Indicators, acid-base titrating with

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. 

An acid-base titration is a procedure that is used where a base of known concentration is added to an acid of unknown concentration (or vice-versa) in order to determine the concentration of the unknown. In addition, it is possible to determine the Ka of the acid being titrated (or Kb of the base) as well as an appropriate indicator. Acid-base titrations are often the topic of AP test questions and are frequently used in the laboratory questions. You should know about titrations from a conceptual level, be able to perform calculations for titrations, and know how to properly perform one in the laboratory. We ll begin with the conceptual explanation of titrations. 

Emphasis was therefore put on analytical procedures able to determine many elements in parallel and/or requiring almost no previous separation. procedures preferred were X-ray fluorescence using a Am source and Si(Li)-detector, atomic absorption spectrophotometry, gamma spectrometry using tracer isotopes and Ge(Li)-detector and acid-base titrations with recording of the pH-volume derivative. Table 2 summarises the use of these methods for the different elements, and it also gives a rough indication of interferences, sensitivity and accuracy obtained. 

Acetic acid is a weak acid. It is available at different concentrations. Highly concentrated acetic acid at 98% and above is called glacial acetic acid because its freezing point range is between 13.3 °C (98%) and 16.7 °C (100%). Glacial acetic acid is flammable. The concentration of acetic acid can easily be determined using acid-base titration with phenolphthalein as an indicator. The water used should be free from CO, prepared by boiling before use. 

Ethylenediamine, (I I,NCH,), is a strong organic base miscible with water and alcohol. It is a colourless and viscous liquid with a density of 0.898 and a melting point of 8 °C. The pH of a 25% aqueous solution is 11.5. Like triethanolamine, it is an aliphatic amine soluble in water and, therefore, can be determined by the acid-base titration with methyl orange as an indicator. 

Simple manual acid-base titrations with indicators are virtually free from bias and are capable of good reproducibility. Replicate titrations on the same-sized sample should agree within 0.10 ml or less, with normal care. With exceptional care it is sometimes possible to obtain replicates agreeing within 0.02 ml. 

Figure 4.9A shows the laboratory setup for an acid-base titration with a known volume of acid and a few drops of indicator in a flask. An acid-base indicator is a substance whose color is different in acid than in base the indicator used in the figure is phenolphthalein, which is pink in base and colorless in acid. (We examine indicators in Chapters 18 and 19.) Base is added from a buret, and the OH ions react with the H+ ions. As the titration nears its end (Figure 4.9B), the drop of added base ereates a temporary excess of OH, causing some indicator molecules to change to the basic color they return to the acidic color when the flask is swirled. There are two key stages in the titration ... 

It has been shown that for most acid-base titrations the inflection point, which corresponds to the greatest slope in the titration curve, very nearly coincides with the equivalence point. The inflection point actually precedes the equivalence point, with the error approaching 0.1% for weak acids or weak bases with dissociation constants smaller than 10 , or for very dilute solutions. Equivalence points determined in this fashion are indicated on the titration curves in figure 9.8. 

A double end point, acid—base titration can be used to determine both sodium hydrosulfide and sodium sulfide content. Standardized hydrochloric acid is the titrant thymolphthalein and bromophenol blue are the indicators. Other bases having ionization constants in the ranges of the indicators used interfere with the analysis. Sodium thiosulfate and sodium thiocarbonate interfere quantitatively with the accuracy of the results. Detailed procedures to analyze sodium sulfide, sodium hydro sulfide, and sodium tetrasulfide are available (1). 

As pointed out in Chapter 4, an acid-base indicator is useful in determining the equivalence point of an acid-base titration. This is the point at which reaction is complete equivalent quantities of acid and base have reacted. If the indicator is chosen properly, the point at which it changes color (its end point) coincides with the equivalence point To understand how and why an indicator changes color, we need to understand the equilibrium principle involved. 

