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5.5:

EDTA: Conditional Formation Constant

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Analytical Chemistry
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JoVE 핵심 Analytical Chemistry
EDTA: Conditional Formation Constant

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Recall that EDTA exists in various forms depending on the pH of the solution. Among the different forms, the fully unprotonated species is thought of as the one that chelates with metal ions.

So, the formation constant expression for a metal–EDTA complex considers only the fully unprotonated form of EDTA, which predominates only at high pH.

At any given pH, different forms of EDTA are in equilibrium, and the concentrations of these forms sum to the total concentration of uncomplexed EDTA.

So, the fraction of EDTA in the fully unprotonated form is needed. Rearranging this expression and substituting it in the formation constant equation gives a modified factor termed the conditional formation constant.

The fraction of EDTA in the fully unprotonated form is a constant at a given pH, so the conditional formation constant is pH-dependent.

The higher the pH, the higher the conditional formation constant, and the more stable the metal–EDTA complex.

5.5:

EDTA: Conditional Formation Constant

Each EDTA molecule has six binding sites: four carboxyl groups and two amino groups. The fully protonated form of EDTA is represented as H6Y2+. However, it can exist in different forms, H5Y+, H4Y, H3Y, H2Y2, and HY3, depending on the pH of the solution. In very basic solutions with pH > 10.17, the fully deprotonated form, Y4, is the predominant species that readily complexes with metal ions in a 1:1 ratio.

For the equilibrium reaction of the metal with the Y4 form of EDTA, the formation constant, Kf, is also known as the stability constant. Note that the Kf can be defined for any of the forms of EDTA in the solution. The value of Kf increases as the positive charge on metal ions increases. At a fixed pH, the different forms of the EDTA are in equilibrium so that the total molar concentration of all forms of EDTA equals the total molar concentration of the uncomplexed EDTA. The term cºEDTA is the total concentration of all forms of uncomplexed EDTA. At a fixed pH, the fraction of total EDTA present as Y4becomes constant, gives an expression where Kf′ is called the conditional formation constant or effective formation constant, which has a fixed value at a given pH. Therefore, it can calculate the equilibrium concentrations of free metal ions and the metal–EDTA complexes.