Iodometry & Iodimetry Titrations,

Preparation & standardisation of Hypo and iodine

Dr. M. Jaya Devi

D. D (Chem.)
Pesticide Management
 Titrant Titration - Definition

a solution of unknown concentration is reacted with a

solution of a known concentration (titrant) to find out
the unknown solution conc.
Titrand

The equivalence point in a titration is the point at

Equivalent Point which the added titrant is chemically equivalent
completely to the analyte in the sample. .

End point is the point where the indicator changes its

color.
End point
It is the point at which some detection technique tells
you that chemical equivalence has been reached.
 Difference between Equivalence Point and End Point?

Equivalence Point End Point

equivalence point in a titration is the point at End point is the point of completion of
which the added titrant is chemically the reaction between two solutions
equivalent completely to the analyte in the
sample

Equivalence point comes before the end point End point is the point where the indicator
changes its color.

The end point may occur before or after

the equivalence point, giving a titration
error. It is for this reason that blank
samples are often used.
 Type of Titration based on the reaction involved

Complexometric Precipitation
acid-base redox titrations
titrations titration

Acid base Involved the Precipitation

titration, in formation of a titration in
Redox titration soluble complex
which an acidic which the
where the titrant between a metal
or basic titrant analyte and
is an oxidising or ion and a
react with an titrant react
reducing agent complexing agent.
analyte that is a to form a
basic or an acid precipitate
The main titrant used in
the complexometric
titration is EDTA(ethylene
diamine tetra acetic
acid).
Acid-base Precipitation Complexometric Redox

Titrations involving iodine (I2)

Permanganimetric Dichromatometric

Iodimetry

Iodometry
 Iodometric and Iodimetric titrations

Redox titrations classified according to the

titrant used.

Permanganimetric Dichromatometric Titrations involving

(titrant - KMnO4) (Titrant - K2Cr2O4) iodine

Iodimetry Iodometry

Titrations that create or

consume I2 are widely used in
quantitative analysis.
 Oxidizing agent & Reducing agent
Oxidizing agent Reducing agent

Oxidising substance will tend to take

Reducing substance will tend to give up
on an electron or electrons and be
an electron or electrons and be oxidized
reduced
substance which get reduced substance which get oxidized

e.g – Fe3+ + e - Fe2+ e.g – 2I- I2 + 2e-

Oxidation: It can be defined as loss of electrons or increase in oxygen content.

Reduction: It can be defined as gain of electrons or increase of hydrogen content.

Both processes are combined and occur together -REDOX reaction

 Iodometry titration

Principle

iodometric titration, is a method of volumetric chemical

analysis, a redox titration where the appearance or
disappearance of elementary iodine indicates the end
point.

When an analyte that is an oxidizing agent is

added to excess iodide to produce iodine, and
2I- I2 + 2e
the iodine produced is determined
by titration with sodium thiosulfate, the
I2 + 2Na2S2O3 2NaI + Na2S4O6 method is called iodometry.

Iodide ion is a weak reducing agent and will reduce strong oxidizing agents.
 Iodometry (Indirect)
First step: Second step :

Conversion of iodide into iodine Second important reaction used in the

iodometry is reduction of iodine with
2I- → I2 + 2e- thiosulfate

2S2O32- + I2 → S4O62- + 2I-

(Oxidation rxn, by reducing agent) (reduction rxn, by oxidizing agent)

Note: both reactions - it is better to avoid low pH

Thiosulfate is unstable in the presence of acids, and

Iodides in low pH (acidic condition) can be oxidized by air oxygen to iodine.

Both processes can be source of titration errors.

