The Conductance of Aqueous Electrolytes

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Abstract
In the interionic attraction theory of electrolytes the properties of the solutions are considered to be due to the interplay of electrostatic forces and thermal vibrations. The first of these tends to give the ions a definite arrangement, and the second acts to produce a random distribution. Using these ideas Debye and Hückel have accounted for the change of ion activities with concentration, and the same workers, followed by Onsager, have explained varying ion mobilities. With new experimental data the authors show that Onsager's equation is the correct expression for very dilute solutions of strong electrolytes, and that the data at higher concentrations can be accounted for by semi‐empirical equations, which are, however, of the form to be expected from the types of approximations made in obtaining Onsager's theoretical equation. The same considerations are useful in dealing with the ionic portion of weak electrolytes. New data are given for the conductances of chloroacetic acid. The degrees of dissociation of solutions of this acid have been determined by a method in which allowance is made for changing ion mobilities, and ion activities have been computed using the Debye‐Hückel equation. These results yield a value of the thermodynamic ionization constant of the acid which holds to a concentration as high as the assumptions are valid for the solutions involved. The interionic attraction theory is thus shown to be useful in interpreting data for both strong and weak electrolytes.

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