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Estimation of Phenol/ aniline (indirect iodometry)

Organic Chemistry Practical

CHP516
Course Coordinators
Dr. Anupama Kumar & Dr. J.D. Ekhe
Department of Chemistry
28 September,2021
 Estimation of Phenol: Principle 2
 There are two methods for estimation of phenolic group :
1) Bromate bromide method ( Brominating agents is KBrO₃ and KBr) in presence of HCl 2)Acetylation method

KBrO₃ + 5KBr + 6HCl → 3Br₂ + 6KCl + 3H2O

3Br2 ≡ 94 g of phenol

1 Br2 ≡ 94 / 3 g of phenol

However,
1mol Br2 ≡ 2 equivalents of Br

Therefore
When excess KI is added to this mixture, equivalent iodine is 1 equivalent of Br ≡ 94 / (3*2) g of phenol
displaced by the excess Bromine.
Br₂ + 2KI → 2KBr + I₂
Br2 ≡ I2 ≡ 2 Na2S2O3
Iodine liberated is titrated with sodium thiosulfate
I₂ + 2Na₂S₂O₃ → Na₂S₄O₆ + 2NaI Br ≡ I ≡ Na2S2O3 ≡ 94 / (3*2) g of phenol
1000 mL of 1N hypo ≡ 1000 mL of 1N Br ≡ 1000 mL of 1N I ≡ M / (Z*2) g of phenol
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Estimation of Phenol: Procedure
 APPARATUS: Burette, pipette, conical flask, beakers, glass tubes, spatula etc.
 REAGENTS: Brominating mixture, sodium thiosulphate solution (0.1 N), Conc. HCL, KI solution 15 – 20
%, dil. H₂SO₄, Solid NaHCO₃, starch solution.
 PROCEDURE:
1) Take 25ml of phenol sample in a conical flask and 25 ml of distilled water. Then add 5ml of conc. HCl to it.

2) To this solution add brominating mixture drop by drop. Initially the yellow color will disappear but as
bromination reaction completes the yellow color will persist. Add 2ml of excess brominating agent after this point,
the total volume of brominating mixture added should be noted carefully. Keep this solution in the dark for fifteen
minutes with occasional shaking.

3) Add 5ml of 20% KI solution for 5 minutes to allow the reaction to proceed.

4) Titrate with 0.1 N Sodium thiosulfate solution till brown color changes to pale yellow. Now add starch to this
solution.

5) The solution will turn navy blue or black. Continue titration till solution turns colorless .

6) Similarly perform the blank titration by following all the above steps without adding 25ml of phenol.
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Estimation of Phenol: Procedure
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Estimation of Phenol: Calculation

 Volume of Hypo solution required for blank solution= V1ml

 Volume of Hypo solution required for phenol sample= V₂ ml
 Normality of hypo solution = Nx
 Molecular weight of the given phenol= M g
 Number of equivalents bromine consumed by the given organic compound = Z
 (V1 - V₂) ml of hypo solution ≅ Equivalents of bromine consumed by the given Phenol
 1000ml of 1N of hypo solution ≅ 1000 ml 1N I ≅ 1000 ml 1N Br ≅ M/2 *z gm phenol
Estimation of Phenol: Calculation 6
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