Neutralization titrations Titration curves

A plot of pH against the volume of alkali added (mL) is known as a neutralization or titration curve (Fig. 22.2). The curve is generated by a potentiometric titration in which pH is measured after each addition of alkali (or acid). The significant feature of the curve is the very sharp and sudden change in pH near to the equivalence point of the titration. For a strong acid and alkali this will occur at pH 7. If either the acid or base concentration is unknown, a prehminary titration is necessary to find the approTumate equivalence point followed by a more accurate titration as described on p. 146. The ideal pH range for an indicator is 4.S-9.5. 

Although not commonly used, thermometric titrations have one distinct advantage over methods based on the direct or indirect monitoring of plT. As discussed earlier, visual indicators and potentiometric titration curves are limited by the magnitude of the relevant equilibrium constants. For example, the titration of boric acid, ITaBOa, for which is 5.8 X 10 °, yields a poorly defined equivalence point (Figure 9.15a). The enthalpy of neutralization for boric acid with NaOlT, however, is only 23% less than that for a strong acid (-42.7 kj/mol... 

When the concentrations of HA and A are equal, equation 9.9 reduces to = [HaO ]) ot pH = pKa. Thus, the piweak acid can be determined by measuring the pH for a solution in which half of the weak acid has been neutralized. On a titration curve, the point of half-neutralization is approximated by the volume of titrant that is half of that needed to reach the equivalence point. As shown in Figure 9.20, an estimate of the weak acid s piQ can be obtained directly from the titration curve. 

A quantitative analysis for NH3 in several household cleaning products is carried out by titrating with a standard solution of HGl. The titration s progress is followed thermometrically by monitoring the temperature of the titration mixture as a function of the volume of added titrant. Household cleaning products may contain other basic components, such as sodium citrate or sodium carbonate, that will also be titrated by HGl. By comparing titration curves for prepared samples of NH3 to titration curves for the samples, it is possible to determine that portion of the thermometric titration curve due to the neutralization of NH3. 

Neutralization. The choice of a reagent for pH adjustment depends on cost ease and safety of storage and handling effectiveness, eg, for removing heavy metals, buffet characteristics of the pH titration curve as they affect pH control and avadabihty. The three principal reagents for neutralization of acid wastes are sodium hydroxide, sodium carbonate, and hydrated calcium hydroxide. 

It was noted that the content of functional groups on the surface of studied A1,03 was 0,92-10 mol/g of acid character for (I), FOS-IO mol/g of basic character for (II). The total content of the groups of both types was 1,70-lO mol/g for (III). The absence of appreciable point deviations from a flat area of titration curves in all cases proves simultaneously charges neutralization character on the same adsoi ption centers and non-depending on their density. The isoelectric points of oxide surfaces have been detenuined from titration curves and have been confirmed by drift method. 

If a sample contains groups that can take up or lose a proton, (N//, COO//), then one must expect the pH and the concentration to affect the chemical shift when the experiment is carried out in an acidic or alkaline medium to facilitate dissolution. The pH may affect the chemical shift of more distant, nonpolar groups, as shown by the amino acid alanine (38) in neutral (betaine form 38a) or alkaline solution (anion 38b). The dependence of shift on pH follows the path of titration curves it is possible to read off the pK value of the equilibrium from the point of inflection... 

As the titration begins, mostly HAc is present, plus some H and Ac in amounts that can be calculated (see the Example on page 45). Addition of a solution of NaOH allows hydroxide ions to neutralize any H present. Note that reaction (2) as written is strongly favored its apparent equilibrium constant is greater than lO As H is neutralized, more HAc dissociates to H and Ac. As further NaOH is added, the pH gradually increases as Ac accumulates at the expense of diminishing HAc and the neutralization of H. At the point where half of the HAc has been neutralized, that is, where 0.5 equivalent of OH has been added, the concentrations of HAc and Ac are equal and pH = pV, for HAc. Thus, we have an experimental method for determining the pV, values of weak electrolytes. These p V, values lie at the midpoint of their respective titration curves. After all of the acid has been neutralized (that is, when one equivalent of base has been added), the pH rises exponentially. 

Figure 26.1 A titration curve for alanine, plotted using the Henderson-Hasselbalch equation. Each of the two legs is plotted separately. At pH < 1, alanine is entirely protonated at pH = 2.34, alanine is a 50 50 mix of protonated and neutral forms at pH 6.01, alanine is entirely neutral at pH = 9.69, alanine is a 50 50 mix of neutral and deprotonated forms at pH > 11.5, alanine is entirely deprotonated.

Look carefully at the titration curve in Figure 26.1. In acid solution, the amino acid is protonated and exists primarily as a cation. In basic solution, the amino acid is deprotonated and exists primarily as an anion. In between the two is an intermediate pH at which the amino acid is exactly balanced between anionic and cationic forms and exists primarily as the neutral,... 

