Direct Titrations

Method. An amino-acid such as glycine, NHjCH,COOH, cannot be estimated by direct titration with standard alkali solution, owing to the opposing effects of the basic and the acidic groups. If, however, the amino-acid is first... 

Types of Chelometric Titrations. Chelometric titrations may be classified according to their manner of performance direct titrations, back titrations, substitution titrations, redox titrations, or indirect methods. 

Direct Titrations. The most convenient and simplest manner is the measured addition of a standard chelon solution to the sample solution (brought to the proper conditions of pH, buffer, etc.) until the metal ion is stoichiometrically chelated. Auxiliary complexing agents such as citrate, tartrate, or triethanolamine are added, if necessary, to prevent the precipitation of metal hydroxides or basic salts at the optimum pH for titration. Eor example, tartrate is added in the direct titration of lead. If a pH range of 9 to 10 is suitable, a buffer of ammonia and ammonium chloride is often added in relatively concentrated form, both to adjust the pH and to supply ammonia as an auxiliary complexing agent for those metal ions which form ammine complexes. A few metals, notably iron(III), bismuth, and thorium, are titrated in acid solution. 

Direct titrations are commonly carried out using disodium dihydrogen ethylenediaminetetraace-tate, NajHjY, which is available in pure form. The reaction of the chelon with the indicator must be rapid for a practical, direct titration. Where it is slow, heating of the titration medium is often expedient, or another indicator is employed. 

BackTitrations. In the performance of aback titration, a known, but excess quantity of EDTA or other chelon is added, the pH is now properly adjusted, and the excess of the chelon is titrated with a suitable standard metal salt solution. Back titration procedures are especially useful when the metal ion to be determined cannot be kept in solution under the titration conditions or where the reaction of the metal ion with the chelon occurs too slowly to permit a direct titration, as in the titration of chromium(III) with EDTA. Back titration procedures sometimes permit a metal ion to be determined by the use of a metal indicator that is blocked by that ion in a direct titration. Eor example, nickel, cobalt, or aluminum form such stable complexes with Eriochrome Black T that the direct titration would fail. However, if an excess of EDTA is added before the indicator, no blocking occurs in the back titration with a magnesium or zinc salt solution. These metal ion titrants are chosen because they form EDTA complexes of relatively low stability, thereby avoiding the possible titration of EDTA bound by the sample metal ion. 

Substitution Titrations. Upon the introduction of a substantial or equivalent amount of the chelonate of a metal that is less stable than that of the metal being determined, a substitution occurs, and the metal ion displaced can be titrated by the chelon in the same solution. This is a direct titration with regard to its performance, but in terms of the mechanism it can be considered as a substitution titration (or replacement titration). 

This reaction occurs quickly and is of known stoichiometry. A titrant of SCN is easily prepared using KSCN. To indicate the titration s end point we add a small amount of Fe + to the solution containing the analyte. The formation of the red-colored Fe(SCN) + complex signals the end point. This is an example of a direct titration since the titrant reacts with the analyte. 

If the titration reaction is too slow, a suitable indicator is not available, or there is no useful direct titration reaction, then an indirect analysis may be possible. Suppose you wish to determine the concentration of formaldehyde, 1T2CO, in an aqueous solution. The oxidation of 1T2CO by... 

Unfortunately, it often happens that there is no suitable indicator for this direct titration. Reacting Ca + with an excess of the Mg -EDTA complex... 

Another reducing titrant is ferrous ammonium sulfate, Fe(NH4)2(S04)2 6H2O, in which iron is present in the +2 oxidation state. Solutions of Fe + are normally very susceptible to air oxidation, but when prepared in 0.5 M 1T2S04 the solution may remain stable for as long as a month. Periodic restandardization with K2Cr20y is advisable. The titrant can be used in either a direct titration in which the Fe + is oxidized to Fe +, or an excess of the solution can be added and the quantity of Fe + produced determined by a back titration using a standard solution of Ce + or... 

Example 9.13 shows how this equation is applied to an analysis based on a direct titration. 

EDTA is one member of a class of aminocarboxylate ligands that form very stable 1 1 complexes with metal ions. The following table shows log Kf values for several ligands with Ca + and Mg +. Which ligand is the best choice for the direct titration of Ca + in the presence of Mg + ... 

To determine moderate amounts of Cr(III) and Cr(VI) in samples that have both oxidation states present, Cr(VI) is analyzed by direct titration in one sample, and the total chromium is found in a second sample after oxidation of the Cr(III). The Cr(III) concentration is determined as the difference. Trace quantities of Cr(VI) in Cr(III) compounds can be detected and analyzed by (3)-diphenylcarbazide. Trace quantities of Cr(III) in Cr(VI) may be detected and analyzed either photometrically (102) or by ion chromatography using various modes of detection (103). 

Fe (III) is determined by direct titration with EDTA at pH 3 using sulfa salicylic acid as indicator ... 

Zn is determined by direct titration with EDTA with xelenol indicator after iron elimination with acetate ions and copper - with sulfide ions. 

Direct titration [119,120] In order to know the number of exchangeable hydrogen ions at different dissociation stayes, various salts of weak acids were used. Data observed in Table 8 shows an increase in the exchange capacity with an increase in the pH of the solution, indicating the presence of weak acid capacity [118]. 