 Iodimetry titration

Iodimetric titrations use a solution of iodine as one of the

solution for titration and the other solution could be sodium
thiosulphate, sodium sulphite, etc

the iodine present in a mixture or solution is directly titrated

with a reducing agent like sodium thiosulphate and estimated

When an analyte that is a reducing agent is titrated directly with a

standard iodine solution, this titration method is called "iodimetric
titration
 Iodometry and Iodimetry

Iodometry (Indirect) Iodimetry (Direct)

used to determine the amount of oxidizing

Used to quantify reducing agent (Analyte)
agent (Analyte)

liberated iodine is titrated with standard an analyte is directly titrated with the
solution of thio sulphate. iodine solution.

the species whose quantity is to be

the species whose quantity is to be
determined is titrated with iodine
determined is titrated with Iodine. In the
solution. In the reaction iodide gets
reaction Iodine is gets converted into
converted into iodine and then released
iodide, which can be detected using starch
iodine is titrated with standard
solution as indicator.
thiosulphate.

It is an indirect method because iodine is It is a direct method. (One reaction)

not directly used in titration. (Two
reaction)
Standard solution: Sodium thisoufate Standard solution: Iodine (I2)
 Iodometry (Indirect) Iodimetry (Direct)
Indicator (Starch) has to be added near the end Indicator (Starch) has to be added at the
of titration (when the brown color of I2 becomes beginning of titration
pale)
End point is disappearance of blue color End point is permanent blue color

Na2S2O3 Na2S2O3

Iodine
E.P. colourless

oxidant
+
KI→I2

Iodine as Reductant + starch

oxidant

Add starch E.P.

 Procedure for preparation of 0.1 N Sodium thiosulphate
(Na2S2O3.5H20):

Weigh about 24.8 g of Sodium thiosulphate

(Equivalent wt = Molecular wt=248) in 100 ml beaker

Add distilled water and dissolve using glass rod.

Transfer quantitatively in 1000 ml volumetric flask and make

up with distilled water.

The normality of a solution is the gram equivalent weight of a solute per

liter of solution. It may also be called the equivalent concentration. It is
indicated using the symbol N, eq/L, or meq/L for units of concentration
 Procedure for preparation of 0.1 N Iodine (I2):
Weigh about 12.69 g of iodine, (Equivalent wt = Molecular
wt=126.9) in 100 ml beaker.

Transfer to a 250 ml capacity iodine flask containing 30 to

40 g of KI (potassium iodide), dissolve in about 100 ml of
water.

Transfer quantitatively into 1000 ml volumetric flask

(amber colour) and make up with distilled water.
Why iodine is kept in the dark?
The reaction mixture should be kept in
the dark for 10 minutes before titration
because light accelerates a side reaction in
which iodide ions are oxidized to iodine by
atmospheric oxygen.
Why are iodine solutions made up using
potassium iodide solution?
Iodine is sparingly soluble in water.
However it reacts with iodide forming
-
I3 ions (triiodide ions), which are very
soluble. In this way the iodine is kept in
solution.
 Procedure for preparation of Starch (1%):

Weigh about 1 g of starch in a 100 ml beaker make slurry

with about 20 ml distilled water.

Add this slurry to 250 ml beaker containing about 80 ml

boiling water.

Boil it to get clear solution and cool down.

Transfer it into an indicator bottle.

Why starch is used as an indicator in iodometric/iodimeric titration?

Starch forms a dark blue complex with iodine. The end point in iodimetry corresponds to
a sudden color change to blue. Likewise the end point in iodometry corresponds to a
sudden loss of blue color due to the complex.
 Procedure for standardization of Sodium thiosulphate
(Na2S2O3.5H20) solution:

Reagent:
1. Potassium iodate (KIO3): primary substance and strong oxidizing
agent
2. Potassium iodide (KI):
3. Sulfuric acid (2N)
4. Sodium thiosulphate
5. Distilled water

Glassware:
1. Burette
2. Pipette
3. Conical flask
4. Measuring cylinder,
 Procedure for standardization of Sodium thiosulphate
(Na2S2O3.5H20) solution:

Weigh about 0.07 - 0.08 g of potassium iodate (KIO3) Potassium iodate is a

in a 250 ml conical flask primary substance

What is liberated iodine?

Dissolve it completely in 50 ml distilled water.
Add 2 g of potassium iodide (KI) and dissolve it.
Potassium iodate is often used as
a reference material to
standardize a sodium thiosulfate
solution which is a familiar
titrant for redox titrations.

