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Volhard’s Method

Volhard’s method involves the titration of chlorides, bromides and iodides in an acidic medium.
Here, a known excess amount of silver nitrate solution reacts with the chloride in solution.
When all the chloride is converted to silver chloride, the silver nitrate left behind is estimated
by back titration against a standard solution of potassium thiocyanate. After all the silver is
consumed in the reaction with thiocyanate, the next excess of thiocyanate reacts with the ferric
ammonium sulfate indicator and gives a red color caused by formation of the ferrous
thiocyanate complex.

In the Vollhard method Chloride is precipitated from a solution using escess silver ions.
Ag+(aq)+Cl−(aq)⟶AgCl(s)AgX+X(aq)+ClX−X(aq)⟶AgClX(s)
After precipitation the solution is filtered and ammonium thiocyanate is added to the silver
supernate with a small amount of ferric ammonium sulfate as an indicator where thiocyanate
reacts preferentially with the silver:
Ag+(aq)+SCN−(aq)⟶AgSCN(aq)AgX+X(aq)+SCNX−X(aq)⟶AgSCNX(aq)
Once the all of the silver has reacted with thiocyanate the Fe3+FeX3+ will then react to
form Fe[SCN]2+Fe[SCN]X2+which produces a dark red color and indicates an equivalent
point. and the chloride concentration is calculated by difference.
Fe3+(aq)+SCN−(aq)⟶Fe[SCN]2+(aq)FeX3+X(aq)+SCNX−X(aq)⟶Fe[SCN]X2+X(aq)
Since the silver in the precipitate, why will you have to filter AgClAgCl before you can start
back titration instead of treating the solution? Would filtering also necessary
for AgBrAgBr and AgIAgI?

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