By I.M. Kolthoff
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Sum [A+] 10~" + [A~] may not 2 . 1 5 = c [H+] = [A+] = When . 3 X 10~6 4 Therefore the correct value of [A] which is practically identical with Similar calculations c IQr*, The corresponding c. 10~ 14, (8), [H+] = if 10~ 12 X X X 10~ 4 10~ 4 10~ 4 , , . results in ACID-BASE INDICATORS 36 When c = 10~ 4 the first , [H+] [A-] [A+] approximation gives: = = is 4 4 X X 10-*, 10-*, negligibly small. 2 X X smaller than 10- 5 10- 5 K , . ay the ampholyte [H+] is is obtained if may be Thus the same considered as a monobasic acid at this dilution.
Formed is so strong as to be completely ionized. Applying the mass action law to the equilibrium involved in equation (26), we find that : [HA] X [OH-] _ ~ [A-] X [H 2 0] Considering the concentration of water as constant, we obtain: - - [HA] X [OH-] = The quantity XHA Khydr. is called the hydrolysis constant. * : X [OH-] = KW9 write K = -gr-^ (5) (29) We have already stated that in the salt solution [HA] is equal the salt in solution is Completely ionized, and its = c where c is the hydrolysis may be disregarded, then [A~j salt concentration.
The largest portion exists as an inner salt, +NH RCOO3 (Hybrid ion), NH instead of neutral molecules, 2 RCOOH, as required by the The calculations in the preceding section were older conception. based upon the latter concept, although it is not valid. We that these calculations yield correct results, the significance attributed to the acidic and basic disalthough sociation constants was incorrect. +A~ the If we let A denote the amino acid 2 RCOOH, shall see later NH A+ hybrid ion, the older view the cation, and A~ the anion, then according to CH+XA-: = K a, [A] (i) [A+JOH-] _ According to the modern concept, we have to deal with the following equilibria: +NH RCOOH 3 <= +NH RCOO- + H+ A+<=*+Aand 3 + H+, NH RCOO- + H O <^ +NH RCOO- + OR-, A- + H +* +A- + OH-.