Arsenic + Antimony

37G Titrations with Iodine 1087
37G TITRATIONS WITH IODINE

The oxidizing properties of iodine, the composition and stability of triiodide solu-
tions, and the applications of this reagent in volumetric analysis are discussed
in Section 20C-3. Starch is ordinarily employed as an indicator for iodometric
titrations.
37G-1 Preparation of Reagents
PROCEDURE
(a) Iodine approximately 0.05 M. Weigh about 40 g of KI into a 100-mL beaker.

Add 12.7 g of I2 and 10 mL of water. Stir for several minutes (Note 1). Intro-
duce an additional 20 mL of water, and stir again for several minutes. Care-
fully decant the bulk of the liquid into a storage bottle containing 1 L of
distilled water. It is essential that any undissolved iodine remain in the beaker
(Note 2).
(b) Starch indicator (sufficient for about 100 titrations). Rub 1 g of soluble starch
and 15 mL of water into a paste. Dilute to about 500 mL with boiling water,
and heat until the mixture is clear. Cool; store in a tightly stoppered bottle. For
most titrations, 3 to 5 mL of the indicator are used.
The indicator is readily attacked by airborne organisms and should be freshly
prepared every few days.
Notes
1. Iodine dissolves slowly in the KI solution. Thorough stirring is needed to hasten
the process.
2. Any solid I2 inadvertently transferred to the storage bottle will cause the con-
centration of the solution to increase gradually. Filtration through a sintered-
glass crucible eliminates this potential source of difficulty.
37G-2 Standardization of Iodine Solutions

Discussion
Arsenic(III) oxide, long a favored primary standard for iodine solutions, is now sel-
dom used because of the elaborate federal regulations governing the use of even
small amounts of arsenic-containing compounds. Barium thiosulfate monohydrate
and anhydrous sodium thiosulfate have been proposed as alternative standards.9
Perhaps the most convenient method of determining the concentration of an iodine
solution is the titration of aliquots with a sodium thiosulfate solution that has been
standardized against pure potassium iodate. Instructions for this method follow.
PREPARATION OF REAGENTS
1. Sodium thiosulfate, 0.1 M. Follow the directions in Sections 37H-1 and 37H-2
for the preparation and standardization of this solution.
2. Starch indicator. See Section 37G-1(b).
9W. M. McNevin and O. H. Kriege, Anal. Chem., 1953, 25(5), 767.

1088 CHAPTER 37 Selected Methods of Analysis
PROCEDURE
Transfer 25.00-mL aliquots of the iodine solution to 250-mL conical flasks, and
dilute to about 50 mL. Take each aliquot individually through subsequent steps.
Introduce approximately 1 mL of 3 M H2SO4, and titrate immediately with
standard sodium thiosulfate until the solution becomes a faint straw yellow. Add
about 5 mL of starch indicator and complete the titration, taking as the end point
the change in color from blue to colorless (Note).
Note
The blue color of the starch/iodine complex may reappear after the titration has
been completed because of the air oxidation of iodide ion.
37G-3 The Determination of Antimony in Stibnite

Discussion
The analysis of stibnite, a common antimony ore, is a typical application of
iodometry and is based on the oxidation of Sb(III) to Sb(V):

