YODIMETRIA, YODOMETRIA

y YODATOMETRIA

There are a lot of redox titrations classified according to the

titrant used.
1) Permanganimetric: Titrant KMnO4

2) Dichromatometric: Titrant K2Cr2O7

3) Titrations involving iodine (I2)
Iodimetry
Iodometry
Titrations that create or consume I2 are widely used in
quantitative analysis.

A reducing agent is the element or compound in a redox

reaction that reduces another species. In doing so, it
becomes oxidized, and is therefore the electron donor in the
redox.

Examples of reducing agents:

The active metals sodium, magnesium, aluminum, and
zinc,

NaH, CaH2, and LiAlH4, which formally contain the Hion.

An oxidaizing agent is the element or compound in a redox

reaction that oxidaizes another species. In doing so, it
becomes reduced, and is therefore the element or compund
that gain electrons.

Examples:
permanganate (MnO4-), chromate (CrO42-), and dichromate
(Cr2O7)2- ions, sodium hypochlorite (bleach) as well as nitric
acid (HNO3), perchloric acid (HClO4), and sulfuric acid (H2SO4)

When a reducing analyte is titrated with iodine (the titrant),

the method is called iodimetry.

Iodimetry: A direct titration with only 1 reaction:

Analyte
unknown

+ titrant (iodine I2) product (iodide I-)

known

When a reducing analyte is titrated with iodine (the titrant),

the method is called iodimetry.
Example: Quantification of Ascorbic Acid (Vitamin C)

C6H8O6 + I2 CH6O6 + 2I- + 2H+

Iodine rapidly oxidizes ascorbic acid, C6H8O6 , to produce
dehydroascorbic acid, C6H6O6 .
Ascorbic acid

Dehydroascorbic acid

Pictures taken from: http://en.wikipedia.org

Iodometry is the titration of iodine (I2) produced when an

oxidizing analyte is added to excess I- (iodide).
Then the iodine (I2) is usually titrated with standard
thiosulfate solution.

Iodometry: Not a direct titration because there are 2 reactions:

analyte
unknown
I2

+
+

I-

I2

titrant (standard thiosulfate)

Known

product

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

Analytical applications:
Iodimetric titrations:

Species analyzed (reducing analytes)

SO2
H2S
Zn2+ , Cd2+ , Hg2+ , Pb2+
Cysteine, glutathione, mercaptoethanol

Section of a protein structure

Source: http://en.wikipedia.org

Glucose (and other reducing sugars)

Analytical applications:
Iodometric titrations:
Species analyzed (oxidizing analytes)
HOCl

Br2
IO3- ,
O2,

IO4H2O2,

O3

NO2Cu 2+
MnO4-,

MnO2

Example: Quantification of Copper

2 Cu

2+

4I-

2CuI

I2

Analyte of
unknown
concentration

I2

2S2O32-

2I-

Titrant
-standrard solutions: sodium
thiosulfate
-known concentration

S4O62-

Fact File 1: Introduction to iodometric and iodimetric titrations

In this lesson: Iodometric titration of copper

Sample: Copper wire (solid)
First: Dissolve the sample
copper wire Cu0 dissolution Cu 2+
Copper ion: oxidizing agent

Second: Pre-treatment of the sample

Fact File 1: Introduction to iodometric and iodimetric titrations

Third: Iodometric titration

2 Cu

2+

4I-

2CuI

I2

Analyte of
unknown
concentration

I2

2S2O32-

2I-

Titrant
-standrard solutions: sodium
thiosulfate
-known concentration

S4O62-

APLICACIONES PARA LAS

VALORACIONES
YODOMETRICAS

Preadjustment of analyte oxidation state

It is necessary to adjust the oxidation state of the analyte to one that can be titrated
with an auxiliary oxidizing or reducing agent.

Ex.

