On the use of dimensionless parameters in acid-base theory. V. Buffers composed of binary mixtures of monovalent weak acids and bases

Abstract

A general theory for buffers consisting of one weak acid and one weak base is developed, particular interest being devoted to the special case of doubly weak salts. The pH course as it varies with the acid/base concentration ratio is presented in equations and graphs. The influence of delta pK' = pK'b-pK'a, which can be negative as well as positive, is discussed and visualized in graphs. The buffer capacity is deduced as a function of pH. The buffer range is, at a maximum, 2.67 times that of a monovalent weak protolyte for delta pK' = 2.7 pH units. The buffer capacity curve has two maxima for delta pK' values bigger than 0.77. For negative delta pK' values the buffer capacity curve has only one maximum, and the buffer range is not better than that of a monovalent protolyte. A general equation for the ionic concentrations is deduced, and as a corollary the degree of hydrolysis of the doubly weak salt is obtained as a function of delta pK'. For solutions of this salt, the relation between concentration and pH is elucidated by equations and graphs.