Back-titration

Ammonia may be estimated by dissolving the gas in a known volume of standard acid and then back-titrating the excess acid. In a method widely used for the determination of basic nitrogen in organic substances (the Kjeldahl method), the nitrogenous material is converted into ammonium sulphate by heating with concentrated sulphuric acid. The ammonia is then driven off by the action of alkali and absorbed in standard acid. 

By the evolution of ammonia with Devarda s alloy in alkaline solution in absence of ammonium ions this is used quantitatively, the ammonia being absorbed in excess standard acid and the excess acid back-titrated. 

Add KI and back-titrate iodine liberated with thiosulfate. Cd/8 = 14.05... 

S H2S + F(excess) = S + 2 1 + 2 Back-titrate excess F with standard thiosulfate solution. 

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. 

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. 

In a back titration, a slight excess of the metal salt solution must sometimes be added to yield the color of the metal-indicator complex. Where metal ions are easily hydrolyzed, the complexing agent is best added at a suitable, low pH and only when the metal is fully complexed is the pH adjusted upward to the value required for the back titration. In back titrations, solutions of the following metal ions are commonly employed Cu(II), Mg, Mn(II), Pb(II), Th(IV), and Zn. These solutions are usually prepared in the approximate strength desired from their nitrate salts (or the solution of the metal or its oxide or carbonate in nitric acid), and a minimum amount of acid is added to repress hydrolysis of the metal ion. The solutions are then standardized against an EDTA solution (or other chelon solution) of known strength. 

Suspend 0.5 g in water use 5-pyrimidinyl)imino]- H3ln2- (violet) pK = 10.9 Yellow with Co +, Back titration. Ca, Cr, Ga... 

This approach is easily extended to back titrations, as shown in the following example. 

Finally, quantitative problems involving multiple analytes and back titrations also can be solved by applying the principle of conservation of electron pairs. 

An alloy of chromel containing Ni, Fe, and Cr was analyzed by a complexation titration using EDTA as the titrant. A 0.7176-g sample of the alloy was dissolved in ITNOa and diluted to 250 mb in a volumetric flask. A 50.00-mb aliquot of the sample, treated with pyrophosphate to mask the Fe and Cr, required 26.14 mb of 0.05831 M EDTA to reach the murexide end point. A second 50.00-mb aliquot was treated with hexamethylenetetramine to mask the Cr. Titrating with 0.05831 M EDTA required 35.43 mb to reach the murexide end point. Einally, a third 50.00-mb aliquot was treated with 50.00 mb of 0.05831 M EDTA, and back titrated to the murexide end point with 6.21 mb of 0.06316 M Cu +. Report the weight percents of Ni, fe, and Cr in the alloy. 

Note that the third titration is a back titration. Titration 1 can be used to determine the amount of Ni in the alloy. Once the amount of Ni is known, the amount of Fe can be determined from the results for titration 2. Finally, titration 3 can be solved for the amount of Cr. 

Instead, an excess of KI is added, reducing the analyte and liberating a stoichiometric amount of The amount of produced is then determined by a back titration using Na2S203 as a reducing titrant. 

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... 

One of the most important applications of redox titrimetry is in evaluating the chlorination of public water supplies. In Method 9.3 an approach for determining the total chlorine residual was described in which the oxidizing power of chlorine is used to oxidize R to 13 . The amount of 13 formed is determined by a back titration with 8203 . 

Moles I3 )tot — (moles I3 )ascorbicacid 3 (moles I3 )back titration or... 

When two reagents are listed, the analysis is by a back titration. The first reagent is added in excess, and the second reagent is used to back titrate the excess. 

For Volhard methods identified by an asterisk ( ) the precipitated silver salt must be removed before carrying out the back titration. 

The %w/w K in a 0.6712-g sample was determined by a Volhard titration. After adding 50.00 mb of 0.05619 M AgNOa and allowing the precipitate to form, the remaining silver was back titrated with 0.05322 M KSCN, requiring 35.14 mb to reach the end point. Report the %w/w K in the sample. 

Conservation of charge for this back titration requires that Moles Ag+ = moles K + moles SCN ... 

Animal fats and vegetable oils are triacylglycerols, or triesters, formed from the reaction of glycerol (1,2, 3-propanetriol) with three long-chain fatty acids. One of the methods used to characterize a fat or an oil is a determination of its saponification number. When treated with boiling aqueous KOH, an ester is saponified into the parent alcohol and fatty acids (as carboxylate ions). The saponification number is the number of milligrams of KOH required to saponify 1.000 g of the fat or oil. In a typical analysis, a 2.085-g sample of butter is added to 25.00 ml of 0.5131 M KOH. After saponification is complete, the excess KOH is back titrated with 10.26 ml of0.5000 M HCl. What is the saponification number for this sample of butter ... 

Solutions containing both Le + and AF+ can be selectively analyzed for Le + by buffering to a pH of 2 and titrating with EDTA. The pH of the solution is then raised to 5 and an excess of EDTA added, resulting in the formation of the AF+-EDTA complex. The excess EDTA is back titrated using a standard solution of Le +, providing an indirect analysis for AF+. 

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