Unit 7.

Oxidation-reduction titration
1. Introduction.
2. Titration curves.
3. Redox indicators.
4. Pre-adjustment of analyte oxidative state.
5. Practical aspects and applications.
1. Introduction

Oxidation-reduction process (Redox). Reaction involves transfer of electrons from

one species to another.
Oxidation: Loss of electrons Reducing agent: gives electrons
Reduction: Electron gain Oxidizing agent: takes electrons

Oxidized form + n e- ↔ reduced form Fe+3 + e- ↔ Fe+2 E0 Fe+2 / Fe+3 = 0.771 V

0.059 𝑅𝑅𝑅𝑅𝑅𝑅
Nernst equation (25ºC): 𝐸𝐸 = 𝐸𝐸 0 − log
𝑛𝑛 𝑂𝑂𝑂𝑂𝑂𝑂𝑂𝑂

Ways to carry out redox reactions:

• Reagents in direct contact, e.g. redox titration.
• Reagents separated physically, e.g. electrochemical cell.
 1. Introduction

The potential (E) associated with a redox reaction, also called cell potential, is the
sum of the potentials of each of the semi-reactions that intervene in it.
For a redox reaction to be spontaneous (ΔG <0), the overall potential must be
positive.
potential for reduction of potential for reduction of
the species that is reduced the species that oxidizes

E = Esp.red.- Esp.oxid >0

Aox + nAe- Ared EA EA > EB
Bred Box + nBe- EB the species Aox oxidizes the Bred species

nB Aox + nA Bred nB Ared + nABox. REDOX REACTION

𝑛𝑛𝐴𝐴 𝑛𝑛𝐵𝐵 𝐸𝐸𝐴𝐴0 − 𝐸𝐸𝐵𝐵0
log 𝐾𝐾𝑒𝑒𝑒𝑒 =
0.059
A redox reaction will be more favorable when:
• Greater difference between the electrode E0 of each half-reaction.
• The greater the n exchanged in each half-reaction.
1. Introduction

Redox titrations: Quantitative analysis methods (volumetric) based on the use of

redox reactions that have the following characteristics:
• Fast kinetics
• Quantitative (high Keq, that is, an appreciable difference between the
standard / normal potentials of the redox pairs involved in it)
• Defined stoichiometry.
• Method for the detection of the equivalence point (main difficulty, few
indicators, potentiometric systems)
• Preparation and use of standard solutions of oxidizing substances does not
present major problems.
• Preparation and use of reducing standard solutions, more difficult, less stable,
are oxidized by air, their concentration decreases over time, ...
 2. Titration curves

Graphical representation of the variation of the potential of the solution, which

contains the species to be titrated, and the volume of added titrant or the
titration %.
After the equivalence point:
the potential is given by the
redox pair of the titrant.
Ecell (Vol)
Before the
equivalence point: At the equivalence point:
the potential is The potential is determined by
controlled by the the stoichiometry of the reaction
redox pair of the and the normal potentials of each
analyte. half-reaction.
Titrant volumen (mL )
or % titration
n1E10 + n2 E20
E=
n1 + n2
Beware for the reactions involving H+ and
OH- , these appear in the above equation.
2. Titration curves

E.g. Fe+2 0.1 M (in 50 mL sulfuric acid) with a Ce+4 0.100 M as oxidant
Ce+4 + 1 e- Ce+3 E0Ce+4/Ce+3 = 1.44 v
Titrant solution
Fe+3 + 1 e- Fe+2 E0Fe+3/Fe+2 = 0.68 v Ce4+ 0.1000 M

1.6
Ferrous solution 0.1 M
1.4
in 50 mL H2SO4
E (volts)

1.2

1 Equivalent point

0.8

0.6
0 20 40 60 80 90 100
mL Ce4+ added
2. Titration curves

E.g. 50.0 mL of 0.125 M solution of Fe+2 ion are titrated with 0.0625 M solution of KMnO4,
the H3O+ ion concentration is 1.0 M during the entire titration

E0 Fe+3/Fe+2 = 0.771 V ; E0 MnO4- / Mn2+ = 1.51 V.

Ve.p. = 20 mL
5 Fe2+ + MnO4- + 8 H+ ↔ 5 Fe3+ + Mn2+ + 4H2O

1,4

1,3

1,2

1,1
Equivalent point
Punto equivalencia
E (volts)

0,9

0,8

0,7

0,6
0 10 15 25 35 45 55
mL permanganate added
2. Titration curves

Considerations:
• Titration curve is symmetric near the equivalent point if the same number of
electrons are exchanged in both half-reactions. When the number of electrons
exchanged is not the same, the equivalence point is shifted to the area where
there is an excess of the redox pair that exchanges a greater number of
electrons.