Principle. By means of potentiometric titration (in nonaqueous media) of a blend of sulfonic and sulfuric acids, it is possible to split the neutralization points corresponding to the first proton of sulfuric acid plus that of sulfonic acid, and to the second proton of sulfuric acid. The first derivate of the titration curve allows identification of the second points the corresponding difference in the volume of titrating agent is used as a starting point in the calculation method (Fig. 4). 

Below is the titration curve for the neutralization of 25 mL of a monoprotic acid with a strong base. Answer the following questions about the reaction and explain your reasoning in each case, (a) Is the acid strong or weak (b) What is the initial hydronium ion concentration of the acid (c) What is K, for the acid (d) What is the initial concentration of the... 

Fig. 1 Typical titration curves. The water curve indicates the amount of alkali needed to titrate the water, and the acid curve is a conventional titration curve. The difference curve is the horizontal difference between the acid and the water curve, and is the adjusted titration curve, e.g., point b is c—a. The pK is the point of inflection, which is also the point at where half of the acid is neutralized.

The slope of the tangent to the curve at the inflection point where oc = is thus inversely proportional to the number of electrons n. The E-oc curves are similar to the titration curves of weak acids or bases (pH-or). For neutralization curves, the slope dpH/doc characterizes the buffering capacity of the solution for redox potential curves, the differential dE/da characterizes the redox capacity of the system. If oc — for a buffer, then changes in pH produced by changes in a are the smallest possible. If a = in a redox system, then the potential changes produced by changes in oc are also minimal (the system is well poised ). 

First of all, the mesomerism of HBI is rendered complex by the presence of several protonable groups actually, HBI might exist, depending on pH, under cationic, neutral, zwitterionic, anionic, and possibly enolic forms (Fig. 3a). The experimental p/sTa s of model analogs of HBI in aqueous solutions have been studied. Titration curves follow two macroscopic transitions at pH 1.8 and pH 8.2, each corresponding to a single proton release [69]. Comparison of theoretical... 

In the process of a weak acid or weak base neutralization titration, a mixture of a conjugate acid-base pair exists in the reaction flask in the time period of the experiment leading up to the inflection point. For example, during the titration of acetic acid with sodium hydroxide, a mixture of acetic acid and acetate ion exists in the reaction flask prior to the inflection point. In that portion of the titration curve, the pH of the solution does not change appreciably, even upon the addition of more sodium hydroxide. Thus this solution is a buffer solution, as we defined it at the beginning of this section. 

First obtain the complete titration curve for the sample. This will involve cautious addition of the NaOH around the inflection points so that you can carefully track the sharp change in the pH at these points. Alternatively, you may choose to use a computer for data acquisition, as in Experiment 18, Part B. Phosphoric acid (H3P04) has three hydrogens to be neutralized. The third hydrogen is lost with only a slight change in pH, however, so you may only see two inflection points. If citric acid is also present (check the can label), there maybe other inflection points as well. 

The information that is available in many chemical plants is a titration curve for each stream to be neutralized. The method outlined below can be used in this... 

The potentiometric titration curves of gels, which relate the pH of the exterior solution to the degree of ionization of the gel, resemble the titration curves of monofunctional acids or bases. However, the dissociation constants differ, often by two orders of magnitude, from the expected value for the functional group, and the slope of the curves is not the usual one. Addition of neutral salt changes the picture markedly and brings the curves closer to expectation. In the case of weak or medium... 

The carbon blacks used by Puri and Bansal (59) seemed to be different from the carbons used by Boehm et al. (35). Titration curves published by Puri and Bansal (59) show distinct breaks at pH 10-11. Other authors (26, 44) did not find this inflection. Possibly, no phenolic groups were present in Puri s samples. As will be shown below, the group neutralized by NaOH, but not by Na COa, was identified as phenolic hydroxyl group. 

Studebaker (63) studied the potentiometric titration of surface oxides in nonaqueous medium. Using sodium aminoethoxide in ethylene diamine, he found indications for the appearance of two breaks in the titration curves. The first break was attributed to carboxyl groups or groups of similar acidity, the second one to phenols. Only two-thirds of the acidity that was determined by NaOH neutralization could be titrated in nonaqueous medium. 

Buffers have their limits, however. The acid s proton reservoir, for excimple, can compensate for the addition of only a certain amount of base before it runs out of protons that can neutralize free hydroxide. At this point, a buffer has done all it can do, and the titration curve resumes its steep upward slope. 

In potentiometric titration a voltage is obtained from an electrode that is sensitive to an ionic species such as H-jO+, i.e., the pH of the solution in this case. We will consider the titration of the mixture of a strong acid (HC1) and a weak acid (CJ+jCOOH) with NaOH (ref. 10). As 2 ml volumes of the base are given to the acidic solution, the pH increases and when one of the acids is neutralized the pH changes very rapidly by a small addition of NaOH. We want to find these maximum points of the first derivative of the titration curve. In the following main program the DATA lines contain 32 data pairs, each consisting of the volume of the added NaOH in ml and the measured pH. 

---