Formation constant conditional

Since the titration is carried out at a pH of 10, some of the EDTA is present in forms other than Y . In addition, the presence of NH3 means that the EDTA must compete for the Cd +. To evaluate the titration curve, therefore, we must use the appropriate conditional formation constant. Erom Tables 9.12 and 9.14 we find that ay4- is 0.35 at a pH of 10, and that acd + is 0.0881 when the... 

After the equivalence point, EDTA is in excess, and the concentration of Cd + is determined by the dissociation of the CdY complex. Examining the equation for the complex s conditional formation constant (equation 9.15), we see that to calculate Ccd we must first calculate [CdY ] and Cedxa- After adding 30.0 mb of EDTA, these concentrations are... 

Calculate the conditional formation constant for the Zn-EDTA complex at pH 9.0 in a solution... 

The number K f = aY. Kf is called the conditional formation constant, or the effective formation constant. It describes the formation of MY" 4 at any particular pH. Later, after we learn to use Equation 12-6, we will modify it to allow for the possibility that not all the metal ion is in the form M"+. 

The conditional formation constant allows us to look at EDTA complex formation as if the uncomplexed EDTA were all in one form ... 

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. 

With the conditional formation constant we can treat EDTA complex formation as if all the free EDTA were in one form. 

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. 

Now consider a titration of Zn2+ by EDTA in the presence of NH3. The extension of Equation 12-7 requires a new conditional formation constant to account for the fact that only some of the EDTA is in the form Y4 and only some of the zinc not bound to EDTA is in the form Zn2+ ... 

Solution In Equation 12-17, we found that aZn2+ = 1.8 X 10 5. Table 12-1 tells us that aYr- = 0.30. Therefore, the conditional formation constant is... 

Equation 12-18 states that the effective (conditional) formation constant for an EDTA complex is the product of the formation constant, Kf. times the fraction of metal in the form M" + times the fraction of EDTA in the form Y4- K" = aM, + aY4 h t. Table 12-1 told us that aY4- increases with pH until it levels off at 1 near pH 11. 

In a direct titration, analyte is titrated with standard EDTA. The analyte is buffered to a pH at which the conditional formation constant for the metal-EDTA complex is large and the color of the free indicator is distinctly different from that of the metal-indicator complex. 

The conditional formation constant for Hg(EDTA)2- must be greater than K f for Mg(FDTA)2, or else Mg2+ is not displaced from Mg(EDTA)2-. 

Formation constants for EDTA are expressed in terms of [Y4-], even though there are six protonated forms of EDTA. Because the fraction (aY4 1 of free EDTA in the form Y4 depends on pH, we define a conditional (or effective) formation constant as K = aYj Kf = MY" 4 /[M"+ [EDTA], This constant describes the hypothetical reaction Mn+ + EDTA MY 1-4, where EDTA refers to all forms of EDTA not bound to metal ion. Titration calculations fall into three categories. When excess unreacted M"+ is present, pM is calculated directly from pM = — log M l+]. When excess EDTA is present, we know both [MY"-4] and [EDTA], so IM"+] can be calculated from the conditional formation constant. At the equivalence point, the... 

The greater the effective formation constant, the sharper is the EDTA titration curve. Addition of auxiliary complexing agents, which compete with EDTA for the metal ion and thereby limit the sharpness of the titration curve, is often necessary to keep the metal in solution. Calculations for a solution containing EDTA and an auxiliary complexing agent utilize the conditional formation constant K" = aM aY4- Kt, where aM is the fraction of free metal ion not complexed by the auxiliary ligand. 

EDTA (ethylenediaminetetraacetic acid) (H02CCH2)2NCH2CH2N-(CH2C02H)2, the most widely used reagent for complexometric titrations. It forms 1 1 complexes with virtually all cations with a charge of 2 or more, effective formation constant Equilibrium constant for formation of a complex under a particular stated set of conditions, such as pH, ionic strength, and concentration of auxiliary complexing species. Also called conditional formation constant. 

TABLE 7 Some reported conditional formation constants for Peacock-Weakley complexes... 

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... 

Calculate the conditional formation constant for the Zn-EDTA complex at pH 9.0. in a solution 0.100 M with respect to ammonia. Can zinc be titrated quantitatively with EDTA solution at this pH ... 

The values for formation constants in Table 11-2 are somewhat misleading in that reactions of Y with protons and of metal ions with other substances in solution represent competition for the metal ion-EDTA reaction. As Ringbom pointed out, we rarely need to know the concentration of every species in solution what is of most concern is the completeness of the reaction of interest. To simplify calculations when there are side reactions, a quantity [Y j is defined as the concentration of all forms of EDTA that are not coordinated to the metal, and a quantity [M ] as the concentration of the metal ion that has not reacted with EDTA. With these quantities a conditional formation constant may be defined as... 

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. )... 

In analogy to a pH titration curve, pM (— log [M]) may be plotted against the fraction titrated. Under the usual titration conditions, in which the concentration of metal ions is small compared with the concentrations of the buffer and the auxiliary complexing agents, the fractions ay and are essentially constant during the titration. The titration curve then can be calculated directly from the conditional formation constant since it also remains constant. 

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... 

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