Electrode acid-base titration

The most obvious sensor for an acid-base titration is a pH electrode.For example, Table 9.5 lists values for the pH and volume of titrant obtained during the titration of a weak acid with NaOH. The resulting titration curve, which is called a potentiometric titration curve, is shown in Figure 9.13a. The simplest method for finding the end point is to visually locate the inflection point of the titration curve. This is also the least accurate method, particularly if the titration curve s slope at the equivalence point is small. 

Potcntiomctric Titrations In Chapter 9 we noted that one method for determining the equivalence point of an acid-base titration is to follow the change in pH with a pH electrode. The potentiometric determination of equivalence points is feasible for acid-base, complexation, redox, and precipitation titrations, as well as for titrations in aqueous and nonaqueous solvents. Acid-base, complexation, and precipitation potentiometric titrations are usually monitored with an ion-selective electrode that is selective for the analyte, although an electrode that is selective for the titrant or a reaction product also can be used. A redox electrode, such as a Pt wire, and a reference electrode are used for potentiometric redox titrations. More details about potentiometric titrations are found in Chapter 9. 

The indicator electrode employed in a potentiometric titration will, of course, be dependent upon the type of reaction which is under investigation. Thus, for an acid-base titration, the indicator electrode is usually a glass electrode (Section 15.6) for a precipitation titration (halide with silver nitrate, or silver with chloride) a silver electrode will be used, and for a redox titration [e.g. iron(II) with dichromate] a plain platinum wire is used as the redox electrode. 

Table 15.6 indicates common reagents and solvents and the appropriate electrode combination for a variety of acid-base titrations. 

Alkalinity is measured by acid-base titration with methylorange or phe-nolphthalein as indicator. Phenolphthalein changes color at pH 8.3, whereas methylorange changes color at pH 4.3. At pH 8 the neutralization of the strong alkali ingredients like NaOH is essentially complete. Further reduction of the pH to 4 will also measure carbonates and bicarbonates. Colorimetric tests and glass electrode systems are used to determine pH. 

Polarisation titrations are often referred to as amper-ometric or biamperometric titrations. It is necessary that one of the substances involved in the titration reaction be oxidisable or reducible at the working electrode surface. In general, the polarisation titration method is applicable to oxidation-reduction, precipitation and complex-ation titrations. Relatively few applications involving acid/base titration are found. Amperometric titrations can be applied in the determination of analyte solutions as low as ICE5 M to 10-6 M in concentration. 

Conductometric titrations. Van Meurs and Dahmen25-30,31 showed that these titrations are theoretically of great value in understanding the ionics in non-aqueous solutions (see pp. 250-251) in practice they are of limited application compared with the more selective potentiometric titrations, as a consequence of the low mobilities and the mutually less different equivalent conductivities of the ions in the media concerned. The latter statement is illustrated by Table 4.7108, giving the equivalent conductivities at infinite dilution at 25° C of the H ion and of the other ions (see also Table 2.2 for aqueous solutions). However, in practice conductometric titrations can still be useful, e.g., (i) when a Lewis acid-base titration does not foresee a well defined potential jump at an indicator electrode, or (ii) when precipitations on the indicator electrode hamper its potentiometric functioning. 

In overall form this equation resembles that for the glass electrode (Chapter 6) and a pM-EDTA curve resembles an acid-base titration curve. The mercury electrode is most usefully employed when coloured or turbid solutions are being titrated, or when dilute solutions and weak complexes lead to poor colour changes. 

It is possible to monitor the course of a titration using potentiometric measurements. The pH electrode, for example, is appropriate for monitoring an acid-base titration and determining an end point in lieu of an indicator, as in Experiment 10 in Chapter 5. The procedure has been called a potentiometric titration and the experimental setup is shown in Figure 14.11. The end point occurs when the measured pH undergoes a sharp change—when all the acid or base in the titration vessel is reacted. The same... 

