REDOX TITTRATIONS

Aliya Nur Hasanah

Analytical Chemistry Laboratory
2013

TITRATION WHICH IS BASED ON OXIDATION

AND REDUCTION REACTION BETWEEN
ANALYTE AND TITRANT

Redox Reactions :
Fundamental Term

Oxidation process : loss of electron

Reduction process : gain of electron
Reducing agent is oxidized
Oxidizing agent is reduced

NERSNT EQUATION
It is customary to describe redox reaction in
electrochemical terms because transfer electron may
also be carried out in an electrochemical cell
Nernst Equation
To relate electrochemical potentials to activities
(concentration) of species in the system, we can
draw on the thermodynamics relationship involving
free energy change and activities, namely :
G = G0 + RT ln Q
G = -nFE
- nFE = -nFE0 + RT ln Q
E = E0 - RT/nF ln Q
E = E0 - 0,05916/n log Q

 E0 = electrochemical potential for the reaction

when all species are in their standard state
Its describe the tendency of the ion to
reductizes

REDOX TITRATION CURVEs

To evaluate a redox titration we must know the
shape of its titration curve
For redox titration, it is convenient to monitor
electrochemical potential coz we are dealing
with electron
Nernst equation relates the electrochemical
potential to the concentrations of reactants and
products participating in a redox reaction

 Consider, for example a titration in which the

analyte in a reduced state, Ared is titrated with a
titrant in an oxidized state Tox.
The titration reaction is :
A red + T ox
T red + Aox
the electrochemical potential for the reaction is
the difference between the reduction potentials
for the reduction and oxidation half reaction;
thus
Erxn = ETox/Tred EAox/Ared

 Before the equivalence point the titration

mixture consists of appreciable quantities of
both the oxidized and reduced forms of the
analyte, but very little unreacted titrant.
The potential, therefore, is best calculated using
the nernst equation for the analytes half
reaction
EAox/Ared = E0Aox/Ared RT/nF ln [Ared]/[Aox]

 After each addition of titrant, the reaction

between the analyte and titrant reaches a
state of equilibrium. The reactions
electrochemical potential, Erxn, therefore
is zero, and
E Tox/Tred = E Aox/Ared

 After the equivalence point, the potential is

easiest quast to calculate using the Nernst
equation for the titrants half reaction, since
significant quantities of its oxidized and
reduced forms are present
ETox/Tred = E0Tox/Tred RT/nF ln [Tred]/[Tox]

Example
Calculate the titration curve for the titration of 50 mL of 0,1 M Fe2+
with 0,1 M Ce4+ in a matrix of 1M HClO4. (after 5 mL, 50 mL and 60
mL titrant added).
Eo Fe3+/Fe2+ = +0,767 Volt. Eo Ce 4+/Ce 3+ = 1,70 Volt
the reaction is
Fe 2+ + Ce 4+
Fe 3+ + Ce 3+
assume analyte and titrant react completely

Answer
We calculate volume we need to reach the equivalent point. From
the stoichiometry we know that :

So volume Ce4+ needed were :

Before equivalent point :

Easier for us to measure the potential from analyte half potential reaction

Substituting these concentration into potential halfs reaction, gives us :

Equivalent Point :

Mol of [Fe2+] and [Ce4+] equal but so small, so we cant calculate the potential
from reactant or titrant halfs reaction only. We have to combine the two
Nernst Equation.

Adding together this two Nernst equation, give us :

At the equivalent point , the titration reaction stoichiometry requires that

So the ratio of concentration become one and the log become zero, the
potential then:

After adding 60 mL titrant : (the condition are after equivalent point),

we can calculate the potential from potential of titrant halfs reaction

Substituting these concentration gives us :

Evaluating the end point

Finding the end point with visual indicator

Redox indicator : substances that do not participate in
the redox titration, but whose oxidized and reduced
forms differ in color
When added to a solution containing analyte, the
indicator imparts a color that depends on the solutions
electrochemical potential
Since the indicator changes color in response to the
elctrochemical potential, and not to the presence or
absence of a specific species, these compounds are called
general redox indicator
Specific redox indicator : react with the presence of a
specific species

Types of indicators used to signal end point :

