Precipitation Titrations Precipitation titrations are those titrations in which the titration reaction results in the formation of a precipitate or a slightly soluble salt. The basic requirements are that the precipitation reaction attains equi- librium very quickly after each addition of titrant; the interferences are absent and the indicator shows a clear end point. Few precipitation reactions are used in such titrations the main reason the lack of suitable indicators to detect end point in precipitation reaction. However, the estimations of halides — CI, Br’, I — using Ag (1) commonly known as argentometric titrations are very old and important methods of analysis. Thace will he coneidared in Aatail type of indicators employed. 1. Mohr’s Method - developed in 1856 by Mohr-this method involves the titration of halides against silver nitrate is a neutral medium, using a 2% solution of potassium chromate as an indicator. Addition of anexcess of silver nitrate near the equivalence point result in the formation of a brick red precipitate which marks the end point. Ag* + CI" ——> Agel | (white) 2 Ag’ + CrOy —— Ag, CrO, } (red) The solution should be neutral but not basic so as to precipitate Ag as Ag(OH),, with too much acid the end point will be delayed due to Towering of CrO,> concentration according to the reaction. Ht +Cr0,7 + HCrO, 139au Aninrouucuon ww Anuyucue Cnemisiry Under proper conditions Mobr’s method is accurate and applicable to low CI" concentration. 2. Volhard’s Method. This method involves the titration of Ag(1) with NH,SCN using ferric salt as an indicator. Being titration Ag (SCN) is formed. At the end point excess of NH,SCN reacts with Fe(III) to form deep red [Fe SCN]J**. The amount of thiocyanate which will give a visible colour is very small. Thus the end point error is very small. However, the solution should be shaken vigorously at the end point as Ag ions are absorbed on the precipitate. In Volhard’s method, one can easily deter- mine chloride ions in acidic solution (in basic media Fe™* will hydrolyse). An excess of AgNO; is added to chloride solution and the excess is back titrated with NH,SCN using ferric alum as in indicator. AgSCN is less to soluble than AgCl; this results in the reaction : AgCl + SCN” -» AgSCN + CI" This will consume more NH,SCN and the chloride content will appear lower. This error can be eliminated by filtering off AgCI before back titration. If little nitrobenzene is added, it will adhere to AgCl and protect it from reaction with thiocyanate but nitrobenzene slows down the dicators for the detection of end'point in the estimation of Ag* ions ( or CI ion) against chloride solution (or AgNO) solution). The following indicators are usually employed for the purpose : @ Fluorescein : (Used in the determination of CI” ions in a neutral or weak acidic solution). poe Ho G4 Jo, on coo Bt nak ee Fluorescein(1), Dichloroflurescein(tI), Eosin(II1) Fig. 11.1. Fluorescein(N. Dichloroflurescein(IN). and Eosin(IIN)Tuidenvewe