Iodometry

DELA CRUZ, TRECIA
MT118
PROF. RACHEL ANN MENDOZA

Iodometry
Iodometry, also known as iodometric titration, is a method of volumetric chemical analysis, a redox titration where
the appearance or disappearance of elementary iodine indicates the end point.
Note that iodometry involves indirect titration of iodine liberated by reaction with the analyte, whereas iodimetry
involves direct titration using iodine as the titrant.
Basic principles:
Iodometry is commonly used to analyse the concentration of oxidizing agents in water samples, such as oxygen
saturation in ecological studies or active chlorine in swimming pool water analysis. To a known volume of sample,
an excess but known amount of iodide is added, which the oxidizing agents oxidizes iodide
to iodine. Iodine dissolves in the iodide-containing solution to give triiodide ions, which have a dark brown color.
The triiodide ion solution is then titrated against standard thiosulfate solution to give iodide again
using starch indicator:
I3 + 2 e 3 I (Eo = + 0.5355 V)
Together with reduction potential of thiosulfate:
S4O62 + 2 e 2 S2O32 (Eo = + 0.08 V)
The overall reaction is thus:
I3 + 2 S2O32 S4O62 + 3 I (Eo = + 0.4555 V)
For simplicity, the equations will usually be written in terms of aqueous molecular iodine rather than the triiodide
ion, as the iodide ion did not participate in the reaction in terms of mole ratio analysis.
The disappearance of deep blue color due to the decomposition of the iodine-starch clathrate marks the end point
The reducing agent used does not necessarily need to be thiosulfate, stannous chloride, sulfites, sulfides, arsenic(III),
and antimony(III) are commonly used alternatives. At higher pH (> 8)) At low pH would also react with the
thiosulfate:: :S2O32 + 2 H+ SO2 + S + H2O
Some reactions involving certain reductants are reversible at certain pH, thus the pH of the sample solution should be
carefully adjusted before the performing the analysis. For example, the reaction:
H3AsO3 + I2 + H2O H3AsO4 + 2 H+ + 2 I
is reversible at pH < 4.
The volatility of iodine is also a source of error for the titration, this can be effectively prevented by ensuring an
excess iodide is present and cooling the titration mixture. Strong light, nitrite and copper ions catalyzes the
conversion of iodide to iodine, so these should be removed prior to the addition of iodide to the sample.
For prolonged titrations, it is advised to add dry ice to the titration mixture to displace air from the erlenmeyer flask
so as to prevent the aerial oxidation of iodide to iodine. Standard iodine solution is prepared from potassium iodate
and potassium iodide, which are both primary standards):
IO3 + 8 I + 6 H+ 3 I3 + 3 H2O
Applications:
Iodometry in its many variations is extremely useful in volumetric analysis. Examples include the determination of
copper(II), chlorate, Hydrogen peroxide, and dissolved oxygen:
2 Cu2+ + 4 I 2 CuI + I2
6 H+ + ClO3 + 6 I 3 I2 + Cl + 3 H2O
2 H+ + H2O2 + 2 I I2 + 2 H2O
2 H2O + 4 Mn(OH)2 + O2 4 Mn(OH)3
2 Mn3+ + 2 I I2 + 2 Mn2+
Available chlorine refers to chlorine liberated by the action of dilute acids on hypochlorite. Iodometry is commonly
employed to determine the active amount of hypochlorite in bleach responsible for the bleaching action. In this
method, excess but known amount of iodide is added to known volume of sample, in which only the active
(electrophilic) can oxidize iodide to iodine. The iodine content and thus the active chlorine content can be
determined with iodometry.
The determination of arsenic(V) is the reverse of the standardization of iodine solution with sodium arsenite, where a
known and excess amount of iodide is added to the sample:
As2O5 + 4 H+ + 4 I As2O3 + 2 I2 + 2 H2O
For analysis of antimony(V), some tartaric acid is added to solubilize the antimony(III) product.
Other applications are:
Determination of hydrogensulfites and sulfites
Sulfites and hydrogensulfites reduce iodine readily in acidic medium to iodide. Thus when a diluted but excess
amount of standard iodine solution is added to known volume of sample, the sulfurous acid and sulfites present
reduces iodine quantitatively:
SO32 + I2 + H2O SO42 + 2 H+ + 2 I
HSO3 + I2 + H2O SO42 + 3 H+ + 2 I
Determination of sulfides and hydrogensulfides
Although the sulfide content in sample can be determined straightforwardly as described for sulfites, the results are
often poor and inaccurate. A better, alternative method with higher accuracy is available, which involves the addition
of excess but known volume of standard sodium arsenite solution to the sample, during which arsenic trisulfide is
precipitated:
As2O3 + 3 H2S As2S3 + 3 H2O
The excess arsenic trioxide is then determined by titrating against standard iodine solution using starch indicator.
Note that for the best results, the sulfide solution must be dilute with the sulfide concentration not greater than 0.01
M.
Determination of hexacyanoferrate(III)
When iodide is added to a solution of hexacyanoferrate(III), the following equilibrium exists:
2 [Fe(CN)6]3 + 2 I 2 [Fe(CN)6]4 + I2
Under strongly acidic solution, the above equilibrium lies far to the right hand side, but is reversed in almost neutral
solution. This makes analysis of hexacyanoferrate (III) troublesome as the iodide and thiosulfate decomposes in
strongly acidic medium. To drive the reaction to completion, an excess amount of zinc salt can be added to the
reaction mixture containing potassium ions, which precipitates the hexacyanoferrate(II) ion quantitatively:
2 [Fe(CN)6]3 + 2 I + 2 K+ + 2 Zn2+ 2 KZn[Fe(CN)6] + I2
The precipitation occurs in slightly acidic medium, thus avoids the problem of decomposition of iodide and
thiosulfate in strongly acidic medium, and the hexacyanoferrate(III) can be determined by iodometry as usual.
Reference:
https://en.wikipedia.org/wiki/Iodometry

Iodometry

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DELA CRUZ, TRECIA

PROF. RACHEL ANN MENDOZA

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