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Assays by precipitation
-Quantitative precipitation is possible in volumetric or titrimetric analysis. -But it is possible only when the end-point of precipitation can be determined. -For visual end-point detection Indicator. -Argentimetry is an example of precipitation titration. -Solubility product principle addresses the mechanism of the titration & colour change of indicators. -Solution of slightly soluble salt: BA B+ + A solid solution -Law of mass action: K = [B+] [A ] [BA] or, K x constant = [B+] [A ] Ksp or SBA = [B+] [A ] is called solubility product constant at(25C). -Let us consider a sparingly soluble salt B mAn. BmAn mB+ + nA Hence, SBmAn = [B+ ]m. [A ]n -In a saturated solution of slightly soluble salt BA [B+] = [A ] = S S is the molar solubility of the salt , hence, S = SBA Indicators in argentimetric titrations:1.Potassium chromate(Mohr method),2.Ammonium Iron(iii)sulphate ((Volhard method), 3)Adsorption indicators. 1.Potassium Chromate(Mohr method) -Used in titration of chloride ion with silver nitrate(V.S.) -Used in neutral solution. -Gives red colour precipitate of silver chromate at the end-point. 2) Ammonium Iron(iii)sulphate (Mohr method): -Analytes are chloride ,bromides & iodides in acid solution (Nitric acid). -Silver nitrate(V.S.) is used in excess to consume halides. -Silver ions are back titrated with ammonium thiocyanate solution(V.S) -Silver thiocyanate(ppt.) is a product of back-titration. -Indicator used is ferric alum(ammonium iron(iii)sulphate) solution. -Indicator gives pink colour at the end-point. MX + AgNO3 MNO3 +AgX -On back-titration: AgNO3 + NH4SCN AgSCN +NH4NO3 -At the end-point excess thiocyanate combines with ferric ion to give red colour with the formation of iron(III)hexacyanoferrateIII): 2Fe+ + 6SCN- Fe+[Fe(SCN)6]3- Red colour -Coagulants dibutylphthalate or nitrobenzenes are used to remove AgCl ppt. Or filtration is used to remove AgCl.

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3)Adsorption indicator: -Adsorption indicators are acidic or basic dyes. -These change colour on adsorption to the precipitate at the end-point. AgNO3 + NaCl NaNO3+ AgCl -Silver chloride precipitate adsorbs chloride ion on the surface of the precipitate(primary adsorption). -Precipitate has tendency to adsorb its own ions.-Positively charged ion(here Na+) present in solution further adsorbed on the around the layer of Pri. adsorption called secondary adsorption. -As the end-point is reached, silver ions are in excess, these ions form layer of primary adsorption.-Nitrate(anion) forms secondary adsorption layer. -However, competition between the anions present(nitrate) in the solution & dye(fluorescein or ichlorofluorescein) begins. -Dye is preferentially adsorbed. -Combination of the dye & Ag+ ions on the surface of the precipitate gives the characteristic orange end-point colour.

Application: 1)Direct titration with silver nitrate i)Sodium chloride intravenous infusion: Determination of the percentage of w/v NaCl -Sample equivalent to 0.2g of sodium is titrated against 0.1M silver nitrate. -Indicator used is potassium chromate(5%w/v, 1ml) ii)Potassium iodide. iii)Sodium nitroprusside. 2)Ammonium thiocyanate titration of silver salts: NH4SCN + AgNO3 AgSCN + NH4NO3 i)Silver nitrate ii)Toughened silver nitrate iii)Sodium chloride tablet iv)Cabromal, v) Potassium chloride, vi)Thiamine hydrochloride: