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IODOMETRY

Iodometry is a redox titration method that uses iodine and thiosulfate. Iodine reacts quantitatively with many substances and can be used to determine reducing or oxidizing agents by titrating with iodine or thiosulfate, respectively. The end point is detected using a blue starch complex. Iodine solutions are prepared by dissolving iodine in potassium iodide and standardized against thiosulfate or arsenic oxide. Copper sulfate can be assayed by iodometric titration where iodine liberated from the reaction of copper sulfate and potassium iodide is titrated with thiosulfate using starch.

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38 views3 pages

IODOMETRY

Iodometry is a redox titration method that uses iodine and thiosulfate. Iodine reacts quantitatively with many substances and can be used to determine reducing or oxidizing agents by titrating with iodine or thiosulfate, respectively. The end point is detected using a blue starch complex. Iodine solutions are prepared by dissolving iodine in potassium iodide and standardized against thiosulfate or arsenic oxide. Copper sulfate can be assayed by iodometric titration where iodine liberated from the reaction of copper sulfate and potassium iodide is titrated with thiosulfate using starch.

Uploaded by

Satish Kumar
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IODOMETRY

Iodometry is one of the most important redox titration methods. Iodine reacts
directly, fast and quantitively with many organic and inorganic substances. Its to
its relatively low, pH independent redox potential, and reversibility of the
iodine/iodide reaction, iodometry can be used both to determine amount of
reducing agents (by direct titration with iodine) and of oxidizing agents (by
titration of iodine with thiosulfate). In all cases the same simple and reliable
method of end point detection, based on blue starch complex, can be used.

Reversible iodine/iodide reaction mentioned above is

2I- ↔ I2 + 2e-

obviously whether it should be treated as oxidation with iodine or reduction with


iodides depends on the other redox system involved.

Second important reaction used in the iodometry is reduction of iodine with


thiosulfate:

2S2O32- + I2 → S4O62- + 2I-

In the case of both reactions it is better to avoid low pH. Thiosulfate is unstable in
the presence of acids, and iodides in low pH can be oxidized by air oxygen to
iodine. Both processes can be source of titration errors.

Iodine is very weakly soluble in the water, and can be easily lost from the solution
due to its volatility. However, in the presence of excess iodides iodine creates I 3-
ions. This lowers free iodine concentration and such solutions are stable enough to
be used in lab practice. Still, we should remember that their shelf life is relatively
short (they should be kept tightly closed in dark brown bottles, and standardized
every few weeks). Iodine solutions are prepared dissolving elemental iodine
directly in the iodides solution. Elemental iodine can be prepared very pure
through sublimation, but because of its high volatility it is difficult to weight. Thus
use of iodine as a standard substance, although possible, is not easy nor
recommended.

STANDARDISATION OF SODIUMTHIOSULPHATE

Iodine solutions can be easily normalized against arsenic (III) oxide (As 2O3) or
sodium thiosulfate solution.

It is also possible to prepare iodine solutions mixing potassium iodide with


potassium iodate in the presence of strong acid:

5I- + IO3- + 6H+ → 3I2 + 3H2O

Potassium iodate is a primary substance, so solution prepared this way can have
exactly known concentration. However, this approach is not cost effective and in
lab practice it is much better to use iodate as a primary substance to standardize
thiosulfate, and then standardize iodine solution against thiosulfate.

ASSAY OF COPPERSULPHATE

Copper sulphate is assayed by Iodometric method, where the liberated iodine from
KI by a suitable oxidizing agent such as copper sulphate is titrated with a standard
solution of sodium thiosulphate using starch as indicator.
Here copper sulphate reacts with KI in presence of acetic acid and form cupric
iodide
(CuI2). Since cupric iodide is unstable, it immediately dissociates to give a
molecule of iodine and cuprous iodide. The liberated iodine is then titrated with
standard solution of sodium thiosulphate.

CuSO4 + 2KI à CuI2 + K2SO4


Cupric iodide
2CuI2 ==== 2CuI + I2
Cuprous iodide
I2 + Na2S2O3 Na2S4O6 + 2NaI
Since the conversion of cupric iodide to cuprous iodide is reversible; the backward
reaction can be prevented by adding a small amount of Potassium thiocynate
(KSCN), which converts Cuprous iodide to Cuprous thiocyanate.
CuI + KSCN CuSCN + KI

White precipitate

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