Add 5 ml of 2 N sulfuric acid. Titrate In the

immediately the liberated iodine against 0.1 N
sodium thiosulphate solution till pale yellow
colour.
standardization, iodine (triiodide)
liberated by potassium iodate in
an acidic potassium iodide
solution is titrated with a sodium
thiosulfate solution.
 Add 1 ml of 1 % starch indicator solution (blue colour appears).
Continue titration till blue colour disappears.

End point will be disappearance of blue colour.

Calculation:

Weight of primary standard (KIO3) x 1000

Normality = -----------------------------------------------------------
Titer value x Equivalent weight of (KIO3)

Equivalent weight of KIO3 = 35.67

 Procedure for standardization of Iodine (I2):

Pipette out 25 ml of standard iodine solution in a 250 ml conical flask .

Titrate against sodium thiosulphate solution till dark brown colour

turns into pale yellow colour.

Add 1 ml of 1% starch solution (solution turns dark blue).

End point will be disappearance of blue colour.

Normality of std. Na2S2O3 solution X volume of std. Na2S2O3 consumed

Calculation: Normality = -----------------------------------------------------------------------------------------------------
Volume of I2 solution
 Detection of the end point in iodine titrations
How does starch indicate iodine?

Starch consists of two types of molecules, amylose - a

soluble starch and amylopectin.

When starch is mixed with iodine in water, an intensely blue

colored starch/iodine complex is formed.

Starch can not be used in alcoholic solution because

alcohol hinders the adsorption of I2 on Starch
Detection of the end point in iodine titrations

The sensitivity of the blue color decreases with

temperature due to gelatinization of starch and
volatility of Iodine

In strong acid medium: starch hydrolyses giving

products which give with iodine non reversible
reddish color masking the end point change.

Starch indicator solution must be freshly prepared

when it stands decomposition takes place and its
sensitivity is decreased.
A preservative can be added
 pH range of some common acid-base indicators

S.
Indicator Acid Alkali pH range
No.
Yellow (1) 1.2 - 2.8 (1)
1 Thymol blue Red-yellow
Blue (2) 8 - 9.6 (1)
2 Bromophenol Yellow-Blue 3.0 - 4.6
3 Methyl orange Red- Yellow 3.1 - 4.4
4 Methyl red Red-Yellow 4.2 - 6.3
5 Litmus Red Blue 4.5 - 8.3
6 Methyl purple Purple- Green 4.8 - 5.4
7 Bromo thymol blue Yellow Blue 6.0 - 7.6
8 Phenol red Yellow Red 6.8 - 8.4
Colorless -
9 Phenolphthalein 8.3 - 10.0
Pink
10 Alizarin yellow Yellow- Violet 10.1 – 12.0
 Volumetric method in PFA
Sl. No. Pesticide Formulation Volumetric analysis
1. Analysis of COC Iodometry titration (IS-1506:1977, Reaffirmed 2012,
Tech. IS-1486:1978, Reaffirmed 2012 & 2017)
2. Analysis of Sulfur Iodimetry titration (IS-6444:1979, Reaffirmed 2012
& 2017-DP), IS-3383:1982, Reaffirmed 2014-wp, IS-
1050:1984, Reaffirmed 2009 & 2014, Sulphur
solution
3. Analysis of ANA Acid base titration (IS- 13138:1991 Reaffirmed 2012
& 2017, tech-IS - 13070:1991, Reaffirmed 2012 &
2017)
4. Analysis of Carbofuran Acid base titration (IS-9360-1980, Reaffirmed 2012
& 2017, tech -IS-11019:1984, Reaffirmed 2005 &
2014, Technical)
5. Analysis of Captan Argentometric titration (IS-11785:1986, Reaffirmed
2012 & 2017, tech-IS-14251:1995, Reaffirmed 2004
& 2014), GC-FID
6. Analysis of Dicofol Argentometric titration (IS-5279:1969, Reaffirmed
2002 & 2012 & 2017, tech IS-5278:1969, Reaffirmed
2012 & 2017)
 Volumetric method in PFA
Sl. No. Pesticide Formulation Volumetric analysis
7. Analysis of 2,4-D Amine Salt Acid –base titration (IS-1827:1989
(Reaffirmed 2004), Second Revision, IS-
4321:1989, Reaffirmed 2004, Technical )
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(Reaffirmed 2009 & 2014), Third Revision, S-
4321:1989, Reaffirmed 2004, Technical )
9. Analysis of 2,4-D Ethyl Ester EC-IS-10243-1993, Reaffirmed 2012 & 2017,
First Revision, Gr. -IS-13513 : 1992,
Reaffirmed 2012 & 2017, WP-IS-10244:1992,
Reaffirmed 2002, 2012 & 2017, First Revison ,
tech-IS-7233:1991, Reaffirmed 2004 & 2014
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10. Analysis of Aluminium TAB-IS - 6438:1980, Reaffirmed 2014, First
phosphide Revisison, POWDER-IS-15219:2002,
Reaffirmed 2014
11. Analysis of Barium Carbonate IS-11151-1984, Reaffirmed 2004 & 2014
(1%P)
 Volumetric method in PFA
Sl. No. Pesticide Formulation Volumetric analysis
12. Analysis of Cuprous Oxide IS-1669:1960, Reaffirmed 2012 & 2014 ,
TECH-IS-1682:1973, Reaffirmed 2012 & 2014
Technical
13. Analysis of Dodine IS-13785:1993, Reaffirmed 2012 & 2017,
TECH-IS-13784:1993, Reaffirmed 2012 & 2017
14. Analysis of Ethephon IS-14409:1996, Reaffirmed 2012 & 2017
(solution), tech-IS-14408:1996, Reaffirmed
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15. Analysis of Mancozeb IS-8708:2006, Reaffirmed 2015, tech-IS-
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16. Analysis of Methyl Bromide IS-1312:1980, Reaffirmed 2004 & 2014

