Oxidation Reduction Reaction

 Reactions of metals or any other organic

compounds with oxygen to give oxides are
labeled as oxidation.

 The removal of oxygen from metal oxides to

give the metals in their elemental forms is
labeled as reduction.

 In other words, oxidation is addition of oxygen

and removal of hydrogen whereas reduction is
addition of hydrogen and removal of oxygen.
 Oxidation Reduction Reaction
Reactions of metals or any other organic compounds
with oxygen to give oxides are labeled as oxidation.

The removal of oxygen from metal oxides to give the

metals in their elemental forms is labeled as
reduction.

In other words, oxidation is addition of oxygen and

removal of hydrogen whereas reduction is addition of
hydrogen and removal of oxygen.
 Chemical reaction
 Reduction-Oxidation reaction commonly known
as RedOx reaction

 Ox1 + Red2 ⇌ Red1 + Ox2

 Chemical reaction based oxidation and reduction

reaction is known as RedOx reaction

Fe2+ + Ce4+ → Fe3+ + Ce3+ (1)

 Titrations Involving Iodine
One of the most common redox titrations
involve either using iodine (I2) as a mild
oxidizing agent or iodide (I-) as a mild
reducing agent.
Iodine as oxidizing agent:
I2 + 2 e - = 2 I -
When iodine is used as the titrant the
method is known as iodimetry.
 Titrations Involving Iodine
I2 is not very soluble in water (only about
1.3 x 10 -3 mol/L). It solubility is increased
in the presence of excess iodide by the
formation
of the triiodide (I3-) species,
I2 + I - = I 3 –
So it is really the triiodide species, though it
will commonly be referred to as iodine
that is involved in the chemical reactions.
 Titrations Involving Iodine
 Due to the difficulty is maintaining the
concentration of I2, (limited solubility in water,
appreciable vapor pressure of the I2.) iodometric
methods are more commonly used. The amount
of I2 produced by the action of the oxidizing
analyte on excess iodide is usually titrated with
standardized sodium thiosulfate, Na2S2O3.
 Titrations Involving Iodine
Iodide as reducing agent:
2 I- = I2 + 2 e -
When iodine is produced by the addition of
an oxidizing analyte to an excess of
iodide, the method is as iodometry.
 Titrations Involving Iodine
Thiosulfate (S2O3-2) is commonly used in
titration reactions involving iodine, both
for iodimetric and iodometric methods.
The iodimetric methods generally involve
an excess of standard I2 (as I3 -) followed
by back titration with standard thiosulfate.
 Titrations Involving Iodine
In the iodometric methods, an excess of
iodide is added to the sample of an
oxidizing analyte and a stoichiometric
amount of iodine (I2 or I3- ) is produced.
This iodine is titrated with a standard
solution of thiosulfate. This reaction is
shown on the following slide.
Titrations Involving Iodine
 Titrations Involving Iodine
The reaction with iodine needs to occur in
a solution whose pH < 9 to prevent side
reactions which produce iodates (IO3-).
Generally acetic acid is added to the
analyte mixture before titration to assure
the proper pH. In some cases,
appropriate pH buffers may also be added.
 Titrations Involving Iodine
The titrant solution of thiosulfate cannot
be prepared directly. It is made to an
approximate concentration and then
standardized with a primary standard
oxidizing agent by iodometry. The
thiosulfate solution is unstable if the pH <
5, undergoing the following
disproportionation reaction.
S2O3-2 + 2 H+ < == > H2SO3 + S
 Titrations Involving Iodine
 This disproportionation reaction is
prevented by using freshly boiled
deionized water as the solvent and adding
a small amount of NaOH. Although the
thiosulfate needs to be stored in a basic
solution, as mentioned earlier, its reaction
as a reductant titrant needs to occur in an
acid solution.
 Chapter 16 – Iodine Methods
 The indicator for both iodimetric and
iodometric titrations is a starch solution; in
the presence of iodine, it shows a blue or
purple color. The starch indicator should
not be added when I2 is in large excess
because the desorption of I2 from the
starch molecule is not reversible.
 Starch Indicator

 The repeating
amylose unit in
the starch
molecule. Starch
is a polymer of
amylose.
 Starch Indicator

 The starch-iodine
complex where the
sugar chain forms a
helix about I6 units.
 Iodimetric titrations: Titrations with
standard iodine (actually I3)

Species analyzed Oxidation reaction

SO2 SO2 + H2O < == > H2SO3
H2SO3 + H2O < == > SO24- + 4H+ + 2e-

H2S H2S < == > S(s) + 2H+ + 2e-

Zn2+, Cd2+, M2+ + H2S  MS(s) + 2H+

Hg2+, Pb2+ MS(s) < == > M2+ + S + 2e-
Iodimetric titrations: Titrations with standard iodine
(actually I3)

Species analyzed Oxidation reaction

Cysteine, glutathione, 2RSH < == > RSSR + 2H+ +
2e-
mercaptoethanol

Aldehydes H2CO + 3OH- < == > HCO2- + 2H2O +

2e-

Glucose (and other reducing sugar)

O
RCH + 3OH- < == > HCO2- + 2H2O + 2e-

Ascorbic acid See next slide

(or vitamin C)
Ascorbic acid (or vitamin C)
Iodometric titrations: Titrations of iodine (actually
I3) produced by the analyte
Species analyzed Reaction

HOCl HOCl + H+ + 3I- < == > Cl - + I3- + H2O

Br2 Br2 + 3 I- < == > 2 Br - + I3-

IO3- 2 IO3- + 16 I - + 12 H+ < == > 6 I3- + 6 H2O

IO4- 2 IO4- + 22 I - + 16 H+ < == > 8 I3 - + 8 H 2 O

O2 O2 + 4 Mn(OH)2 + 2 H2O < == > 4 Mn(OH)3

Mn(OH)3 + 6 H+ + 6 I - < == > 2 Mn2+ + 2 I3- + 6 H2O

H 2 O2 H 2 O2 + 3 I - + 2H+ < == > I3- + 2 H2O

Iodometric titrations: Titrations of iodine (actually
I3) produced by the analyte
Species analyzed Reaction

O3 O3 + 3 I - + 2 H+ < == > O2 + I3- + H2O

NO2- 2 HNO2 + 2 H + + 3I - < == > 2 NO + I3- + 2 H2O

S2O82- S2O82- + 3 I - < == > 2 SO42- + I3-

Cu2+ 2 Cu2+ + 5 I - < == > 2 CuI(s) + I3-

MnO4- 2 MnO4- + 16 H+ + 15 I - < == > 2 Mn2+ + 5 I3- + 8 H2O

MnO2 MnO2(s) + 4 H + + 3I - < == > Mn2+ + I3- + 2 H2O