3 I2 H2O 8 SbO4 2I 2H
SbO3 3
The position of this equilibrium is strongly dependent on the hydrogen ion concen-
tration. To force the reaction to the right, it is common practice to carry out the
titration in the presence of an excess of sodium hydrogen carbonate, which con-
sumes the hydrogen ions as they are produced.
Stibnite is an antimony sulfide ore containing silica and other contaminants.
Provided that the material is free of iron and arsenic, the analysis of stibnite for its
antimony content is straightforward. Samples are decomposed in hot concentrated
hydrochloric acid to eliminate sulfide as gaseous hydrogen sulfide. Care is needed
to prevent loss of volatile antimony(III) chloride during this step. The addition of
potassium chloride helps by favoring formation of nonvolatile chloro complexes
such as SbCl 3
4 and SbCl6 .
Sparingly soluble basic antimony salts, such as SbOCl, often form when the
excess hydrochloric acid is neutralized; these react incompletely with iodine and
cause low results. The difficulty is overcome by adding tartaric acid, which forms a
soluble complex (SbOC4H4O 6 ) from which antimony is rapidly oxidized by the
reagent.
PROCEDURE
Dry the unknown at 110°C for 1 hr, and allow it to cool in a desiccator. Weigh
individual samples (Note 1) into 500-mL conical flasks. Introduce about 0.3 g of
KCl and 10 mL of concentrated HCl to each flask. Heat the mixtures (use the
hood) to just below boiling until only white or slightly gray residues of SiO2
remain.
Add 3 g of tartaric acid to each sample and heat for an additional 10 to 15 min.
Then, with good swirling, add water (Note 2) from a pipet or buret until the volume
is about 100 mL. If reddish Sb2S3 forms, discontinue dilution and heat further to
eliminate H2S; add more HCl if necessary.
37H Titrations with Sodium Thiosulfate 1089
Add 3 drops of phenolphthalein, and neutralize with 6 M NaOH to the first faint
pink of the indicator. Discharge the color by the dropwise addition of 6 M HCl, and
then add 1 mL in excess. Introduce 4 to 5 g of NaHCO3, taking care to avoid losses
of solution by spattering during the addition. Add 5 mL of starch indicator, rinse
down the inside of the flask, and titrate with standard 0.05 M I2 to the first blue
color that persists for 30 s.
Report the percentage of Sb2S3 in the unknown.
Notes
1. Samples should contain 1.5 to 2 mmol of antimony; consult with the instructor
for an appropriate sample size. Weighings to the nearest milligram are adequate
for samples larger than 1 g.
2. The slow addition of water, with efficient stirring, is essential to prevent the for-
mation of SbOCl.
37H TITRATIONS WITH SODIUM THIOSULFATE

Numerous methods are based on the reducing properties of iodide ion:
2I S I2 2e
Iodine, the reaction product, is ordinarily titrated with a standard sodium thiosul-
fate solution, with starch serving as the indicator:
I2 2S2O2
3 S 2I S4O6
2
A discussion of thiosulfate methods is found in Section 20B-2.
37H-1 Preparation of 0.1 M Sodium Thiosulfate
PROCEDURE
Boil about 1 L of distilled water for 10 to 15 min. Allow the water to cool to room
temperature; then add about 25 g of Na2S2O3 # 5H2O and 0.1 g of Na2CO3. Stir
until the solid has dissolved. Transfer the solution to a clean glass or plastic bottle,
and store in a dark place.
37H-2 Standardization of Sodium Thiosulfate against

Potassium Iodate
Discussion
Solutions of sodium thiosulfate are conveniently standardized by titration of the
iodine produced when an unmeasured excess of potassium iodide is added to a
known volume of an acidified standard potassium iodate solution. The reaction is

3 5I 6H S 3I2 3H2O
IO
Note that each mole of iodate results in the production of three moles of iodine.
The procedure that follows is based on this reaction.

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37G Titrations with Iodine 1087

37G TITRATIONS WITH IODINE

37G-1 Preparation of Reagents

(a) Iodine approximately 0.05 M. Weigh about 40 g of KI into a 100-mL beaker.

37G-2 Standardization of Iodine Solutions

9W. M. McNevin and O. H. Kriege, Anal. Chem., 1953, 25(5), 767.

37G-3 The Determination of Antimony in Stibnite

37H TITRATIONS WITH SODIUM THIOSULFATE

A discussion of thiosulfate methods is found in Section 20B-2.

37H-1 Preparation of 0.1 M Sodium Thiosulfate

37H-2 Standardization of Sodium Thiosulfate against

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