic centimetre; we are thus able to detect the presence of this number of ions. This result illustrates the enormous difference between the delicacy of the methods of detecting ions and those for detecting uncharged molecules; we have seen that we can easily detect ten ions per cubic centimetre, but there is no known method, spectroscopic or chemical, which would enable us to detect a billion (1012) times this number of uncharged molecules. The formation of the water-drops round the charged ions gives us a means of counting the number of ions present in a cubic centimetre of gas; we cool the gas by sudden expansion until the supersaturation produced by the cooling is sufficient to cause a cloud to be formed round the ions, and the problem of finding the number of ions per cubic centimetre of gas is thus reduced to that of finding the number of drops per cubic centimetre in the cloud. Unless the drops are very few and far between we cannot do this by direct counting; we can, however, arrive at the result in the following way. From the amount of expansion of the gas we can calculate the lowering produced in its temperature and hence the total quantity of water precipitated. The water is precipitated as drops, and if all the drops are the same size the number per cubic centimetre will be equal to the volume of water deposited per cubic centimetre, divided by the volume of one of the drops. Hence we can calculate the number of drops if we know their size, and this can be determined by measuring the velocity with which they fall under gravity through the air.
The theory of the fall of a heavy drop of water through a viscous fluid shows that v = 29ga2/μ, where a is the radius of the drop, g the acceleration due to gravity, and μ the coefficient of viscosity of the gas through which the drop falls. Hence if we know v we can deduce the value of a and hence the volume of each drop and the number of drops.
Charge on Ion.—By this method we can determine the number of ions per unit volume of an ionized gas. Knowing this number we can proceed to determine the charge on an ion. To do this let us apply an electric force so as to send a current of electricity through the gas, taking care that the current is only a small fraction of the saturating current. Then if u is the sum of the velocities of the positive and negative ions produced in the electric field applied to the gas, the current through unit area of the gas is neu, where n is the number of positive or negative ions per cubic centimetre, and e the charge on an ion. We can easily measure the current through the gas and thus determine neu; we can determine n by the method just described, and u, the velocity of the ions under the given electric field, is known from the experiments of Zeleny and others. Thus since the product neu, and two of the factors n, u are known, we can determine the other factor e, the charge on the ion. This method was used by J. J. Thomson, and details of the method will be found in Phil. Mag. [5], 46, p. 528; [5], 48, p. 547; [6], 5, p. 346. The result of these measurements shows that the charge on the ion is the same whether the ionization is by Röntgen rays or by the influence of ultra-violet light on a metal plate. It is the same whether the gas ionized is hydrogen, air or carbonic acid, and thus is presumably independent of the nature of the gas. The value of e formed by this method was 3.4✕10−10 electrostatic units.
H. A. Wilson (Phil. Mag. [6], 5, p. 429) used another method. Drops of water, as we have seen, condense more easily on negative than on positive ions. It is possible, therefore, to adjust the expansion so that a cloud is formed on the negative but not on the positive ions. Wilson arranged the experiments so that such a cloud was formed between two horizontal plates which could be maintained at different potentials. The charged drops between the plates were acted upon by a uniform vertical force which affected their rate of fall. Let X be the vertical electric force, e the charge on the drop, v1 the rate of fall of the drop when this force acts, and v the rate of fall due to gravity alone. Then since the rate of fall is proportionate to the force on the drop, if a is the radius of the drop, and ρ its density, then
Xe + 43πρ ga 3 | = | v1 | , |
43π ρga 3 | v |
Thus if X, v, v1 are known e can be determined. Wilson by this method found that e was 3.1✕10−10 electrostatic units. A few of the ions carried charges 2e or 3e.
Townsend has used the following method to compare the charge carried by a gaseous ion with that carried by an atom of hydrogen in the electrolysis of solution. We have
where D is the coefficient of diffusion of the ions through the gas, u the velocity of the ion in the same gas when acted on by unit electric force, N the number of molecules in a cubic centimetre of the gas when the pressure is Π dynes per square centimetre, and e the charge in electrostatic units. This relation is obtained on the hypothesis that N ions in a cubic centimetre produce the same pressure as N uncharged molecules.
We know the value of D from Townsend’s experiments and the values of u from those of Zeleny. We get the following values for Ne✕10−10:—
Gas. | Moist Gas. | Dry Gas. | ||
Positive Ions. | Negative Ions. |
Positive Ions. | Negative Ions. | |
Air | 1.28 | 1.29 | 1.46 | 1.31 |
Oxygen | 1.34 | 1.27 | 1.63 | 1.36 |
Carbonic acid | 1.01 | .87 | .99 | .93 |
Hydrogen | 1.24 | 1.18 | 1.63 | 1.25 |
Mean | 1.22 | 1.15 | 1.43 | 1.21 |