SEMINAR

TOPIC:IODIMETRY
&
IODOMETRY
Presented by
ANJANA SURENDRAN
ANJU VIJAYAN
ANUPAMA C P
ARYA MM
AYSHA AFEEFA A
iodimetry & iodometry 1
IODIMETRY

PREPARATION OF 0.1M IODINE SOLN

STANDARDISATION OF 0.1M IODINE SOLN
ENDPINT DETECTION
APPLICATIONS OF IODIMETRIC ITRATIONS

IODOMETRY
PREPARATION OF 0.1M OF SODIUM
THIOSULPHATE SOLN
STANDARDISATION OF 0.1M SODIUM
THIOSULPHATE SOLN
DETCTION OF ENDPOINT
APPLICATIONS OF IODOMETRIC TITRATION
iodimetry & iodometry 2
INTRODUCTION
Iodimetry and Iodometry are two important redox
titrations.

IODIMETRY(direct titrations):Determinations
involving direct titration with iodine due to the
oxidising power of iodine in aqueous soluton.
 IODOMETRY(indirect titrations):
iodine-sodium thiosulphate titration
The titration in which equivalent amount of iodine is
liberated against standard solution of sodium thiosulphate

iodimetry & iodometry 3

IODIMETRY
Iodine is a mild oxidising agent.The normal reduction
potential of the reaction
I2 +2e- 2I- is 0.5345 volt
• In most direct titrations,iodine in potassium iodide is
employed since iodine is readily soluble in solution of
iodide and also decrease the volatility of iodine.Hence the
reacting species is triiodide.
I3- + 2e- 2I- (reduction potential is 0.5355volt)

iodimetry & iodometry 4

o Thiosulphate (S2O32-), As(111), Sb(111),sulphide, sulphite,
Sn(11),ferrocyanide are some of the important reducing agents
which are strong enough to be directly titrated with iodine.so
iodine reduced to iodide ions in presence of these reducing
agents.
o The reducing power of such substance depends upon [H+]
conc. Hence to make the rxn quantitative,proper control of pH
is essential

 DETECTION OF ENDPOINT

 Self indicator … a solution of I2 in aq iodide has intense yellow

to brown colour.one drop of 0.05M I2 sol. Imparts a
precipitate of pale yellow colour to 100ml of water,so that in
other wise colourless solutions.
Iodimetry & iodometry 5
However in practice starch solution is used as indicator.
Starch impart blue colour to iodine solution. Not used in
strongly acidic soln…starch hydrolysis.
Starch solution should be freshly prepared or stabilized by
addition of preservative such as mercuric iodide HgI or
formamide
PREPARATION OF 0.1N IODINE SOLUTION

Weigh accurately about 12.7g of reagent grade iodine place it in

a beaker.
add the beaker 40g of KI (free from iodate) and 25ml of water.
stirr to dissolve whole of the I2 and transfer the soln into glass
stoppered bottle {of dark brown glass).
 dilute to 1oooml.
 Keep the soln in cool and dark place.
Iiodimetry
6
STANDARDISATION OF 0.1 N IODINE SOLUTION

The I2 soln may be standardised by the following

Primary standard Arsenic trioxide
Secondary standard sodium thiosulphate soln

Standardisation using Arsenic trioxide

principle:-
•The substance which is present in aq soln as arsenious acid(H3AsO3)
is oxidised by iodine according to eqn:-
H3ASO3 +I2+ H2O H3AsO4 +2HI
•Arsenic trioxide is slowly soluble in cold water more rapidly soluble
in hot water and readily soluble in NaOH soln to form sodium
arsenite.
As2O3+6NaOH 2Na2AsO3+ 3H20
•If I2 is added to this alkaline soln, some of its tended to form
sodium hypoiodite(NaIO) or similar compounds,which donot
readily react with arsenious ion.
iodimetry & iodometry 7
•The exess of NaOH is therefore neutralized with HCl using
methylorange as indicator untill yellow colour is changed to pink.
•Sodium bicarbonate is added to neutralize the hydriodic acid
formed in the reversible reactions.