In acid-base titrations the end point is generally detected by a pH-sensitive indicator. In the EDTA titration a metal ion-sensitive indicator (abbreviated, to metal indicator or metal-ion indicator) is often employed to detect changes of pM. Such indicators (which contain types of chelate groupings and generally possess resonance systems typical of dyestuffs) form complexes with specific metal ions, which differ in colour from the free indicator and produce a sudden colour change at the equivalence point. The end point of the titration can also be evaluated by other methods including potentiometric, amperometric, and spectrophotometric techniques. 

In Sections 10.11-10.16 it is shown how the change in pH during acid-base titrations may be calculated, and how the titration curves thus obtained can be used (a) to ascertain the most suitable indicator to be used in a given titration, and (b) to determine the titration error. Similar procedures may be carried out for oxidation-reduction titrations. Consider first a simple case which involves only change in ionic charge, and is theoretically independent of the hydrogen-ion concentration. A suitable example, for purposes of illustration, is the titration of 100 mL of 0.1M iron(II) with 0.1M cerium(IV) in the presence of dilute sulphuric acid ... 

A. Internal oxidation-reduction indicators. As discussed in Sections 10.10-10.16, acid-base indicators are employed to mark the sudden change in pH during acid-base titrations. Similarly an oxidation-reduction indicator should mark the sudden change in the oxidation potential in the neighbourhood of the equivalence point in an oxidation-reduction titration. The ideal oxidation-reduction indicator will be one with an oxidation potential intermediate between... 

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. 

The intensity and colour of the fluorescence of many substances depend upon the pH of the solution indeed, some substances are so sensitive to pH that they can be used as pH indicators. These are termed fluorescent or luminescent indicators. Those substances which fluoresce in ultraviolet light and change in colour or have their fluorescence quenched with change in pH can be used as fluorescent indicators in acid-base titrations. The merit of such indicators is that they can be employed in the titration of coloured (and sometimes of intensely coloured) solutions in which the colour changes of the usual indicators would... 

The objective of an acid-base titration is to determine the amount of an acid or base in a solution. Because an indicator is itself a weak acid, it may appear that adding an indicator would alter equilibrium concentrations and influence the titration. However, a useful indicator gives a noticeable color to a solution at a concentration of lO M. This is negligible compared with the concentration of the solution being titrated, which is usually in the... 

For end-point detection, any method usual in acid-base titration can be used with electrometric indication the precautions for protection against the... 

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. 

To select an indicator for an acid-base titration it is necessary to know the pH of the end point before using equation (5.5) or standard indicator tables. The end point pH may be calculated using equations (3.27), (3.29) or (3.30). Alternatively, an experimentally determined titration curve may be used (see next section). As an example, consider the titration of acetic acid (0.1 mol dm 3), a weak acid, with sodium hydroxide (0.1 mol dm-3), a strong base. At the end point, a solution of sodium acetate (0.05 mol dm 3) is obtained. Equation (3.28) then yields... 

FIGURE 5.2 A family of acid-base titration curves for a 0.10 M strong acid (HC1) and three weak acids, as indicated (0.10 M each), titrated with 0.10 M NaOH (strong base). HAc is a representation of acetic acid. 

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. 

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. 

For the titration of a strong base with a weak acid, the equivalence point is reached when the pH is greater than 7. The half equivalence point is when half of the total amount of base needed to neutralize the acid has been added. It is at this point that the pH = pK of the weak acid. In acid-base titrations, a suitable acid-base indicator is used to detect the endpoint from the change of colour of the indicator used. An acid-base indicator is a weak acid or a weak base. The following table contains the names and the pH range of some commonly used acid-base indicators. 

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... 

Titration is used to determine the amount of an acid in a given solution. A measured volume of the acid is titrated with a solution of a strong base, usually sodium hydroxide (NaOH), of known concentration. The NaOH is added in small increments until the acid is consumed (neutralized), as determined with an indicator dye or a pH meter. The concentration of the acid in the original solution can be calculated from the volume and concentration of NaOH added. 

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. 

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