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Determination of chloride by Volhard method

Done by: Samyah Alanazi

Fajan’s method. which means Sliver. • C-Volhard’s method. type of Precipitation titration.Mohr’s Method. Argentometry is a type of titration involving the silver ion • Methods of Argentometric titrations : • It involves precipitation titrimetry: • A. It involves formation of slightly soluble precipitate at end point.Introduction • Precipitation titration s a perfect method for determine halogens and some metal ions. Argentometry. . • B. So. is derived form a latin word Argentum .

There is always some error in this method because a dilulet chromate solution is used due to the intense color of the indicator. Therefore. the pH of solution should be kept at about 7. silver will react with the hydroxide ions forming AgOH. In acidic solutions. the first drop of Ag+ in excess will react with the chromate indicator giving a reddish precipitate.is consumed. in alkaline solutions. chromate will be converted to dichromate. Therefore. AgCl is formed first and after all Cl. • 2 Ag+ + CrO42. for example. neutral medium should be used since. Chromate forms a precipilate with Ag+ but this precipitate has a greater solubility than that of AgCl. .Mohr Method • This method utilizes chromate as an indicator. This will require additional amount of Ag+ for the Ag2 CrO4 to form.= Ag2CrO4 • In this method.

Fajans Method • Fluorescein and its derivatives are adsorbed to the surface of colloidal AgCl. • Ag+ + FI-= AgF • • Since fluorescein and its derivatives are weak acids. the pH of the solution should be slightly alkaline to keep the indicator in the anion form but. at the same time. is not alkaline enough to convert Ag+ into AgOH . . Fluorescein derivatives that are stronger acids than fluorescien (like eosin) can be used at acidic pH without problems. After all chloride is used. This method is simple and results obtained are repoducible. the first drop of Ag+ will react with fluorescein (FI-) forming a reddish color.

Volhard Method • This is an indirect method for chloride determination where an excess amount of standard Ag+ is added to the chloride solution containing Fe3+ as an indicator.solution untill a red color is obtained which results from the reaction: • • Fe3+ + SCN. The excess Ag+ is then titrated with standard SCN.titrant increase the solubility of the precipitate leading to significant errors. This problem had been overcome by two main procedures: • . The medium should be acidic to avoid the formation of Fe(OH)3 . However. the use of acidic medium together with added SCN.= Fe(SCN)2+ • • The indicator system is very sensitive and usually good results are obtained.

a German Chemist . which surrounds the precipitate and shields it from the aqueous medium. The second procedure involves filtration of the precipitate directly after precipitation. . • It is a back titration procedure.solution • The Volhard’s method was first described by the Jacob Volhard . in 1874. which protects the precipitate from coming in contact with the added SCN. used for determining the anions that precipitate with silver.Cont. • The first includes addition of some nitrobenzene.

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• 2.oxalate and arsenate do not interfere.It is useful where the titration have to be performed at low pH. • 3.Advantages • 1.Give accurate result due to back titration. .The strong acidic environment give advantage for halide analysis because ions like carbonate .

• Sometimes adsorption of Ag+ may give false end point. • Time consuming. .limitations • Can not be used where solution has to be neutral.

as AgCl by the addition of a known excess of standard AgNo3 THEN the remaining unreacted AgNo3 ia back titrated against standard KSCN using Ferric Ammonium Sulphate as indicator. .Principle • It depends upon the precipitation of Cl.

Equations  Ag+ + Cl‾ (white ppt)  Ag+ (excess) + SCN ‾ titration)  Fe+ ++ + SCN ‾ point AgCl + Ag+ (excess) AgSCN FeSCN ++ (back (brown color) end .

mix well 2 ml Ferric ammonium Sulphate.HNO3. mix well 2 ml con. mix well Titrate with Potassium thiocyanate solution until get light brown color (end point).Procedure Standardization of Potassium Thiocyanate (KSCN) : 20 ml AgNO3 80 ml distilled water. . Calculate the normality of KSCN.

rejecting the first few millimeters of the filtrate. 40 ml D. mix well  Titrate with Potassium thiocyanate until get the light brown color.  Calculate the concentration of unknown chloride. mix well (note the white ppt) Shake well for few minutes to coagulate the precipitated AgCl.  add 2 ml Ferric ammonium sulphate indicator.       Titration of unknown solution of chloride: 10 ml unknown solution of chloride 2 ml HNO3 ??.W. . ??  Transfer 60 of the filtrate into a clean glass stoppered flask. mix well 20 ml AgNO3. mix well ?? Filter through a dry filter paper.

HNO3 helps the coagulation of AgCl ppt and that facilitate its filtration or coating. Ag+ will be ppted as AgOH and Fe OH3. B. C.HNO3 prevent ppted of other Ag3 salts like carbonate and sulfide because these salts are soluble in HNO3.Facts 1. 2.Concentrated Nitric Acid is added because the titration must be done in acidic medium to prevent the precipitate of Iron(III) as hydrated oxide (iron hydroxide) A.Silver thiocyanate solubility is slightly lower than solubility of silver chloride. and during titration thiocyanate can replace chlorides in the existing precipitate: • AgCl(s) + SCN. 3.→ AgSCN(s) + Cl-.To dilute sample.In alkaline medium. .

Once the precipitate is covered with non polar liquid. However. These liquids are better at wetting precipitate than water.. there exist much simpler and easier procedure that gives the same result. Before titration we add some small volume of a heavy organic liquid that is not miscible with water (like nitrobenzene. . it is separated from the water and unable to dissolve or to prevent this error the precipitate must be filtered off before titration with SCN.Solutions • To avoid problems we can filtrate precipitated AgCl before titration. chloroform or carbon tetrachloride).

as both AgBr and AgI have much lower solubilities than AgSCN.• Precipitate solubility is not a problem during determination of I.and Br-. .

087 M .Calculations 1.1 x 20 = M SCN‾ x 23 M SCN‾ = 0.Calculate the concentration of KSCN: Ex: If volume of KSCN = 23 M1 x V1 = M2 x V2 MAg+ x VAg+ = MSCN‾ x VSCN ‾ 0.

1 x 20 = 2 m moles  Un reacted m moles of Ag+ (m moles of KSCN used) = MKSCN x VKSCN U = 0.017 m moles  Reacted m moles of Ag (m moles of Chloride) = T – U = 2 .1983 m moles / ml .2.0.2 = 0.087 x 0.983 m moles / 10 ml = 0.017= 1.983 = 1.2 ml  Total m moles of Ag+ = M x V T = 0.Calculate the concentration of chloride : Ex: If volume of KSCN = 0.