Na3AsO3+I2+2NaHCO3 Na3AsO4+2NaI+2CO2 +H2

Procedure:-

Weigh accurately about 1.25g of arsenic trioxide and solution is

prepared by 3g of NaOH in 10ml of water.
dissolve the solid completely.now add 50 ml of water,2 drops of methyl
orange indicator and hydrochloric acid untill the yellow colour changes
to pink.
then add 1ml conc.HCl exess and transfer the solution to 250ml
volumetrical flask ,mke up with water and mix well to make it
homogeneous.
iodimetry & iodometry 8
Transfer 25 ml of arsenite soln to concal flask and dilute it with
50 ml of Water.
Add carefully small portion of solid sodium bicarbonate to
neutralize the acid.
Add 5ml of starch indicator and titrate with iodine soln untill
the appearance of deep blue colour.

iodimetry & iodometry 9

Standardisation using sodiumthiosulphate

Procedure:-

Rinse and fill the burette with Na2S2O3 soln.

pipette out 25ml standardised 0.1N iodine soln into conical
flask.
add sodium thiosulphite to conical flask from burette untill
the iodine solution assumes pale yellow colour.
Now add 1ml of freshly prepared starch indicator an intense
blue colour is developed.
titrate dropwise with constant shaking,untill the blue colour
just disappears.
 2Na2S2O3+I2 Na2S4O6+ 2NaI

iodimetry & iodometry 10

APPLICATIONS OF IODIMETRIC TITRATIONS

1. DIRECT TITRATION WITH IODINE SOLUTION

Assay of sodium thiosulphate IP

2Na2S2O3 + I2 Na2S4O6 +2NaI

 Weigh accurately about 0.5gm dissolve in 20ml of water

Titrate with 0.05M iodine with using starch solution added
towards the end of titrations as indicator.

iodimetry & iodometry 11

Assay of Ascorbic acid IP

Ascorbic acid H2SO4 Dehydroascorbic acid

Weigh accurately about 0.1gm and dissolve in a mixture of 100 ml

of freshly boiled and cooled water.
 add 25ml of 1M H2SO4.
Immediately titrate with 0.05M I2 using starch soln as indicator

iodimetry & iodometry 12

 Assay of Analgin
Weigh accurately about 0.4gm,dissolve in a mixture of 40ml of
Indicator is not used.
ethanol and 10ml of 0.01M HCl .
Titrate with 0.05M I2 soln untill a yellow colour stable for 30
seconds is produced.
2.BACK TITRATION
Assay of Dimercarpol IP
Weigh accurately about 0.1gm,dissolve in 40ml of methanol
Add 20ml of 0.1M HCl and 50ml of 0.05M I2.
Allow to stand for 10 minutes
Titrate with 0.1M sodium thiosulphate.
Repeat the titration without the substance being examined.

iodimetry & iodometry 13

 Assay of sodium meta bisulphite IP

weigh accurately about 0.1gm ,dissolve in 50ml of 0.1M I2

Add 1ml of HCl
Titrate the exess of I2 with 0.1M sodium thiosulphate using
Starch soln-indicator

iodimetry & iodometry 14

 IODOMETRY
•Iodometric titrtn - oxidising agents such as
KMnO4,K2Cr2O7,CuSO4,peroxides etc are treated with excess of
KI to liberate I2 which is titrated against a standard soln of
sodium thiosulphate as a reducing agent using starch as an
indicator,-neutral /faintly acidic medium.

PRINCIPLE:-

•Oxidising agent oxidises KI in presence of mineral acid

•Liberate I2- its amt is measured by titrtn with std sodium
thiosulphate soln-starch soln indicator

iodimetry & iodometry 15

•Solubility of iodine in water is ow and dissolve in KI to form
triiodide.
• I2(aq) +I- I3
•Stable I2 & I3- are weak oxidisig agents than KMnO4,K2Cr2O7,or
Ce(SO4) 2.The I3- is unstable so dissociates.
• I3- I2 +I-
•The liberated iodine is neutral against standard soln of sodium
thiosulphate pentahydrate(Na2S2O3.5H2O).
• I3- +2S2O32- 3I- +S4O62-
• I2 +2S2O32- 2I- +S4O62-

iodimetry & iodometry 16

PREPARATION OF STANDARD SOLUTION OF
SODIUM THIOSULPHATE

•The equivalent of sodium thiosulphate penta hydrate is 248.18g

mol wt
•Approximately 0.1 M soln is prepared by dissolving sodium
thiosulphate in 1L of water.

