Lecture 1 – Precipitation

Titration – Part 3
Dr Rajdeep Ray
Department of Pharmaceutical Chemistry
Faculty of Pharmacy
RUAS

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Learning Objective

At the end of this lecture, students will be knowing –

• Disadvantages of Volhard’s method

• Modification of Volhard’s method

• Fajans method

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Disadvantage of Volhard’s Method

• During the filtration process, the sample may be lost

• Filtration process has be performed in order to prevent the interaction of precipitated silver chloride with
thiocyanate ions

• In case of iodide estimation, iron (III) indicator should not be added until excess of silver is present ,since the
dissolved iodide reacts with iron (III) ions
Fe3+ + 2I- 2Fe2+ + I2

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Modification of Volhard’s Method

• In order to prevent the reaction between precipitated silver chloride and

thiocyanate and to avoid the filtration process:-

- A coating reagent is added in the reaction such as nitrobenzene, dibutyl

phthalate, potassium nitrate
- Such method is known as modified Volhard’s method

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Fajan’s Method

• Fajan’s method is the most recent and most accurate silver halide method

• This technique employs the indicator absorption method

• In this approach, dichlorofluorescein served as an indicator, and excess methyl

chloride ions are absorbed on the surface of silver chloride.

• At the endpoint, the indicator adheres to the silver salt precipitate’s surface
resulting in the indicator’s color changes as a result of the adsorption process

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Fajan’s Method (contd.)

• Sample: Generally, it can be used for Cl-, Br-, I- & SCN-. [Fluorescein ind. is used
for Cl-, Br-, I- & SCN- but Eosin ind. is used for Br-, I-& SCN-(Not for Cl-)]

• Type of titration: direct titration

• Standard Solution: Standard silver nitrate solution

• Indicator: Adsorption indicators like eosin, fluorescein

• Color at end point: Depending upon the use of indicator

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Fajan’s Method (contd.)
Adsorption Indicators

• Based on the properties of colloids, adsorption indicators act

• An adsorption indicator is an organic compound (dye) that tends to be adsorbed onto the surface of
the solid in a precipitation titration

• Ideally, the adsorption occurs near the equivalence point

• It results not only in a color change but also in a transfer of color from the solution to the solid (or the
reverse)
Examples: Acid dyes: Fluorescein, eosin as sodium salts
Basic dyes: Rhodamine 6G and Phenosafranine as halogen salts
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Fajan’s Method (contd.)

Eosin
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Fajan’s Method (contd.)

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Fajan’s Method (contd.)

• When dichlorofluorescein is used as an indicator; the end-point is

marked by the green suspension turning pink

• The color change from orange to bright pink takes place when Eosin Y
indicator is used

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References

Books

• Kar, A. (2005). Pharmaceutical Drug Analysis. India: New Age International.

• Harvey, D. (2000) Modern analytical chemistry. Boston, McGraw-Hill, Massachusetts

Internet Resources

• https://www.canterbury.ac.nz/media/documents/science-outreach/chloride_volhard.pdf

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