Chemical Analysis: An Advanced Text and Reference by Herbert August Laitinen, Walter E. Harris

By Herbert August Laitinen, Walter E. Harris

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Interpretations of pH values are soundest when associated with dilute aqueous solutions of simple solutes; they become unsound when associated with nonaqueous solvents, colloids, or solutions of high ionic strength. For most applications the pH value may be regarded as a practical and comparative measure of acidity, and no attempt need be made to interpret it rigorously in terms of single-ion activity. In many calculations the hydrogen ion concentration is more accessible than the activity. For example, the electroneutrality condition is written in terms of concentrations rather than activities.

Ka CA- + [HI] Solution of strong acid A strong acid, by definition, is one for which (3-11) is complete to the right, so that [HA] is essentially zero. From (3-14) [H'] = + CHA [OH-] (3-18) The total concentration of hydrogen ion is that from the strong acid plus that from the water (equal to [OH-]). Unless the solution is extremely dilute (CHA< M), the second term may be neglected. Consider, for example, CHA= M. As a first approximation [H'] = M, and therefore [OH-] = 10-'4/10-6 = M; this represents only a 1% correction on the first approximation.

G. BATES: J. Phys. , 74:706 (1970); 73:3014 (1969). T. H. GRONWALL, V. K. LA MER, and K. SAM)VED: Phys. , W:358 (1928); v. K. LA MER, T. H. GRONWALL, and L. J. GRIEFF: J. Phys. , 35:2245 (1931). J. 11 I2 13 14 I5 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 E. , . 26:93 (1925). and H. s. , 28:419 (1941); R. H. STOKES a n d R. A. ROBINSON: J. Amer. Chem. , 70:1870 (1948). E. GLUECKAUF: Trans. , 51:1235 (1955). D. G. MILLER: J. Phys. , @:I296 (1956). R. M. DIAMOND: J. Amer. Chem.

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