Conditional Formation Constants

To take into account the effect of pH on the free ligand concentration in a complex-ation
reaction, it is useful to introduce a conditional formation constant, or effec-tive formation
constant. Such constants are pH-dependent equilibrium constants that apply at a single pH only.
For the reaction of Fe31 with oxalate, for example, we can write the formation constant K1 for
the first complex as

At a particular pH value, a2 is constant, and we can combine K1 and a2 to yield a new

conditional constant K19:

The use of conditional constants greatly simplifies calculations because cT is often known or is
easily computed, but the free ligand concentration is not as eas-ily determined. The overall
formation constants, b values, for the higher complexes, [Fe(ox)2]2 and [Fe(ox)3]32, can also be
written as conditional constants.

Complexation reactions have many uses in analytical chemistry. One of the earliest uses, which
is still widespread, is in complexometric titrations. In these titrations, a metal ion reacts with a
suitable ligand to form a complex, and the equivalence point is determined by an indicator or an
appropriate instrumental method. The formation of soluble inorganic complexes is not widely
used for titrations, but the formation of precipitates, particularly with silver nitrate as the
titrant, is the basis for many impor-tant determinations, as discussed in Section 17B-2.

17B-1 Complexation Titrations

Complexometric titration curves are usually a plot of pM 5 –log [M] as a function of the volume
of titrant added. Usually in complexometric titrations, the ligand is the titrant, and the metal ion
is the analyte, although occasionally the roles are reversed. As we shall see later, many
precipitation titrations use the metal ion as the titrant. Most simple inorganic ligands are
unidentate, which can lead to low complex stabil-ity and indistinct titration end points. As
titrants, multidentate ligands, particularly those having four or six donor groups, have two
advantages over their unidentate counterparts. First, they generally react more completely with
cations and thus pro-vide sharper end points. Second, they ordinarily react with metal ions in a
single-step process, whereas complex formation with unidentate ligands usually involves two or
more intermediate species (recall Equations 17-1 through 17-4).
The advantage of a single-step reaction is illustrated by the titration curves shown in Figure 17-
1. Each of the titrations shown involves a reaction that has an overall equilibrium constant of
1020. Curve A is computed for a reaction in which a metal-ion M having a coordination number
of four reacts with a tetradentate ligand D to form the complex of MD (we have again omitted
the charges on the two reactants for conve-nience). Curve B is for the reaction of M with a
hypothetical bidentate ligand B to give MB2 in two steps. The formation constant for the first
step is 1012 and for the second

Reference:
Skoog, D. A. Fundamentals of Analytical Chemistry, 9th Ed.; Cengage - Brooks/Cole: Belmont,
CA, 2012.