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CHM421 Chapter 4 Part C

1. Iodimetry and iodometry are titration methods that involve iodine to analyze reducing and oxidizing agents, respectively. 2. Iodimetry directly reacts the analyte reducing agent with iodine, while iodometry produces iodine in situ from the reaction of an analyte oxidizing agent with iodide, followed by back-titration with thiosulfate. 3. Examples of iodimetry include titrating ascorbic acid or tin(II), while examples of iodometry include titrating copper or manganese dioxide.

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60 views

CHM421 Chapter 4 Part C

1. Iodimetry and iodometry are titration methods that involve iodine to analyze reducing and oxidizing agents, respectively. 2. Iodimetry directly reacts the analyte reducing agent with iodine, while iodometry produces iodine in situ from the reaction of an analyte oxidizing agent with iodide, followed by back-titration with thiosulfate. 3. Examples of iodimetry include titrating ascorbic acid or tin(II), while examples of iodometry include titrating copper or manganese dioxide.

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Azrina Hafizah
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T I T R I M E T R I C A N A LY S I S

CHAPTER 4C(II)
R E D O X T I T R AT I O N
TITRATION INVOLVE IODINE
1. Iodine is a moderately strong oxidizing agent and can
be used to titrate reducing agents.

2. Advantage of moderate strength as a redox reagent:


Better selectivity. Permanganate oxidize almost
everything present.

3. Titrations with I2 are called iodimetry and iodometry


methods.

4. These titrations are usually performed in neutral or


mildly alkaline (pH 8) to weakly acid solutions.
• If the pH is too alkaline, I2 will disproportionate to
hypoiodate and iodide.
-
I2 + 2OH IO- + H2O + I-

• If pH is too acidic, the starch used for end-point


detection tends to hydrolyze or decompose in strong
acid, and so the end point may be affected. Therefore,
starch is added before the end point, (after the solution
in pale yellow).
Preparation of iodine solution

• Iodine has a low solubility in water but the complex I3-


(triiodide) is very soluble.

• So iodine solution are prepared by dissolving iodine


crystals in a concentrated solution of potassium
iodide in which the following reaction occurs:
- -
I2 + I = I3
solid excess triiodide ion complex
TITRATION INVOLVING IODINE
• Iodimetry: A process in which analyte reacts with
iodine (in a form of I3-) for the analysis of reducing
agents.

• Iodimetry which is based on the direct reaction


between the analyte and iodine. Since iodine is an
oxidizing agent, iodimetry is used for the analysis of
reducing agent.
Example: Quantification of Ascorbic Acid (Vitamin C)

C6H8O6 + I2 → CçH6O6 + 2I- + 2H+

Iodine rapidly oxidizes ascorbic acid, C6H8O6 , to produce


dehydroascorbic acid, C6H6O6 .

Ascorbic acid Dehydroascorbic acid


TITRATION INVOLVING IODINE

• Iodometry is a process in which iodine is produced


in situ by reaction of analyte with iodide, followed
by back-titration with thiosulfate for the analysis of
oxidizing agents.

• Iodometry which is based on the reaction between


the analyte and an unmeasured excess of iodide to
produce iodine, which is measured by titration with
thiosulfate.

• Since iodide is an reductant, iodometry is used for


the oxidizing agent.
Example: Quantification of Copper
(Iodometric titration)

2 Cu2+ + 4I- → 2CuI + I2

Analyte of unknown
concentration

I2 + 2S2O32- → 2I- + S4O62-

Titrant
-Standrard solutions: Sodium thiosulfate
-Known concentration
Iodimetric titrations:
a) A reducing analyte
b) One reaction
c) Standard solution: Iodine (I2)

Iodometric titrations:
a) An oxidizing analyte
b) Two reactions
c) Standard solution: Sodium thisoufate
• Remember!!
✓Iodimetry (Analyte reacts with iodine) is for the
analysis of reducing agents.

✓Iodometry (Production of iodine by reaction of


analyte with iodide, followed by back-titration with
thiosulfate) is for the analysis of oxidizing agents.

✓Titrations involving iodine are more selective than


those involving more powerful redox reagents.
SOME SUBSTANCES
DETERMINED BY IODIMETRY

Analyte Reaction with iodine Solution


conditions
H2S H2S + I2 => S + 2I- + 2H+ Acid solution
SO32- SO32- + I2 + H2O => SO42- + 2I-
+ 2H+
Sn2+ Sn2+ + I2 => Sn4+ + 2I- Acid solution
As(III) H2AsO3- + I2 + H2O => HAsO42- pH = 8
+ 2I- + 3H+
N2H4 N2H4 + 2I2 => N2 + 4H+ + 4I-
SOME EXAMPLES OF IODOMETRIC
DETERMINATIONS

Analyte Reaction with iodine

MnO4- 2MnO42- + I0I- + 16H+ => 5I2 + 2Mn2+ +


8H2O
Cr2O72- CrO72- + 6I- + 14H+ => 2Cr3+ + 3I2 +7H2O

IO3- IO3- + 5I- + 6H+ => 3I2 + 3H2O


Ce4+ 2Ce4+ + 2I- => 2Ce3+ + I2

Fe3+ 2Fe3+ + 2I- => 2Fe2+ + I2

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