In an acid-base titration, you carefully measure the volumes of acid and base that react. Then, knowing the concentration of either the acid or the base, and the stoichiometric relationship between them, you calculate the concentration of the other reactant. The equivalence point in the titration occurs when just enough acid and base have been mixed for a complete reaction to occur, with no excess of either reactant. As you learned in Chapter 8, you can find the equivalence point from a graph that shows pH versus volume of one solution added to the other solution. To determine the equivalence point experimentally, you need to measure the pH. Because pH meters are expensive, and the glass electrodes are fragile, titrations are often performed using an acid-base indicator. 

Elemental composition Pb 59.37%, Cl 40.63%. The compound is hydrolyzed in water to Pb02, which is separated, digested with nitric acid, diluted, and analyzed for lead. The aqueous solution containing the hydrolysis product HCl is determined by acid-base titration. The chloride ion is measured by an electrode or ion chromatography, or by titration with a standard solution of... 

The strength of nitric acid can be determined by acid-base titration against a standard solution of a strong base such as NaOH using a color indicator, or by potentiometric titration using a pH meter. Nitrate ion, NO3 in its aqueous solution, may be measured with a nitrate ion-selective electrode or by ion chromatography following appropriate dilution. 

Nitrogen dioxide can be identified by color, odor, and physical properties. It is dissolved in warm water and converted to nitric acid. The latter may be measured by acid-base titration or from analysis of nitrate ion by nitrate ion-specific electrode or by ion chromatography. Alternatively, nitrogen dioxide may be passed over heated charcoal to produce nitrogen and carbon dioxide that may be analysed by GC-TCD or GC/MS (See Nitrogen, Analysis). The characteristic masses for N2 and CO2 formed for their identification are 28 and 44, respectively. 

Acid-base, redox, precipitation and chelometric titrations are usually dealt with in textbooks on analytical chemistry. The titration curves in these titrations can be obtained potentiometrically by use of appropriate indicator electrodes, i.e. a pH-glass electrode or pH-ISFET for acid-base titrations, a platinum electrode for redox titrations, a silver electrode or ISEs for precipitation titrations, and ISEs for... 

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. 

A difference plot, also called a Bjerrum plot, is an excellent means to extract metal-ligand formation constants or acid dissociation constants from titration data obtained with electrodes. We will apply the difference plot to an acid-base titration curve. 

M. Cremer at the Institute of Physiology at Munich discovered in 1906 that a potential difference of 0.2 V developed across a glass membrane with acid on one side and neutral saline solution on the other. The student Klemensiewicz, working with F. Haber in Karlsruhe in 1908, improved the glass electrode and carried out the first acid-base titration to be monitored with a glass electrode.13... 

As in acid-base titrations, indicators and electrodes are commonly used to find the end point of a redox titration. 

A more accurate way to use potentiometric data is to prepare a Gran plot6-7 as we did for acid-base titrations in Section 11-5. The Gran plot uses data from well before the equivalence poinl (Ve) to locate Ve. Potentiometric data taken close to Ve are the least accurate because electrodes are slow to equilibrate with species in solution when one member of a redox couple is nearly used up. 

Materials. Trimethylamine N-oxide dihydrate (98%) from Aldrich and N-dimethyldodecylamine N-oxide (97%) from Fluka Chemie were used as received. N-dimethylhexylamine N-oxide and N-dimethyloctylamine N-oxide were prepared by reaction of the corresponding tertiary amine with hydrogen peroxide (12). Both samples were isolated as crystalline solids and were >99% pure, based on acid/base titrations and spectrometric methods. Both samples were very hygroscopic. Reagent grade NaBr, 0.1 N and 2.0 N HC1 were from J.T. Baker Chemical Co. and the all solutions were prepared using distilled and deionized water. The pH was monitored using an Orion Ross combination pH electrode and an Orion EA 940 meter. 

Other examples of potentiometric titrations include acid-base titrations, in which an indicator electrode provides a response to hydronium ions, such as the glass electrode, quinhydione electrode, or antimony electrode. In precipitation and complexation titrations the indicator electrode should provide the response to the active species in the solution. Thus, during the titration of chloride ions by silver nitrate, a silver electrode is an effective indicator electrode. 

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