17. Analysis of Oxydemeton-Methyl IS-8259:1976 ,Reaffirmed 2012 & 2017, tech-

IS-8258:1976 ,Reaffirmed 2012 & 2017
 Volumetric method in PFA
Sl. No. Pesticide Formulation Volumetric analysis
18. Analysis of Propoxur IS-9665:1981, Reaffirmed 2012 & 2017, tech-
IS-8496:1977, Reaffirmed 2012 & 2017

19. Analysis of Pyrethrin DP-IS-6178:1982, Reaffirmed 2004 & 2014,

(pyrethrum ) EC-IS-4808:1982, Reaffirmed 2004 & 2014
IS-1051:1980, Reaffirmed 2012 & 2017
(Pyrithrum extract)
20. Analysis of Thiobencarb IS-12769:1989, Reaffirmed 2014, IS-
(Benthiocarb) 12768:1989, Reaffirmed 2004 & 2014,
Technical
21. Analysis of Thiram WP-IS-4766:1982, Reaffirmed 2002 & 2014,
First Revision
FS-IS-4783:1982, Reaffirmed 2014, First
Revision, ws-IS-4783:1982, Reaffirmed 2014,
First Revision, IS-4320:1982, Reaffirmed 2002
& 2014 & 2017-tech.
 Volumetric method in PFA
Sl. No. Pesticide Formulation Volumetric analysis
22. Analysis of Trichlorfon DP-IS-7943:1976, Reaffirmed 2012 & 2017
GR-IS-9364:1980 , Tech-IS-7945:1976,
Reaffirmed 2012 & 2017
23. Analysis of Zinc Phosphide IS-1251:1988, Reaffirmed 2009 & 2014,
Technical, Third Revision
24. Analysis of Zineb WP-IS-3899:1981, Reaffirmed 2002 & 2014,
IS-3898:1981, Reaffirmed 1997 & 2014,
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25. Analysis of Ziram Wp-S-3901:1975, Reaffirmed 2002 & 2017
IS-11010:1984, Reaffirmed 2004 & 2014,
Colloidal Suspension
IS-3900:1975, Reaffirmed 2002 & 2014,
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Thank You