Polyprotic Titrations

Titrations of polyprotic acids will have more than one equivalence point and more than one half equivalence point. For the MCAT, assume that the first proton completely dissociates before the second proton begins to dissociate. (This assumption is only acceptable if the second proton is a much weaker add than the first, which is usually the case.) Thus we have a titration curve like the one shown below. 

If the expected equivalence point for a titration is at a pH of 8.2, which of the following would be the best indicator for the titration  

phenolphthalein B. bromthymol blue C. methyl orange D. methyl violet  

On the titration curve of the H2C03 pictured below, at which of the following points is the concentration of  

138- The following is a list of acid dissociation constants for 4 acids. 

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Because many biological systems use polyprotic acids and their anions to control pH, we need to be familiar with pH curves for polyprotic titrations and to be able to calculate the pH during such a titration. The titration of a polyprotic acid proceeds in the same way as that of a monoprotic acid, but there are as many stoichiometric points in the titration as there are acidic hydrogen atoms. We therefore have to keep track of the major species in solution at each stage, as described in Sections 10.16 and 10.17 and summarized in Figs. 10.20 and 10.21. 

This approach can be used to sketch titration curves for other acid-base titrations including those involving polyprotic weak acids and bases or mixtures of weak acids and bases (Figure 9.8). Figure 9.8a, for example, shows the titration curve when titrating a diprotic weak acid, H2A, with a strong base. Since the analyte is... 

The theory of titrations between weak acids and strong bases is dealt with in Section 10.13, and is usually applicable to both monoprotic and polyprotic acids (Section 10.16). But for determinations carried out in aqueous solutions it is not normally possible to differentiate easily between the end points for the individual carboxylic acid groups in diprotic acids, such as succinic acid, as the dissociation constants are too close together. In these cases the end points for titrations with sodium hydroxide correspond to neutralisation of all the acidic groups. As some organic acids can be obtained in very high states of purity, sufficiently sharp end points can be obtained to justify their use as standards, e.g. benzoic acid and succinic acid (Section 10.28). The titration procedure described in this section can be used to determine the relative molecular mass (R.M.M.) of a pure carboxylic acid (if the number of acidic groups is known) or the purity of an acid of known R.M.M. 

Diphenylcarbazide as adsorption indicator, 358 as colorimetric reagent, 687 Diphenylthiocarbazone see Dithizone Direct reading emission spectrometer 775 Dispensers (liquid) 84 Displacement titrations 278 borate ion with a strong acid, 278 carbonate ion with a strong acid, 278 choice of indicators for, 279, 280 Dissociation (ionisation) constant 23, 31 calculations involving, 34 D. of for a complex ion, (v) 602 for an indicator, (s) 718 of polyprotic acids, 33 values for acids and bases in water, (T) 832 true or thermodynamic, 23 Distribution coefficient 162, 195 and per cent extraction, 165 Distribution ratio 162 Dithiol 693, 695, 697 Dithizone 171, 178... 

We can predict the pH at any point in the titration of a polyprotic acid with a strong base by using the reaction stoichiometry to recognize what stage we have reached in the titration. We then identify the principal solute species at that point and the principal proton transfer equilibrium that determines the pH. 

The titration of a polyprotic acid has a stoichiometric point corresponding to the removal of each acidic hydrogen atom. The pH of a solution of a polyprotic acid undergoing a titration is estimated by considering the primary species in solution and the proton transfer equilibrium that determines the pH. 

In the titration of a polyprotic acid, the added base reacts first with the more acidic hydrogen atoms of the neutral acid. For example, the titration of maleic acid takes place in two steps. For removal of one acidic hydrogen atom of maleic acid, p = 1.82 (. al = 1-5 X 10 ) ... 

Titration of Polyprotic Acids Sulfuric Acid and Phosphoric Acid... 

Titrations curves for polyprotic acids have an inflection point for each hydrogen in the formula if the dissociation constant (Ka) for each hydrogen is very different from the others and if any dissociation constant is not too small. The titration curves of the polyprotic acids H2S04 and H3P04 are shown in Figures 5.6 and 5.7. Sulfuric acid has essentially one inflection point (like hydrochloric acid—compare with Figure 5.1(a)), while phosphoric acid has two apparent inflection points. Both hydrogens on the... 

Define monoprotic acid, polyprotic acid, monobasic base, polybasic base, titration curve, and inflection point. 

Compare the alkalimetric titration of a polyprotic acid (e.g., polyaspartic acid) with that of an Al203 dispersion show in either case the effect of the presence of a metal ion (e.g., Cu2+) on the titration curve. 

Polyprotic acids are fairly important and their potentiometric pH titrations are common. For 2-component systems of this kind, it is possible to turn around the computations and come up with explicit, non-iterative solutions. So far we have computed the species concentrations knowing the total component concentrations, which is an iterative process. This is the normal arrangement in titrations where volumes and total concentrations are known and the rest is computed, e.g. the [H+] and thus the pH. Turning around things in this context means that one calculates the titration volume required to reach a given (measured) pH. One knows the i/-value and computes the corresponding x-value. In this way there are explicit equations that can directly be implemented in Excel. 

From an acid-base titration curve, we can deduce the quantities and pK.d values of acidic and basic substances in a mixture. In medicinal chemistry, the pATa and lipophilicity of a candidate drug predict how easily it will cross cell membranes. We saw in Chapter 10 that from pKa and pH, we can compute the charge of a polyprotic acid. Usually, the more highly charged a drug, the harder it is to cross a cell membrane. In this chapter, we learn how to predict the shapes of titration curves and how to find end points with electrodes or indicators. 

The principles developed for titrations of monoprotic acids and bases are readily extended to titrations of polyprotic acids and bases. We will examine two cases. 

J Yarger, R Nieman, and A Bieber,/. Chem. Educ. 74,243-246 (1997). NMR Titration Used to Observe Specific Proton Dissociation in Polyprotic Tripeptides ... 

Acid-Base Indicators Polyprotic Acid Titrations... 

We can predict the pH at any point in the titration of a polyprotic acid with a strong base (see Toolbox 11.1). First, we have to consider the reaction stoichiometry to recognize what stage we have reached in the titration. Next we have to identify the principal solute species at that point and the proton transfer equilibrium that determines the pH. We then carry out the calculation appropriate for the solution, referring to the previous worked examples if necessary. In this section, we see how to describe the solution at various stages of the titration our conclusions are summarized in Tables 11.3 and 11.4. 

TOOLBOX 11.1 How to predict the pH during the titration of a polyprotic acid... 

The pH of the solution of a polyprotic acid at any point in a titration can be predicted by considering the species present at each stage. 

Determine the pH at any point in the titration of a polyprotic acid with a strong base, Toolbox... 

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