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CHAPTER 6
OXIDATION/REDUCTION TITRATION

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An oxidation/reduction reaction: electrons are

transferred from one reactant to another

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Oxidant: Ce4+
reductant: Fe2+

Ce4+/Ce3+ and Fe3+/Fe2+: conjugated

oxidation reduction pair

Overall Reaction

Half-Reaction

The number of equivalence (z):

MnO4-: z=5 (number of accepted electron
Fe2+: z=2 (number of donated electron)

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STANDARD ELECTRODE POTENTIAL

What is standard
electrode?
- 25oC, 1 atm
- Solution: Ion
activity is 1.00 Standard
- Air: pressure is 1 hydrogen
atm electrode,
SHE

Eo(H+/H2) = 0 (V)

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THẾ CỦA MỘT SỐ ĐIỆN CỰC SO SÁNH TẠI

250C – MÔI TRƯỜNG NƯỚC

ÑIEÄN CÖÏC THEÁ (VOLT)

CALOMEL / 0.1M KCl 0.3356

CALOMEL / 1.0M KCl 0.2830
CALOMEL / 3.5M KCl 0.2501
CALOMEL / BAÕO HOØA KCl 0.24453

Ag/AgCl / 0.1M KCl 0.288

Ag/AgCl / 1.0M KCl 0.22234

Ag/AgCl / BAÕO HOØA KCl 0.198

MEASURING STANDARD ELECTRODE POTENTIAL

Eo(Ag+/Ag) = 0.799
(V)

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MEASURING NON-STANDARD ELECTRODE

POTENTIAL

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Example:
Write out Nernst Equation in half-reactions:

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

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5.2. CLASSIFICATION IN REDOX TITRATION

Request of redox reaction:

- The reaction rate must be large
- Reaction have to occurred follow fixed ratio
- Reaction almost occurs completely
- Must be selected appropriately to determine the
equivalence point

a) Pemaganate method
Base on oxidation of MnO4- in acid environment

KMnO4. MnO4- + 8H+ + 5e = Mn2+ + 4H2O

b) Bichromate method
Base on oxidation of Cr2O72- in acid environment
Cr2O72- + 14H+ + 6e = 2Cr3+ + 7H2O

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c) Iodine method
- Eo(I2/I-)= 0.53 V
- indicator: starch
- Sodium thiosunfate (Na2S2O3)
I2 + 2e = 2I-
I2 + 2 S2O32- = 2I- + S4O62-

d) Other methods
Xeri method (Ce(SO4)2 oxidant), Bromate method,
vanadate method. …

5.3. DETERMINE EQUIVALENCE POINT-

INDICATOR
5.3.1. Self-indicator
Indicator is oxidant or reductant which its color
differ from conjugated species’s color.
Example: Titrating H2C2O4 with KMnO4
2MnO4- + 5C2O42- + 16H+ = 2Mn2+ + 10 CO2 +
8H2O
Purple Colorless
Indicator is KMnO4 because a drop excess
makes change color from colorless to light
purple

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5.3.2. Indicator is inserted from outside

Specific indicator
Special indicator can react selectively with oxidant or
reductant of conjugated redox pair and cause change
color.

Example: Starch (iod method); starch combines

with I2 to form a deep blue complex
I2 + 2 Na2S2O3 = 2NaI + Na2S4O6
At equivalence point: I2 react completely
with Na2S2O3 and solution is disappeared deep
blue color

Irreversible indicator
Color of Oxidant species differs from color of
reductant species and the changes is irreversible
• Example: methyl orange hay methyl red (red in
[oxidated]
acid medium) colorless compound.
KBrO3
3 Sb3+ + BrO3- + 6H+ = 3 Sb5+ + Br- + 3H2O
BrO3- +5Br- + 6H+ = 3Br2 + 3H2O
Redû Sb3+
Br2 oxidate methyl orange to form H+,
methyl
colorless compound. orange
Colorless

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Color changes for general redox indicators depend

only on the potential of the system

a color change appears when

Potential Range

E0In – 0,059/n < E0In < E0In + 0,059/n

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5.4 CONSTRUCTING REDOX TITRATION CURVES

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Titration of 50.00 mL of 0.0500 M Fe2+

with 0.1000 M Ce4+ in a medium that is
1.0 M in H2SO4 at all times.

Ce(SO4)2
z=1, Veq= 100,00 ml
V, C=
0.0500 M

V0, C0
Page 492-494 100 mL
FeSO4
0.100M

The solution contains no cerium species before we add

titrant. In any case, we don’t have enough information
to calculate an initial potential.

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This reaction is rapid and reversible so that the

system is at equilibrium at all times throughout
the titration. Consequently, the electrode
potentials for the two halfreactions are always
identical

Pre-equivalence point:

Equivalence point:

Post-equivalence point:
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Symmetric

Asymmetric

In general, redox
titration curves are
symmetric when the
analyte and titrant
react in a 1:1 molar
ratio

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REDOX TITRATION
• Pemaganate method:

E0= 1.51 V

MnO4- is the strong oxidant in acid medium

- Use for determining concentrations of reductants
- Don’t need to use indicators because KMnO4 is
an self –indicator.
- But: KMnO4 is not an primary standard(impure,
easy to react with other reductans)

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REDOX TITRATION
• Dichromate method:

Cr2O72- + 14H+ + 6e = 2Cr3+ + 7H2O E0= 1.33 V

- Cr2O72- is the strong oxidant in acid environment, but

weaker than MNO4- in acid medium.
- Use for determining concentrations of reductants
- K2Cr2O7 is a primary standard
- K2Cr2O7 can react in HCl
- Indicators: diphenylamin, diphenylbenzidin, natri
diphenylsunfonat.

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REDOX TITRATION

• Iodine method:
- Eo(I2/I-)= 0.53 V
- indicator: Starch is an specific indicator
- Sodium thiosunfate (Na2S2O3)
I2 + 2e = 2I-
I2 + 2 S2O32- = 2I- + S4O62-
- Iodine is a weak oxidizing agent used primarily
for the determination of strong reductants and
and oxidants
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SOME COMMON WAYS IN IODINE METHOD

• 1) Direct Titration

• I2 + 2e = 2I-
• I2 + 2 S2O32- = 2I- + S4O62-

Indicator is starch

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SOME COMMON WAYS IN IODINE METHOD

• 2) Substitude Titration and back Titration

a) Determine the concentration of reductants
Red1+ I2 (excess exactly)  ox1 + 2I-

I2 + 2 S2O32- = 2I- + S4O62-

b) Determine the concentration of oxidants

Ox1+ 2I- (excess exactly)  Red1 + I2

I2 + 2 S2O32- = 2I- + S4O62-

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HOME
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