MnO4when MnO4- is used as an oxidizing titrant, the solution
remains colorless until the first drop of excess MnO4- is
added. The first tinge purple signals the end point
Starch (Specific Indicator)
forms a dark blue complex with I2 and can be used to
signals the presence of excess I2 (color change : colorless
to blue), or the completion of a reaction in which I2 is
consumed (color change : blue to colorless)
Thiocyanate (specific indicator)
forms a soluble red-colored complex Fe(SCN)2+, with Fe3+

REDOX TITRATION METHODS

Titration Involving Iodine : Iodometry and Iodimetry

Titration With Oxidizing Agent : Permanganometry,

Cerimetry, potassium dichromate

Iodimetry
Titration with I2 solution

Titration performed in neutral or mildy alkaline (pH 8) to

a weakly acid solution
Reason avoiding the pH too acid : starch as indicator

tends to hydrolyze in strong acid, reducing power of

some reducing agent decreases in acid solution, iodide

produced in the reaction tends to be oxidized by dissolved

oxygen in acid solution
Indicator : Starch

Iodometry
Add excess of Iodide (I-) to a solution of an oxidizing agent, I2
produced in an equivalent amount to the oxidizing agent
I2 present can be titrated with reducing agent such as sodium
thiosulfate
I2 + 2S2O32- 2I- + S4O62End point titration detected with starch (by disappearance of the blue

starch-I2 color)
Most titration performed in acid solution

Example : assay of potassium dichromate

Structure of the repeating unit of the

sugar amylose.
Schematic structure of the starchiodine complex. The amylose chain
forms a helix around I6 unit.

View down the starch helix,

showing iodine, inside the helix

Permanganometry
Use potassium permanganate as oxidizing titrant
Acts as self indicator for end point detection

Oxidation with Ce4+

Ce4+ + e = Ce3+
yellow

1.7V in 1 N HClO4

colorless

1.61V in 1N HNO3
1.47V in 1N HCl
1.44V in 1M H2SO4

Indicator : ferroin, diphenylamine

Preparation and standardization:

Ammonium hexanitratocerate, (NH4)2Ce(NO3)6, (primary standard grade)
Ce(HSO4)4,

Standardized with Sodium oxalate.

(NH4)4Ce(SO4)42H2O

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

Oxidation with potassium dichromate

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

K2Cr2O7 is a primary standard.

Indicator : diphenylamine sulphonic acid

End point colour : violet

Eo = 1.36 V

Ex. Redox titration ( hydroquinone vs dichromate standard

solution )

3 HO

Cr2O72 + 14H+ + 6e
Eo= 1.33

2 Cr3+ + 7 H2O

HO

OH

OH + Cr2O72 + 8H+

Eo= Eocathode Eoanode = 1.33 0.700

0.63 V

3O

colorless to violet

Eo= 0.700

O + 2 Cr3+ + 7 H2O

K = 10 nEo/0.05916 = 10 6(0.63) / 0.05916 = 10 64

redox indicator : diphenylamine

+ 2H+ + 2e

Very large : quantitative : complete reaction

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 1:1:3 The reaction
with water involves the following reactions :

C5H5NI2 + C5H5NSO2 + C5H5N + H2O 2 C5H5NHI + C5H5NSO3

C5H5N+SO3 + CH3OH 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 desiccantprotected 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.

Pyridine free Karl Fisher reagent

In recent years, pyridine, and its objectionable odor, have been replaced in the
Karl Fisher reagent by other amines, particularly imidazole.
(1) Solvolysis

2ROH + SO2 RSO3

(2) Buffering

B + RSO3 + ROH2+ BH+SO3R + ROH

(3) Redox

BI2

+ ROH2+

+ BH+SO3R + B + H2O

BH+SO4R + 2 BH+I

HOME WORK
You wish to standardize the solution of KMnO4 0,010 M against standard
Na2C2O4 (Mr = 134). If you want to use between 30 and 45 mL of the reagent
for the standardiization, what range of weights of the primary standard
should you take?

HOME WORK
Derive a curve for the titration of 50 mL of 0,025 M U 4+ with 0,1 M Ce 4+ after
adding 5 mL , 25mL, and 30 mL of Ce 4+ . Assume that the solution Is 1.0 M in
H2SO4 throughout the titration ( [H+] for such a solution will be about 1.0 M)
The analytical reaction is :
U 4+ + 2H2O + 2 Ce 4+

From the handbook :

Ce 4+ + e
UO 2 2+ + 4H+ + 2e

UO22+ + 2 Ce 3+ + 4H+

Ce 3+
U 4+ + 2H2O

Eo = +1.44 V
Eo = +0,334 V