Preadjustment by auxiliary reagent

Fe(II), Fe(III)

Fe(II)
4

Titration

Ce4+
Preoxidation :

Peroxydisulfate ( (NH4)22S) 2O8 )

Sodium bismuthate ( NaBiO 3)
Hydrogen peroxide (H2O2)

Prereduction : Stannous chloride ( SnCl2)

Chromous chloride
Jones reductor (zinc coated with zinc amalgam)
Walden reductor ( solid Ag and 1M HCl)
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Reagents used in redox titration

Reducing agents
1) ammonium iron(II) sulfate hexahydrate (Mohrs salt)

FeSO 4(NH4)2SO4 6H2O

2) iron(II) ethylene diamine sulfate (Oespers salt) FeC2H4(NH3)2(SO4)2 4H2O

3) Sodium thiosulfate pentahydrate
4) Arsenic trioxide: arsenious oxide

Na2S2O35H2O
As2O3

5) Sodium oxalate and oxalic acid dihydarte

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Na2(COO)2 ,

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(COOH)22H2O

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Standardization of thiosulfate solution:

Primary standard : potassium iodate (KIO3), K2Cr2O7, KBrO3
Titration reactions:
KIO3 + 5KI + 6HCl
I2 + 2Na2S2O3
KIO3

3I2 + 6KCl + 3 H2O

2NaI + Na2S4O6

3I2

6Na2S2O35H2O

6 Equivalent

S2O32- +H+ HSO3- +S(s)

pH, Microorganisms, Concentration, Cu2+, Sunlight

Stabilizer for sodium thiosulfate solution : Na2CO3

Na2S2O3 + H2O + CO2
H2S2O3
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Na2CO3 + H2S2O3

H2SO3 + S
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16-2 Finding the end point

A redox indicator is a compound
that changes color
when it goes from its oxidized
to its reduced state.

or
For ferroin, with E = 1.147 V
we expect the color change to occur in the approximate range
1.088 V to 1.206 V with respect SHE
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Starch-Iodine Complex
Starch is the indicator of choice for those procedures
involving iodine because it forms an intense blue colour
with iodine.
Starch is not a redox indicator;
it responds specifically to the presence of I2,
not to a change in redox potential.

Structure of the repeating unit

of the sugar amylose.
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Arsenious oxide, As4O6

As4O6 + 6H2O = 4H3AsO3

H3AsO3 + I3 + H2O = H3AsO4 + 3I + 2H+

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Reagents used in redox titration

Oxidizing agents

1) Potassium permanganate KMnO4 :

Permanganometry

2) Ceric sulfate / Ceric ammonium sulfate

3) Potassium dichromate K2Cr2O7
4) Iodine I2 :

Ce(SO4)22(NH4)2SO4 4H2O : Cerimetry

Dichrometry

Iodimetry, Iodometry

5) Potassium iodate

KIO3

: Iodatimetry

6) Potassium bromate KBrO3 : Bromatimetry

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Permanganate titration

Oxidation with permanganate : Reduction of permanaganate

KMnO4 Powerful oxidant that the most widely used.
1) In strongly acidic solutions (1M H2SO4 or HCl, pH

MnO4 + 8H+ + 5e = Mn2 + + 4H2 O

1)

Eo = 1.51 V

KMnO4 is a self-indicator.

2) In feebly acidic, neutral, or alkaline solutions

MnO4 + 4H+ + 3e = MnO2 (s) + 2H2 O

Eo = 1.695 V

3) In very strongly alkaline solution (2M NaOH)

MnO4 + e = MnO42

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Eo = 0.558 V

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Permanganate titration

Duration of colour in end point (30 seconds)

MnO4 + 3Mn2+ + 2H2O 5MnO2 + 4H+

K=1*1047

Stability of aqoues solution of MnO4MnO4 + 2H2O 4MnO2 (s) + 3O2 (g) +4OH-

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Standardization of KMnO4 solution

Potassium permanganate is not primary standard, because traces of MnO2
are invariably present.

