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Modified Limit Test for Chloride (Volhard Method)

  • The modified limit test for chloride is based on the Volhard titration method, where chloride ions (Cl⁻) are precipitated with silver nitrate (AgNO₃) and the excess silver nitrate is titrated with ammonium thiocyanate (NH₄SCN).

  • The process involves two key reactions:

Chemical Reactions:

a. Precipitation of chloride ions:

Ag⁺ (aq) + Cl⁻ (aq) → AgCl (s)

b. Titration of excess silver nitrate:

Ag⁺ (aq) + SCN⁻ (aq) → AgSCN (s)

Procedure:

1.Prepare Test Solution:

  • Prepare a solution from the sample, ensuring the chloride ions are in a soluble form.

2.Add Silver Nitrate (AgNO₃):

  • Add a known excess of AgNO₃ to the test solution to precipitate chloride ions as silver chloride (AgCl).

3.Acidify with Nitric Acid (HNO₃):

  • Add a small amount of nitric acid to prevent the precipitation of other silver salts, ensuring the reaction proceeds correctly.

4.Titrate Excess AgNO₃ with NH₄SCN:

  • Titrate the excess silver nitrate with ammonium thiocyanate (NH₄SCN) using ferric ammonium sulfate as an indicator.

  • The endpoint is reached when a red complex forms between ferric ions and thiocyanate (after all excess silver ions have reacted).

5.Calculate Chloride Ion Concentration:

  • Calculate the concentration of chloride ions in the sample based on the volume of NH₄SCN used in the titration.


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