Redox Titrations

Lecture 2

Nov 15, 2002



Homework Chapter 15

Problems 11, 12, 13, 16, 17

Due Wed, Nov 20
Titrations Involving Iodine
One of the most common redox titrations
involve either using iodine (I
2
) as a mild
oxidizing agent or iodide (I
-
) as a mild
reducing agent.
Iodine as oxidizing agent:
I
2
+ 2 e
-
= 2 I
-
When iodine is used as the titrant the
method is known as iodimetry.

Titrations Involving Iodine
I
2
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 (I
3
-
) species,
I
2
+ 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
Iodide as reducing agent:
2 I
-
= I
2
+ 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 (S
2
O
3
-2
) is commonly used in
titration reactions involving iodine, both for
iodimetric and iodometric methods. As
shown in Tables 15-2 the iodimetric
methods generally involve an excess of
standard I
2
(as I
3
-
) 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 (I
2
or I
3
-
) is produced.
This iodine is titrated with a standard
solution of thiosulfate. This reaction is
shown on the following slide.

Titrations Involving Iodine
The reaction with iodine needs to occur in a
solution whose pH < 9 to prevent side
reactions which produce iodates (IO
3
-
).
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.
S
2
O
3
-2
+ 2 H
+
< == > H
2
SO
3
+ 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.
Titrations Involving Iodine
TABLE 15-2 Iodimetric titrations: Titrations with
standard iodine (actually I
3

)

Species analyzed Oxidation reaction
SO
2
SO
2
+ H
2
O < == > H
2
SO
3
H
2
SO
3
+ H
2
O < == > SO
2
4-
+ 4H
+
+ 2e
-


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

Zn
2+
, Cd
2+
, M
2+
+ H
2
S MS(s) + 2H
+
Hg
2+
, Pb
2+
MS(s) < == > M
2+
+ S + 2e
-



TABLE 15-2 Iodimetric titrations: Titrations with
standard iodine (actually I
3

) {continued}

Species analyzed Oxidation reaction
Cysteine, glutathione, 2RSH < == > RSSR + 2H
+
+ 2e
-
mercaptoethanol

Aldehydes H
2
CO + 3OH
-
< == > HCO
2
-
+ 2H
2
O + 2e
-

Glucose (and other reducing sugar)
O
RCH + 3OH
-
< == > HCO
2
-
+ 2H
2
O + 2e
-

Ascorbic acid See next slide
(or vitamin C)

Ascorbic acid (or vitamin C)
TABLE 15-3 Iodometric titrations: Titrations of iodine
(actually I
3

) produced by the analyte

Species analyzed Reaction

HOCl HOCl + H
+
+ 3I
-
< == > Cl
-
+ I
3
-
+ H
2
O

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

IO
3
-
2 IO
3
-
+ 16 I
-
+ 12 H
+
< == > 6 I
3
-
+ 6 H
2
O

IO
4
-
2 IO
4
-
+ 22 I
-
+ 16 H
+
< == > 8 I
3
-
+ 8 H
2
O

O
2
O
2
+ 4 Mn(OH)
2
+ 2 H
2
O < == > 4 Mn(OH)
3
2 Mn(OH)
3
+ 6 H
+
+ 6 I
-
< == > 2 Mn
2+
+ 2 I
3
-
+ 6 H
2
O

H
2
O
2
H
2
O
2
+ 3 I
-
+ 2H
+
< == > I
3
-
+ 2 H
2
O
TABLE 15-3 Iodometric titrations: Titrations of iodine
(actually I
3

) produced by the analyte {continued}

Species analyzed Reaction

O
3
O
3
+ 3 I
-
+ 2 H
+
< == > O
2
+ I
3
-
+ H
2
O

NO
2
-
2 HNO
2
+ 2 H
+
+ 3 I
-
< == > 2 NO + I
3
-
+ 2 H
2
O

S
2
O
8
2-
S
2
O
8
2-
+ 3 I
-
< == > 2 SO
4
2-
+ I
3
-


Cu
2+
2 Cu
2+
+ 5 I
-
< == > 2 CuI(s) + I
3
-


MnO
4
-
2 MnO
4
-
+ 16 H
+
+ 15 I
-
< == > 2 Mn
2+
+ 5 I
3
-
+ 8 H
2
O

MnO
2
MnO
2
(s) + 4 H
+
+ 3 I
-
< == > Mn
2+
+ I
3
-
+ 2 H
2
O