Standardization by titration of sodium oxalate (primary standard) :

2KMnO4 + 5 Na2(COO)2 + 8H2SO4 = 2MnSO4 + K2SO4 + 5Na2SO4 + 10 CO2 + 8H2O

2KMnO4

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5 Na2(COO)2

10 Equivalent

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Preparation of 0.1 N potassium permanganate solution

KMnO4 is not pure.
Distilled water contains traces of organic reducing substances
which react slowly with permanganate to form hydrous managnese dioxide.

Manganesse dioxide promotes the autodecomposition of permanganate.

1)

Dissolve about 3.2 g of KMnO4 (mw=158.04) in 1000ml of water,

heat the solution to boiling, and keep slightly below the boiling point for 1 hr.
Alternatively , allow the solution to stand at room temperature for 2 or 3 days.

2)

Filter the liquid through a sintered-glass filter crucible to remove solid MnO2.

3)

Transfer the filtrate to a clean stoppered bottle freed from grease with cleaning
mixture.

4)

Protect the solution from evaporation, dust, and reducing vapors, and keep it in the
dark or in diffuse light.

5)

If in time managanese dioxide settles out, refilter the solution and restandardize it.

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Applications of permanganometry
(1) H2O2
2KMnO4 + 5 H2O2 + 3H2SO4 = 2MnSO4 + K2SO4 + 5O2 + 8H2O

(2) NaNO2
2NaNO2 + H2SO4 =

Na2SO4

+ HNO2

2KMnO4 + 5 HNO2 + 3H2SO4 = 2MnSO4 + K2SO4 + 5HNO3 + 3H2O

(3) FeSO4
2KMnO4 + 510 FeSO4 + 8H2SO4 = 2MnSO4 + K2SO4 + 5Fe2(SO4)3 + 8H2O

(4) CaO
CaO + 2HCl = CaCl2 + H2O
CaCl2 + H2C2O4 = CaC2O4 + 2HCl

(excess oxalic acid)

2KMnO4 + 5 H2C2O4 + 3H2SO4 = 2MnSO4 + K2SO4 + 10CO2 + 8H2O (back tit)

(5) Calcium gluconate

[CH2OH(CHOH)4COO]2Ca + 2HCl = CaCl2 + 2CH2OH9CHOH)4COOH
(NH4)2C2O4 + CaCl2 = CaC2O4 + 2 NH4Cl
CaCl2

+ H2SO4 =

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H2C2O4 + CaSO4

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+ 5 H2C2O4 + 3H2SO
4 = 2MnSO4 + K2SO4 + 10CO2 + 8H2O

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Oxidation with Ce4+

Ce4+ + e = Ce3+

1.7 V in 1 N HClO4

yellow

1.61 V in 1N HNO3

colorless

1.47 V in 1N HCl
1.44 V in 1M H2SO4
Indicator : ferroin, diphenylamine

Preparation and standardization:

Ammonium hexanitratocerate, (NH4)2Ce(NO3)6, (primary standard grade)

Sodium oxalate.

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Applications of cerimetry

(1) Menadione (2-methylnaphthoquinon: vitamin K3)

HCl, Zn

O
CH3

OH
CH3

Reduction

2 Ce(SO4)2

OH

(2) Iron

2FeSO4 + 2 (NH4)4Ce(SO4)4 = Fe2(SO4)3 + Ce2(SO4)3 + 4 (NH4)2SO4

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Oxidation with potassium dichromate

Cr2O72 + 14H+ + 6e = 2Cr3+ + 7H2O

Eo = 1.36 V

K2Cr2O7 is a primary standard.

