Visual indicators

The utility of acid-base titrimetry improved when NaOH was first introduced as a strong base titrant in 1846. In addition, progress in synthesizing organic dyes led to the development of many new indicators. Phenolphthalein was first synthesized by Bayer in 1871 and used as a visual indicator for acid-base titrations in 1877. Other indicators, such as methyl orange, soon followed. Despite the increasing availability of indicators, the absence of a theory of acid-base reactivity made selecting a proper indicator difficult. 

The need for the indicator s color transition to occur in the sharply rising portion of the titration curve justifies our earlier statement that not every equivalence point has an end point. For example, trying to use a visual indicator to find the first equivalence point in the titration of succinic acid (see Figure 9.10c) is pointless since any difference between the equivalence point and the end point leads to a large titration error. 

Derivative methods are particularly well suited for locating end points in multi-protic and multicomponent systems, in which the use of separate visual indicators for each end point is impractical. The precision with which the end point may be located also makes derivative methods attractive for the analysis of samples with poorly defined normal titration curves. 

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... 

The precision of the end point signal depends on the method used to locate the end point and the shape of the titration curve. With a visual indicator, the precision of the end point signal is usually between +0.03 mb and 0.10 mb. End points determined by direct monitoring often can be determined with a greater precision. 

Finding the End Point with a Visual Indicator Most indicators for complexation titrations are organic dyes that form stable complexes with metal ions. These dyes are known as metallochromic indicators. To function as an indicator for an EDTA titration, the metal-indicator complex must possess a color different from that of the uncomplexed indicator. Furthermore, the formation constant for the metal-indicator complex must be less favorable than that for the metal-EDTA complex. 

A -visual indicator used to signal the end point in a complexation titration. 

Spectrophotometric titration curves for the titration of an analyte, A, with a titrant, T, to form a product, P, in the presence of a visual indicator. Titration curves are shown for cases where (a) only A absorbs (b) only T absorbs (c) only P absorbs (d) A and T absorb (e) P and T absorb and (f) only the visual indicator absorbs. 

Description of the Method. The operational definition of water hardness is the total concentration of cations in a sample capable of forming insoluble complexes with soap. Although most divalent and trivalent metal ions contribute to hardness, the most important are Ca + and Mg +. Hardness is determined by titrating with EDTA at a buffered pH of 10. Eriochrome Black T or calmagite is used as a visual indicator. Hardness is reported in parts per million CaCOs. 

Inorganic Analysis Complexation titrimetry continues to be listed as a standard method for the determination of hardness, Ca +, CN , and Ch in water and waste-water analysis. The evaluation of hardness was described earlier in Method 9.2. The determination of Ca + is complicated by the presence of Mg +, which also reacts with EDTA. To prevent an interference from Mg +, the pH is adjusted to 12-13, precipitating any Mg + as Mg(OH)2. Titrating with EDTA using murexide or Eri-ochrome Blue Black R as a visual indicator gives the concentration of Ca +. 

Cyanide is determined at concentrations greater than 1 ppm by making the sample alkaline with NaOH and titrating with a standard solution of AgN03, forming the soluble Ag(CN)2 complex. The end point is determined using p-dimethylaminobenzalrhodamine as a visual indicator, with the solution turning from yellow to a salmon color in the presence of excess Ag+. 

Chloride is determined by titrating with Hg(N03)2, forming soluble HgCb-The sample is acidified to within the pH range of 2.3-3.8 where diphenylcarbazone, which forms a colored complex with excess Hg +, serves as the visual indicator. Xylene cyanol FF is added as a pH indicator to ensure that the pH is within the desired range. The initial solution is a greenish blue, and the titration is carried out to a purple end point. 

Because the product of the reaction, I3-, is itself colored, the color of the solution containing the analyte changes with each addition of titrant. For this reason it is difficult to find a suitable visual indicator for the titration s end point. 

Initial attempts at developing precipitation titration methods were limited by a poor end point signal. Finding the end point by looking for the first addition of titrant that does not yield additional precipitate is cumbersome at best. The feasibility of precipitation titrimetry improved with the development of visual indicators and potentiometric ion-selective electrodes. 

In a titrimetric method of analysis the volume of titrant reacting stoichiometrically with the analyte provides quantitative information about the amount of analyte in a sample. The volume of titrant required to achieve this stoichiometric reaction is called the equivalence point. Experimentally we determine the titration s end point using a visual indicator that changes color near the equivalence point. Alternatively, we can locate the end point by recording a titration curve showing the titration reaction s progress as a function of the titrant s volume. In either case, the end point must closely match the equivalence point if a titration is to be accurate. Knowing the shape of a titration... 

In this experiment the concentrations of Ga + and Mg + in aqueous solutions are determined by titrating with EDTA. The titration is followed spectrophotometrically by measuring the absorbance of a visual indicator. The effect of changing the indicator, the pH at which the titration is carried out, and the relative concentrations of Ga + and Mg + are also investigated. 

Suggest an appropriate visual indicator for each of the titrations in problem 1. 

Tartaric acid, H2C4H4O6, is a diprotic weak acid with a pK i of 3.0 and a pK 2 of 4.4. Suppose you have a sample of impure tartaric acid (%purity > 80) and that you plan to determine its purity by titrating with a solution of 0.1 M NaOH using a visual indicator to signal the end point. Describe how you would carry out the analysis, paying particular attention to how much sample you would use, the desired pH range over which you would like the visual indicator to operate, and how you would calculate the %w/w tartaric acid. 

End Point Determination Adding a mediator solves the problem of maintaining 100% current efficiency, but does not solve the problem of determining when the analyte s electrolysis is complete. Using the same example, once all the Fe + has been oxidized current continues to flow as a result of the oxidation of Ce + and, eventually, the oxidation of 1T20. What is needed is a means of indicating when the oxidation of Fe + is complete. In this respect it is convenient to treat a controlled-current coulometric analysis as if electrolysis of the analyte occurs only as a result of its reaction with the mediator. A reaction between an analyte and a mediator, such as that shown in reaction 11.31, is identical to that encountered in a redox titration. Thus, the same end points that are used in redox titrimetry (see Chapter 9), such as visual indicators, and potentiometric and conductometric measurements, may be used to signal the end point of a controlled-current coulometric analysis. For example, ferroin may be used to provide a visual end point for the Ce -mediated coulometric analysis for Fe +. 

Wet-Chemical Determinations. Both water-soluble and prepared insoluble samples must be treated to ensure that all the chromium is present as Cr(VI). For water-soluble Cr(III) compounds, the oxidation is easily accompHshed using dilute sodium hydroxide, dilute hydrogen peroxide, and heat. Any excess peroxide can be destroyed by adding a catalyst and boiling the alkaline solution for a short time (101). Appropriate ahquot portions of the samples are acidified and chromium is found by titration either using a standard ferrous solution or a standard thiosulfate solution after addition of potassium iodide to generate an iodine equivalent. The ferrous endpoint is found either potentiometricaHy or by visual indicators, such as ferroin, a complex of iron(II) and o-phenanthroline, and the thiosulfate endpoint is ascertained using starch as an indicator. 

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