By I M Kolthoff
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2 Noyes and Mclnnes: J. Am. Chem. , 4#, 239 (1920). ACID-BASE INDICATORS 54 (c) A, A. NOTES has pointed out a number of other objections ARRHENIUS. It is difficult to understand, for example, why a normal hydrochloric acid solution should show an inappreciable vapor pressure of hydrogen chloride, in spite of the fact that conductivity measurements show 15% of the electrolyte to remain undissociated. Other phenomena, such as the influence of electrolytes on the to the theory of solubility of slightly soluble salts, the so-called neutral salt effect in catalytic phenomena, and the light absorption by strong electrolytes, are not elucidated by the classical theory of ARRHENIUS.
A-] + a (13) also that and L By " J COH-] combining these equations, we obtain: K b CH+]' - |. (7) ACID-BASE INDICATORS 42 In order to solve this equation, it is necessary to assume first approximation that [A] is equal to c a, just as was done in calculating the [H+] of a pure ampholyte solution. Should the error introduced by this approximation prove to be too large, the calculation can be repeated using for [A] the value as a - c a - [A-]. The form above equation is rather complicated. For many practical applications it can be reduced to a more convenient form.
Michaelis and Davidsohn: Biochem. , 47, 250 (1912). A. Bork: Z. physik. , 189, 58 (1927). S. Andrews and C. L. A. Schmidt: J. Biol. , 73, 651 (1927). For more recent literature, cf. Landolt-Bornstein-Koth, Physikalisch-Chemische Tabellen, Vol. 8 (1931). we make use [H+] in a solution If of the simple equation (8) to calculate the of pure ampholyte, in which the [A] is ex- tremely large, and if id* and Kb are at least 10,000 times as great as w , then we find: K [H+]= /uLAjf A. EU^ (12) This simplification thus leads to the same expression which Michaelis derived for [H+ ] at the isoelectric point.