Indicator : diphenylamine sulphonic acid

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Ex. Redox titration ( hydroquinone vs dichromate standard solution )

Cr2O72 + 14H+ + 6e
3

HO

3 HO

2 Cr3+ + 7 H2O

OH

Eo= 1.33

OH + Cr2O72 + 8H+

+ 2H+ + 2e

Eo= 0.700

O + 2 Cr3+ + 7 H2O

3O

Eo= Eocathode Eoanode = 1.33 0.700 = 0.63 V

K = 10 nEo/0.05916 = 10 6(0.63) / 0.05916 = 10 64
redox indicator : diphenylamine

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colorless to

violet

Very large : quantitative : complete reaction

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Iodimetry and iodometry

Iodimetry:
a reducing analyte is titrated directly with iodine (to
produce I).

I2 + V.C 2I- +
iodometry :
an oxidizing analyte is added to excess I to produce
iodine, which is then titrated with standard thiosulfate
solution.
I- + Cu2+ I2 + Cu+

I2 + S2O32- 2I- + S4O62-

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standard I31) Iodine only dissolves slightly in water. Its solubility is

enhanced by interacting with I-

2) An excellent way to prepare standard I3- is to add a weighed

quantity of potassium iodate to a small excess of KI. Then
add excess strong acid (giving pH 1) to produce I3- by
quantitative reverse disproportionation:

3) Cu2++4I- 2CUI + I2
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Stability of I2 Solutions
In acidic solutions of I3- are unstable because the
excess I is slowly oxidized by air:

In neutral solutions, oxidation is insignificant in the

absence of heat, light, and metal ions.

At pH 11, triiodide disproportionates to hypoiodous

acid (HOI), iodate, and iodide.
I2 + OH- IO- + I- + H+
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3IO- IO3- + 2I-

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Determining water with the Karl Fisher Reagent

The Karl Fisher reaction :
I2 + SO2 + 2H2O

2HI + H2SO4

For the determination of small amount of water, Karl Fischer(1935) proposed a

reagent prepared as an anhydrous methanolic solution containing iodine, sulfur
dioxide and anhydrous pyridine in the mole ratio 1:3:10. The reaction with water
involves the following reactions :

C5H5NI2 + C5H5NSO2 + C5H5N + H2O

C5H5N+SO3 + CH3OH

2 C5H5NHI + C5H5NSO3

C5H5N(H)SO4CH3

Pyridinium sulfite can also consume water.

C5H5N+SO3 + H2O

C5H5NH+SO4H

It is always advisable to use fresh reagent because of the presence of various side
reactions involving iodine. The reagent is stored in a desiccant-protected container.

The end point can be detected either by visual( at the end point, the color changes
from dark brown to yellow) or electrometric, or photometric (absorbance at 700nm)
titration methods. The detection of water by the coulometric technique with Karl
Fischer reagent is popular.

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BROMATOMETRIA
Es el mtodo de las oxidoreductimetrias donde se emplean
las reacciones de in bromato, (BrO3)1-

(BrO3)1- + 6 H+
Pot +1,45 v

6e-

Br1-

3 H2O

Por tanto, el equivalente gramo ser 1/6 del Peso Formula.

(167,01 / 6) = 27,84
Puede observarse que el medio tiene que ser
necesariamente cido. Como el bromato necesita realizarse
en caliente y en medio fuertemente cido.

Durante la titulacin los iones bromato se reducen a bromuro, que

al aparecer en el medio, en presencia de iones bromato,
reaccionan con este oxidndose.

(BrO3)1- + 6 H+

+ 5 Br1-

3 Br2

3 H2O

El bromo libre que se forma colorea la solucin de amarillo plido.

Este color es imposible de observar con precisin en el punto de
equivalencia. Pero existen colorantes organicos que se oxidan
irreversiblemente con el bromo y la solucin coloreada con ellos
se decolora. Algunos de estos colorantes son el anaranjado de
metilo y el rojo de metilo.
La solucin patrn que se emplea en bromatometra es la 0,10N,
preparada por pesada directa de la sal seca. Pero puede usarse
la solucin 0,010N (contiene 2,7835 g de sal por litro)
Se emplea para valorar, por ejemplo, fenoles