Explanation of linearity

Consider a weak acid, HA. At low pH, ionization is suppressed so that [ HA ] is not affected by pH. The expression

reduces to: some constant = [ H+ ] [ A- ]
taking logs and rearranging:
log [ A- ] = a constant - log [ H+ ]
A plot of - log [ A- ] versus pH will have a slope of 1. The same reasoning works for high pH where [ A- ] is independent of pH shows that a plot of -log [ HA ] versus pH has a slope of -1. Further analysis along these lines would confirm the slopes of 2 and -2 when additional equilibria come into play.

  • Graphs for Solubility Equilibria