A. Direct titration. The solution containing the metal ion to be determined is buffered to the desired pH (e.g. to PH = 10 with NH4-aq. NH3) and titrated directly with the standard EDTA solution. It may be necessary to prevent precipitation of the hydroxide of the metal (or a basic salt) by the addition of some auxiliary complexing agent, such as tartrate or citrate or triethanolamine. At the equivalence point the magnitude of the concentration of the metal ion being determined decreases abruptly. This is generally determined by the change in colour of a metal indicator or by amperometric, spectrophotometric, or potentiometric methods. 

An interesting application is the titration of calcium. In the direct titration of calcium ions, solochrome black gives a poor end point if magnesium is present, it is displaced from its EDTA complex by calcium and an improved end point results (compare Section 10.51). 

Murexide may be employed for the direct EDTA titration of calcium at pH =11 the colour change at the end-point is from red to blue-violet, but is far from ideal. The colour change in the direct titration of nickel at pH 10-11 is from yellow to blue-violet. 

This colour change can be observed with the ions of Mg, Mn, Zn, Cd, Hg, Pb, Cu, Al, Fe, Ti, Co, Ni, and the Pt metals. To maintain the pH constant (ca 10) a buffer mixture is added, and most of the above metals must be kept in solution with the aid of a weak complexing reagent such as ammonia or tartrate. The cations of Cu, Co, Ni, Al, Fe(III), Ti(IV), and certain of the Pt metals form such stable indicator complexes that the dyestuff can no longer be liberated by adding EDTA direct titration of these ions using solochrome black as indicator is therefore impracticable, and the metallic ions are said to block the indicator. However, with Cu, Co, Ni, and Al a back-titration can be carried out, for the rate of reaction of their EDTA complexes with the indicator is extremely slow and it is possible to titrate the excess of EDTA with standard zinc or magnesium ion solution. 

Cu, Ni, Co, Cr, Fe, or Al, even in traces, must be absent when conducting a direct titration of the other metals listed above if the metal ion to be titrated does not react with the cyanide ion or with triethanolamine, these substances can be used as masking reagents. It has been stated that the addition of 0.5-1 mL of 0.001 M o-phenanthroline prior to the EDTA titration eliminates the blocking effect of these metals with solochrome black and also with xylenol orange (see below). 

Patton and Reeder s indicator. The indicator is 2-hydroxy-l-(2-hydroxy-4-sulpho-l-naphthylazo)-3-naphthoic acid the name may be abbreviated to HHSNNA. Its main use is in the direct titration of calcium, particularly in the presence of magnesium. A sharp colour change from wine red to pure blue is obtained when calcium ions are titrated with EDTA at pH values between 12... 

Fast sulphon black F ( C.I.26990). This dyestuff is the sodium salt of 1-hydroxy-8-( 2-hydroxynaphthylazo) -2- (sulphonaphthylazo) -3,6-disulph onic acid. The colour reaction seems virtually specific for copper ions. In ammoniacal solution it forms complexes with only copper and nickel the presence of ammonia or pyridine is required for colour formation. In the direct titration of copper in ammoniacal solution the colour change at the end point is from magenta or [depending upon the concentration of copper(II) ions] pale blue to bright green. The indicator action with nickel is poor. Metal ions, such as those of Cd, Pb, Ni, Zn, Ca, and Ba, may be titrated using this indicator by the prior addition of a reasonable excess of standard copper(II) solution. 

This reaction takes place quite rapidly on boiling, and hence hydrochloric add cannot be used in oxidations which necessitate boiling with excess of cerium(lV) sulphate in add solution sulphuric add must be used in such oxidations. However, direct titration with cerium(IV) sulphate in a dilute hydrochloric add medium, e.g. for iron(II) may be accurately performed at room temperature, and in this respect cerium(IV) sulphate is superior to potassium permanganate [cf. (2) above]. The presence of hydrofluoric add is harmful, since fluoride ion forms a stable complex with Ce(lV) and decolorises the yellow solution. 

In most direct titrations with iodine (iodimetry) a solution of iodine in potassium iodide is employed, and the reactive species is therefore the tri-iodide ion 13. Strictly speaking, all equations involving reactions of iodine should be written with 13 rather than with I2, e.g. 

Discussion. One of the most useful titrations involving iodine is that originally developed by Winkler18 to determine the amount of oxygen in samples of water. The dissolved oxygen content is not only important with respect to the species of aquatic life which can survive in the water, but is also a measure of its ability to oxidise organic impurities in the water (see also Section 10.103). Despite the advent of the oxygen-selective electrode (Section 16.36) direct titrations on water samples are still used extensively.19... 

A similar procedure may also be used for the determination of antimony(V), whilst antimony (III) may be determined like arsenic(III) by direct titration with standard iodine solution (Section 10.113), but in the antimony titration it is necessary to include some tartaric acid in the solution this acts as complexing agent and prevents precipitation of antimony as hydroxide or as basic salt in alkaline solution. On the whole, however, the most satisfactory method for determining antimony is by titration with potassium bromate (Section 10.133). 

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