Conditional formation constant figure

You can see from the example that a metal-EDTA complex becomes less stable at lower pH. For a titration reaction to be effective, it must go to completion (say, 99.9%), which means that the equilibrium constant is large—the analyte and titrant are essentially completely reacted at the equivalence point. Figure 12-9 shows how pH affects the titration of Ca2+ with EDTA. Below pH 8, the end point is not sharp enough to allow accurate determination. The conditional formation constant for CaY2" is just too small for complete reaction at low pH. 

For a titration with EDTA, you can follow the derivation through and find that the formation constant, Kf, should be replaced in Equation 12-11 by the conditional formation constant, K, which applies at the fixed pH of the titration. Figure 12-12 shows a spreadsheet in which Equation 12-11 is used to calculate the Ca2+ titration curve in Figure 12-11. As in acid-base titrations, your input in column B is pM and the output in column E is volume of titrant. To find the initial point, vary pM until V, is close to 0. 

Equation 2.140 shows that formation of the MY(n 4>f complex is Y4- dependent. The species Y4- is pH dependent. Figure 2.21 shows that the species Y4- begins to form above pH 7 and approaches maximum at pH 12. Because of this pH dependency of the Y4" species, conditional formation constants are used to estimate EDTA-metal complexes in solution. Considering that... 

FIGURE 11-3 Conditional formation constants as a function of pH for metal-EDTA complexes. The dotted curve, Zn -I- NH3, represents zinc in the presence of[NHa] + [NH4 ] = 1 M. Adapted from Ringbom. )... 

Titration curves like those of Figure 11-5 can be generalized (Figure 11-6) to a single set based only on conditional formation constants if the quantity pM is used as ordinate instead of pM. When the conditional formation constant is much less... 

FIGURE 11-6 Titration curves of 10 M mptal ion solutions with a ligand forming 1 1 complexes, with conditional formation constants ranging from 10 to 10 . 

FIGURE 11-7 Titration error as a function of conditional formation constant for ApAf values from 0.1 to 4. Adapted from Bingbom. )... 

Figure 11-7 depicts the relation between the titration error and the product Cm STm-l -Figure 11-3 indicates that conditional formation constants of at least 10 ° are possible for most metal ions in a selected pH region. According to Figure 11-7 a titration error of 0.1% should be easily attainable for 0.01 M solutions of such metals. For a 0.1% relative excess of reagent in the titration of 0.01 M metal ion, [Y ] of the reagent then equals 10" M. A value of = 10 then corresponds to a 99.9% conversion of metal ion to EDTA complex since [MY]/Cm = 1000. 

The logarithm of the formation constant of calmagite with calcium is 6.1, a smaller value than with magnesium. The effect of this difference is that the conditional formation constant is not large enough at a pH of about 10 for calmagite to act as a sensitive indicator for calcium (Figure 11-8). Consequently, for a sharp end point in... 

Assume that log P4, for chloride, bromide, and iodide with Zn is — 1, — 0.74, and — 1.25 and with Cd" " is 0.9, 2.53, and 6.1. (a) Calculate the masking index for Zn" " and Cd" " in 1.0 Af chloride, 1.0 Af bromide, and 0.1 Af and 1.0 Af iodide. Assume activity coefficients of unity and that the metal ions are present predominately as their highest complexes, (b) Assuming that the conditional formation constants of Zn" " and Cd with EDTA are the same (Figure 11-3), which condition is most favorable for the titration of zinc in the presence of cadmium ... 

The conditional formation constant for the calciumyEDTA complex at pH 10 is obtained from the formation constant of the complex (see Table 17-3) and the value for EDTA at pH 10 (see Figure 17-4). Thus, if we substitute into Equation 17-25, we get... 

Figure 9.4 shows the minimum pH at which different metals can be titrated with EDTA. The points on the curve represent the pH at which the conditional formation constant K for each metal is 10 (log K = 6), which was arbitrarily chosen as the minimum needed for a sharp end point. Note that the smaller Kf, the more alkaline the solution must be to obtain a K of 10 (i.e., the larger 0 4 must be). Thus, Cd with Kf only about 10 requires a pH of about 8 or above. The... 

The completeness of reaction (and hence the sharpness of the equivalence point) is determined by the conditional formation constant, ay -Kf, which is pH dependent. Because ay - decreases as pH is lowered, pH is an important variable determining whether a titration is feasible. The end point is more distinct at high pH. However, the pH must not be so high that metal hydroxide precipitates. The effect of pH on the titration of Ca was shown in Figure 13-8. 

The redox potentials may first be measured directly on the system in which the transfer takes place. This situation corresponds usually to intramolecular processes, but may also be encountered in bimolecular processes when the formation constant Kj is large enough for all the molecules to be complexed in the conditions of the experiment. The four possible redox states of the system are represented in Figure 6, each state being considered in its equilibrium nuclear configuration. The driving force AG° may be calculated either from Eq. (Al) or from Eq. (A2) ... 

FIGURE 5.1 Distribution diagram showing the formation of vanadate and peroxovanadate species as a function of the concentration of hydrogen peroxide and of pH. Conditions for the simulation 2mmol/L total vanadate 0.1 tmol/L to 10 mmol/L total hydrogen peroxide 0.15 mol/L ionic strength with NaCl pH values, as indicated. The formation constants are from reference 11. 

FIGURE 5.2 Diagram showing the distribution of peroxovanadium species as a function of pH. Simulation conditions total vanadate, 2.0 mmol/L total hydrogen peroxide, 4.0 mmol/L ionic strength, 0.15 mol/L with NaCl pH range, 1 to 10. Formation constants are from reference 11. 

Curve A in Figure 17-6 is a plot of data for the titration in Example 17-4. Curve B is the titration curve for a solution of magnesium ion under identical conditions. The formation constant for the EDTA complex of magnesium is smaller than that of the calcium complex, which results in a smaller change in the p-function in the equivalence-point region. 

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