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Starch indicator is added earlier in Starch is added near the end point
titration. because it get decompose in highly
acidic condition.
End point is blue to colourless End point is brown to pale yellow to
colourless
e.g. Titration of iodine with Na2S2O3 e.g. Titration of Na2S2O3 with
KIO3/KBrO3/ K2Cr2O7
• Conditions for iodometric titrations :
1. This titration is carried out in acidic condition
only for the evaluation of iodine in reaction
2. Iodometric titrations should not be carried out in
highly alkaline conditions because hypoiodide ion
(IO-) is form which is strong oxidising agent than
iodine;
2NaOH + I2 –– NaOI + NaI +H2O
3. During reactions I2 is evolved and it is volatile. So,
carry out titration closed vessel i.e. iodine flask
and in cold condition.
4. Iodine is very slightly soluble in water, so there is
need to add excess of KI to dissolve the I2.;
I2 + KI –– KI3
• 5. Keep the flask in dark place to decrease
the volatalization of iodine.
• 6. The rate of reaction between iodate and
iodide ion is too slow, so sufficient time should
be given for completion of reaction.
• 7. The reaction mixture is kept in dark,
place because during reduction of iodine to I-
light accelerate oxidation of I- to I2 by
atmospheric oxygen.
4I-+ 4H+ +O2 ––2I2 + 2H2O
Iodimetric titration:
Example. I :
Standardisation of iodine with sodium thiosuphate :
• (a) Preparation of 0.05 M iodine solution : Dissolve 2
g of potassium iodide in sufficient water then add 1.3
g of iodine and make up the volume upto 100 ml with
distilled water. Iodine form complex with potassium
iodide which has better solubility in water.
• (b) Preparation of 0.1 M sodium thiosuphate solution
: Dissolve 2.5 g of sodium thiosulphate and 0.02 g of
sodium carbonate in CO2 free water and dilute to 100
ml with water. Sodium thiosulphate is readily degraded
by bacteria which uses it as source of sulphate, so
sodium carbonate is added which makes the solution
alkaline and bacterial activity is negligible in alkaline pH
(9-10).
• Standardisation of iodine with sodium
thiosuphate : Directly titrate prepared iodine
solution against sodium thiosulphate. Iodine is
mild oxidising agent which is reduce by sodium
thiosulphate and sodium thiosulphate oxidise to
tetrathionate. At the end point color change is
brown to colorless.
• Reaction:
Oxidising agent: I2 + 2e– –– 2I–
Reducing agent: 2S2O –– S4O + 2e–
Overall reaction is:
I2 + 2 Na2S2O3 –– 2NaI + Na2 S4O6
I2 = 2 Na2S2O3 = 2 e–
• Example. II :
• Standardisation of iodine with arsenic
trioxide : Arsenic trioxide is best primary
standard for iodine solution. Arsenic trioxide is
dissolved in water to give arsenious acid which
is oxidised by iodine solution. The pH should
be in the range of 6-9. Iodine act as a self
indicator
• Reaction: As2O3 + 3H2O ––2H3AsO3
• H3AsO3 + I2 + H2O –– HAsO4-2 + 4H+ + 2I-
• Example. I : Iodometry
Standardisation of sodium thiosuphate with potassium iodate :
Dissolve accurately weighed 1.3 g of pure and dry potassium iodate
into 250 ml distilled water. Pipette out 25 ml of solution into conical
flask, add 2 g potassium iodide and dilute sulphuric acid 4 ml iodine
liberate in reaction, titrate the liberated iodine with 0.1 M sodium
thiosuphate solution. When the colour of the solution becomes
pale yellow (near to end point) add starch paste as an indicator.
Continue titration until the solution become colourless.
• Reaction :
• IO + 5I– + 6H+ –– 3I2 + 3H2O
• Oxidising agent: 3[I2 + 2e– –– 2I–]
• Reducing agent: 3 [2S2O –– 2e– + S4O]
• Overall reaction is: 3[I2 + 2 Na2S2O3 –– 2 NaI + Na2 S4O6]
• 3I2 = 6 Na2S2O3 = 6e–
Potassium Dichromate Titration :