STABLITY OF Na2S2O3 SOLN

The excess CO2 present in distilled water cause decompositio

of sodium thiosulphate.
S2O32- + H+ HSO3 + S
Decomposition can also be by the action of Thiobacillus
thioparus bacteria

iodimetry & iodometry 17

PRECAUTIONS:

1. Use recently boiled distilled water.

2. Add 3 drops of chloroform,10 mg mercuric iodide to increase

keeping property
add some sodium carbonate to adjust pH in arange of 9 and
10,where bacterial activity doesn’t occur.
alkali hydroxides,sodium carbonate(>0.1g/L)and sodium
tetraborate shold not be added,these accelerate
decomposition.

3. Aviod exposure to light.

iodimetry & iodometry 18

SRANDARDISATION OF 0.1 M SODIUM THIOSULPHATE
SOLUTION

This can be done by following methods:

primary standard
pottasium bromate
potassium iodate
potassium dichromate
secondary standard
iodine solution

iodimetry & iodometry 19

Stadardisation using potassium bromate

•This can be determined by the addition of potassium iodide and

dilute HCl with potassium bromate.
•Reaction b/w potassium iodate formed from potassium bromate
and excess KI in acid soln results liberation of iodine,which can be
titrated with sodium thiosulphate soln using starch soln as
indicator.

KI+H2O HI +KOH
KBrO3+ HI KIO3 +KBr
KIO2I+HBr
KIO3 +5KI+6HCl 3I2+6KCl+3H2O

iodimetry & iodometry 20

Standisation using potassium iodate:

Potassium iodate reacts with KI in acid to iberate iodine

KIO3 +5KI+ 6HCl 3I2 +6KCl+3H2O
titration with sodium thiosulphate-starch soln indicator

Standardisation using potassium dichromate:

Potassium dichromate is reduced by an acid soln of potassium

iodide,and liberates eqivalent qty of iodine.
Titrate against Na2S2O
K2Cr2O7+6KI+14HCl 2CrCl3+8KCl+3I2+H2O

I2+2Na2S2O3 Na2S4O6 +NaI

iodimetry & iodometry 21
Standardiation using standard iodine solution:

Measure a 25ml of standard iodine soln into a conical flask,add

about 150ml istilled water and titrate with Na2S2O3 soln, adding
2ml of starch soln when the liquid is pale yellow in colour.

I2 + 2Na2S2O3 Na2S4O6+2NaI

iodimetry & iodometry 22

DETECTION OF END-POINT

The endpoint of iodometric titrations can be found by adding the

following as indicator:
1. STARCH SOLUTION
2. SODIUM STARCH GLYCOLATE

Starch soln-indicator –preparation

i. Starch mucilage preparation

ii. Starch solution preparation

Sodium starch glycolate indicator-preparation & use

iodimetry & iodometry 23

APPLICATIONS OF IODOMETRIC TITRATIONS

Assay of copper sulphate

2CuSO4+4KI 2CuI2+2K2SO4
2CuI2 2Cu2I2+I2

•tirated with standard sodium thiosulphate solution using

Starch mucilage as indicator.

•Potassium thiocynate is added to convert small qty of

cuprous iodide to cuprous thiocynate-to ensure
completion of rxn (prevent backward rxn)and release I2.

•Endpoint is slow-blue colour to white or flesh colour.

iodimetry & iodometry 24
Assay of chlorinated lime(bleaching powder)

•The chlorine present in the chlorinated lime replaces and liberate

iodine from potassium iodide.
•The liberated iodine is titrated with standard 0.1M sodium
thiosulphate soln.
•Starch mucilage is used as indicator which is added at the end of
titration
CaCl(OCl) +2CH3COOH (CH3COO)2Ca +HCl +HOCl
HCl+HOCl Cl2+H2O
2KI+Cl2 2KCl+I2
I2+Na2S2O3 Na2S4O6 +2NaI
Endpoint-discharge of blue colour

iodimetry & iodometry 25

REFERENCE:
1.Textbook of pharmaceutical titrimetric analysis,
A.A Napolean,fourth edition,2013,page no:8.48 to 8.55.
2. Textbook of phrmaceutical analysis,Kamboj,first edition,
volume 1,2003,page no:429 to 494

iodimetry & iodometry 26

THANK YOU

iodimetry & iodometry 27