A Theoretical study of Oxidation-Reduction Titration Curves

산화${\cdot}$환원 적정곡선의 이론적 고찰

The varation of potential and completeness of reaction in an oxidation-reduction titration of Red$_1$ ($a\;Ox_1+N_1e{\leftrightarrow}b\;Red_1)\;by\;Ox_2\;(C\;Ox_2+n_2e{\leftrightarrow}d\;Red_2)$ is analyzed on the basis of general expressions. It is shown that the reaction deficiency as well as the rate of variation of the potential with titration fraction change in proportion to the $[n_2(a-b)-n_1(c-d)]$ th power of the concentration of the reagents. In particular, at the equivalence point, the expression of the potential contains a concentration dependent term that is proportional to ac-bd. Thus, the equivalence-point potential varies with the concentration of the reagents unless ac=bd is satisfied. It is also shown that the sharpness of the potentiometric titration curve is shown to occur either prior to or after the equivalence point depending upon whether $n_1cn_2b$, the deviation being the same order of magnitude as the relative deficiency at the equivalence point.