and
| α² | = | x | = constant = k. |
| V (1 − α) | y |
This constant k gives a numerical value for the chemical affinity, and the equation should represent the effect of dilution on the molecular conductivity of binary electrolytes.
In the case of substances like ammonia and acetic acid, where the dissociation is very small, 1 − α is nearly equal to unity, and only varies slowly with dilution. The equation then becomes α²/V = k, or α = √(Vk), so that the molecular conductivity is proportional to the square root of the dilution. Ostwald has confirmed the equation by observation on an enormous number of weak acids (Zeits. physikal. Chemie, 1888, ii. p. 278; 1889, iii. pp. 170, 241, 369). Thus in the case of cyanacetic acid, while the volume V changed by doubling from 16 to 1024 litres, the values of k were 0.00 (376, 373, 374, 361, 362, 361, 368). The mean values of k for other common acids were—formic, 0.0000214; acetic, 0.0000180; monochloracetic, 0.00155; dichloracetic, 0.051; trichloracetic, 1.21; propionic, 0.0000134. From these numbers we can, by help of the equation, calculate the conductivity of the acids for any dilution. The value of k, however, does not keep constant so satisfactorily in the case of highly dissociated substances, and empirical formulae have been constructed to represent the effect of dilution on them. Thus the values of the expressions α² / (1 − α√V) (Rudolphi, Zeits. physikal. Chemie, 1895, vol. xvii. p. 385) and α³ / (1 − α)²V (van ’t Hoff, ibid., 1895, vol. xviii. p. 300) are found to keep constant as V changes. Van ’t Hoff’s formula is equivalent to taking the frequency of dissociation as proportional to the square of the concentration of the molecules, and the frequency of recombination as proportional to the cube of the concentration of the ions. An explanation of the failure of the usual dilution law in these cases may be given if we remember that, while the electric forces between bodies like undissociated molecules, each associated with equal and opposite charges, will vary inversely as the fourth power of the distance, the forces between dissociated ions, each carrying one charge only, will be inversely proportional to the square of the distance. The forces between the ions of a strongly dissociated solution will thus be considerable at a dilution which makes forces between undissociated molecules quite insensible, and at the concentrations necessary to test Ostwald’s formula an electrolyte will be far from dilute in the thermodynamic sense of the term, which implies no appreciable intermolecular or interionic forces.
When the solutions of two substances are mixed, similar considerations to those given above enable us to calculate the resultant changes in dissociation. (See Arrhenius, loc. cit.) The simplest and most important case is that of two electrolytes having one ion in common, such as two acids. It is evident that the undissociated part of each acid must eventually be in equilibrium with the free hydrogen ions, and, if the concentrations are not such as to secure this condition, readjustment must occur. In order that there should be no change in the states of dissociation on mixing, it is necessary, therefore, that the concentration of the hydrogen ions should be the same in each separate solution. Such solutions were called by Arrhenius “isohydric.” The two solutions, then, will so act on each other when mixed that they become isohydric. Let us suppose that we have one very active acid like hydrochloric, in which dissociation is nearly complete, another like acetic, in which it is very small. In order that the solutions of these should be isohydric and the concentrations of the hydrogen ions the same, we must have a very large quantity of the feebly dissociated acetic acid, and a very small quantity of the strongly dissociated hydrochloric, and in such proportions alone will equilibrium be possible. This explains the action of a strong acid on the salt of a weak acid. Let us allow dilute sodium acetate to react with dilute hydrochloric acid. Some acetic acid is formed, and this process will go on till the solutions of the two acids are isohydric: that is, till the dissociated hydrogen ions are in equilibrium with both. In order that this should hold, we have seen that a considerable quantity of acetic acid must be present, so that a corresponding amount of the salt will be decomposed, the quantity being greater the less the acid is dissociated. This “replacement” of a “weak” acid by a “strong” one is a matter of common observation in the chemical laboratory. Similar investigations applied to the general case of chemical equilibrium lead to an expression of exactly the same form as that given by C.M. Guldberg and P. Waage, which is universally accepted as an accurate representation of the facts.
The temperature coefficient of conductivity has approximately the same value for most aqueous salt solutions. It decreases both as the temperature is raised and as the concentration is increased, ranging from about 3.5% per degree for extremely dilute solutions (i.e. practically pure water) at 0° to about 1.5 for concentrated solutions at 18°. For acids its value is usually rather less than for salts at equivalent concentrations. The influence of temperature on the conductivity of solutions depends on (1) the ionization, and (2) the frictional resistance of the liquid to the passage of the ions, the reciprocal of which is called the ionic fluidity. At extreme dilution, when the ionization is complete, a variation in temperature cannot change its amount. The rise of conductivity with temperature, therefore, shows that the fluidity becomes greater when the solution is heated. As the concentration is increased and un-ionized molecules are formed, a change in temperature begins to affect the ionization as well as the fluidity. But the temperature coefficient of conductivity is now generally less than before; thus the effect of temperature on ionization must be of opposite sign to its effect on fluidity. The ionization of a solution, then, is usually diminished by raising the temperature, the rise in conductivity being due to the greater increase in fluidity. Nevertheless, in certain cases, the temperature coefficient of conductivity becomes negative at high temperatures, a solution of phosphoric acid, for example, reaching a maximum conductivity at 75° C.
The dissociation theory gives an immediate explanation of the fact that, in general, no heat-change occurs when two neutral salt solutions are mixed. Since the salts, both before and after mixture, exist mainly as dissociated ions, it is obvious that large thermal effects can only appear when the state of dissociation of the products is very different from that of the reagents. Let us consider the case of the neutralization of a base by an acid in the light of the dissociation theory. In dilute solution such substances as hydrochloric acid and potash are almost completely dissociated, so that, instead of representing the reaction as
HCl + KOH = KCl + H2O,
we must write
| + − + − + − H + Cl + K + OH = K + Cl + H2O. |