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Complexometric titration (sometimes chelatometry) is a form of volumetric analysis in which the In practice, the use of EDTA as a titrant is well established . Complexometric Titration Is a type of volumetric analysis wherein colored complex is used to determine the endpoint of titration. Explore more on EDTA. APCH Chemical Analysis. Complexometric Titrations. EDTA. DTA forms stable complexes with most metal ions – the exceptions being the group 1 cations.

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Complexometric Titration – EDTA | Complexometric Titration Reactions

Practical analytical applications of complexation titrimetry were slow to develop because many metals and ligands form a series of metal—ligand complexes. Recall that an acid—base titration curve for a complexometris weak acid has a single end point if its two K a values are not sufficiently different.

InSchwarzenbach introduced aminocarboxylic acids as multidentate ligands. The most widely used of these new ligands—ethylenediaminetetraacetic acid, or EDTA—forms strong 1: The availability of a rdta that gives a single, easily identified end point made complexation titrimetry a practical analytical method. Ethylenediaminetetraacetic acid, or EDTA, is an aminocarboxylic acid.

EDTA, which is shown in Figure 9. The resulting metal—ligand complex, in which EDTA forms a cage-like structure around the metal ion Figure 9. The actual number ckmplexometria coordination sites depends on the size of the metal ion, however, all metal—EDTA complexes have a 1: In addition to its properties as a ligand, EDTA is also a weak acid. The first four values are for the carboxylic acid protons and the last two values are for the ammonium protons.

The specific form of EDTA in reaction 9. The formation constant for CdY 2— in equation 9. To use equation 9. At complexomettia pH a mass balance on EDTA requires that its total concentration equal the combined concentrations of each of its forms.

9.3: Complexation Titrations

As shown in Table 9. To maintain a constant pH during a complexation titration we usually add a buffering agent. We can account for the effect of an auxiliary complexing agentsuch as NH 3in the same way we accounted for the effect of pH.

Because the concentration of NH 3 in a buffer is essentially constant, we can rewrite this equation. To do so we need to know the shape of a complexometric EDTA titration curve.

The analogous result for a complexation titration shows the change in pM, where M is the metal ion, as a function of the volume of EDTA. In this section we will learn how to calculate a titration curve using the equilibrium calculations from Chapter 6. We also will learn how to quickly sketch a good approximation of any complexation titration curve using a limited number of simple calculations.

Calculate the conditional formation constant for the metal—EDTA complex. To evaluate the titration curve, therefore, we first need to calculate the conditional formation constant for CdY 2—. Using these values, the conditional formation constant is. Calculate the volume of EDTA needed to reach the equivalence point. The next task in calculating the titration curve is to determine the volume of EDTA needed to reach the equivalence point.


At the equivalence point we know that. Calculate pM values before the equivalence point by determining the concentration of unreacted metal ions. For example, after adding 5. Calculate pM at the equivalence point using the conditional formation constant.

First, we calculate the concentration of CdY 2—. Calculate pM after the equivalence point using the conditional formation constant.

For example, after adding Substituting into equation 9. We will use this approach when learning how to sketch a complexometric titration curve. The red points correspond to the data in Table 9.

The blue line shows the complete titration curve. Calculate titration curves for the titration of Evta titration includes an auxiliary complexing agent. Compare your results with Figure 9. Click here to review your answer to this exercise. In this section we demonstrate a simple complxeometria for sketching a complexation titration curve. Our goal is to sketch the titration curve quickly, using as few calculations as possible.

Complexometriia is the same example that we used in developing the calculations for a complexation titration curve. You can review the results of that calculation in Table 9. The calculations are straightforward, as we saw earlier.

See the text for additional details. The third step in sketching our titration curve is to add two points after the equivalence point. Beginning with the conditional formation constant.

Our derivation here is general and applies to any complexation titration using EDTA as a titrant. Finally, we complete our sketch by drawing a smooth curve that connects the three straight-line segments Figure 9. A comparison of our sketch to the exact titration curve Figure 9. Sketch titration curves for the titration of Compare your sketches to the calculated titration curves from Practice Exercise 9. The equivalence point of a complexation titration occurs when we react stoichiometrically equivalent amounts of titrand and titrant.

As is the case with acid—base titrations, we estimate the equivalence point of a complexation titration using an experimental end point. A variety of methods are available for locating the end point, including indicators and sensors that respond to a change in the solution conditions.

Most indicators for complexation titrations are organic dyes—known as metallochromic indicators —that form stable complexes with metal ions. If MIn n — and In m — have different colors, then the change in color signals the end point. If the metal—indicator complex is too strong, the change in color occurs after the equivalence point. If the metal—indicator complex is too weak, however, the end point occurs before we reach the equivalence point.

Most metallochromic indicators also are weak acids. Unfortunately, because the indicator is a weak eddta, the color of the uncomplexed indicator also changes with pH. Complexoetria solid lines are equivalent to a step on a conventional ladder diagram, indicating conditions where two or edtx species are equal in concentration. Even if a suitable indicator does not exist, it is often possible to complete an EDTA titration by introducing a small amount of a secondary metal—EDTA complex, if the secondary metal ion forms a stronger complex with the indicator and a weaker complex with EDTA than the analyte.

The experimental approach is essentially identical to that described earlier for an acid—base titration, to which you may refer. See Chapter 11 for more details about ion selective electrodes.


This may be difficult if the solution is already colored. Other absorbing species present within the sample matrix may also interfere. This is often a problem when analyzing clinical samples, such as blood, or environmental samples, such as natural waters.

At the beginning of the titration edfa absorbance is at a maximum. As we add EDTA, however, the reaction. After the equivalence point the absorbance remains essentially unchanged.

Complexometric titration – Wikipedia

The resulting spectrophotometric titration curve is shown in Figure 9. Other common spectrophotometric titration curves are shown in Figures 9. The red arrows indicate the end points for each titration curve.

The best way to appreciate the theoretical and practical details discussed in this section is to carefully examine a typical complexation titrimetric method. Although each method is unique, the following description of the determination of the hardness of water provides an instructive example of a typical procedure. Determination of Hardness of Water and Wastewater. The operational definition of water hardness is the total concentration of cations in a sample capable of forming insoluble complexes with soap.

Calmagite is used as an indicator. Select a volume of sample requiring less than 15 mL of titrant to keep the analysis time under 5 minutes and, if necessary, dilute the sample to 50 mL with distilled water. Add 1—2 drops of indicator and titrate with a standard solution of EDTA until the red-to-blue end point is reached Figure 9.

Why is the sample buffered to a pH of 10?

Complexometric Titration

What problems might you expect at a higher pH or a lower pH? Superimposed on each titration curve is the range of conditions for which the average analyst will observe the end point.

At a pH of 9 an early end point is possible, leading to a negative determinate error. A late end point and a positive determinate error are possible if we use a pH of This displacement is stoichiometric, so the total concentration of hardness cations remains unchanged. Why does the procedure specify that the titration take no longer than 5 minutes?

A time limitation suggests that there is a kinetically controlled interference, possibly arising from a competing chemical reaction. In this case the interference is the possible precipitation of CaCO 3 at a pH of The range of pMg and volume of EDTA over which the indicator complexomwtria color is shown for each titration curve.

Although many quantitative applications of complexation titrimetry have been replaced by other analytical methods, a few important applications continue to be relevant. In the section we review the general application of complexation titrimetry with an emphasis on applications from the analysis of water and wastewater. First, however, we discuss the selection and standardization of complexation titrants.

EDTA is a versatile titrant that can be used to analyze virtually all compexometria ions.