• Constant of the reaction: The voltage change in the vicinity of the equivalence
point increases as the difference between the potentials of the two couples in
the titration increases.
• The shape of the curve for a given system does not depend on the
concentration. Depends on the ratio of reactants.
3. Redox indicators.

Finding the end point:

 Indicators
 Electrodes

• Autoindicators: The titrant is colored and acts as an indicator. When adding an

excess of titrant, it gives the solution appreciable color.
Potassium permanganate: KMnO4 (intense pink) → Mn+2 (colorless)
3. Redox indicators.

• Redox indicators: is a compound that changes color when it goes from its
oxidized to its reduced state. The potential they undergo in the redox process
must match the potential at the equivalence point.
Redox indicator Reduced form Oxidized form E0 (V) n
Difenylamine Colorless Violet 0.76 2
Ferroin Red Blue 1.06 1
Methylene blue Colorless Blue 0.36 2
Diphenylamino Colorless Violet 0.84 2
sulfonic acid

Ind (oxidized) + n e- ↔ Ind (reduced) 0

0.059 𝐼𝐼𝐼𝐼 Re 𝑑𝑑
𝐸𝐸𝐼𝐼𝐼𝐼 = 𝐸𝐸𝐼𝐼𝐼𝐼 − 𝑙𝑙𝑜𝑜𝑜𝑜
𝑛𝑛 𝐼𝐼𝐼𝐼 𝑂𝑂𝑂𝑂𝑂𝑂

𝐼𝐼𝐼𝐼 Re 𝑑𝑑 0.059
0.1 ≥ ≥ 10 º
𝐼𝐼𝐼𝐼 𝑂𝑂𝑂𝑂𝑂𝑂 𝐸𝐸𝐼𝐼𝐼𝐼 = 𝐸𝐸𝐼𝐼𝐼𝐼 ±
𝑛𝑛
3. Redox indicators.

• Specific indicators: react with one of the chemical forms (oxidized or reduced)
of one of the species involved in the reaction.
Starch, forms a dark blue complex with iodine (I2). Useful to detect the final point
of the reactions in which iodine is generated or consumed. It is not a redox
indicator does not respond to a change in redox potential.
4. Pre-adjustment of analyte oxidative state.
The analyte in a redox titration must be in a single oxidation state. So, sometimes
the oxidation state of analyte must be adjusted before it can be titrated.
Requirements:
• Quantitative reaction
• Excess reagent easily eliminated

 Oxidizing Reagents
• Sodium bismuthate (NaBiO3); Used for: Mn2+ to Mn7+, Cr3+ to Cr6+, Ce3+ to Ce6+
Elimination: by filtration (solid)
𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑂𝑂3 𝑠𝑠 + 6𝐻𝐻+ + 2𝑒𝑒 − ↔ 𝐵𝐵𝑖𝑖 3+ + 3𝐻𝐻2 𝑂𝑂 + 𝑁𝑁𝑎𝑎 +

• Potassium or ammonium persulfate ((NH4)2S2O8); Used for: Mn2+ to Mn7+, Cr3+

to Cr6+, Ce3+ to Ce6+ , Slow reaction (Ag+ catalyst) Elimination: by boiling
𝐴𝐴𝑔𝑔+
𝑆𝑆2 𝑂𝑂82− + 2𝑒𝑒 − 2𝑆𝑆𝑂𝑂42−
• Hydrogen peroxide (H2O2); Used for: Mn2+ to Mn4+, Cr3+ to CrO42- in alkaline
medium and Fe2+ to Fe3+, Sn2+ a Sn4+ in acid medium, Elimination: by boiling
𝐻𝐻2 𝑂𝑂2 + 2𝐻𝐻 + + 2𝑒𝑒 − ↔ 2𝐻𝐻2 𝑂𝑂
4. Pre-adjustment of analyte oxidative state.

 Reducing Reagents
• Walden Reducer; Ag in HCl
medium
Ag(s) + Cl- ↔ AgCl(s) + e-
• Jones Reducer; Zncoated with
Zn amalgam
2 Zn(s) + Hg2+ ↔ Zn2+ + Zn(Hg)
• Tin Chloride (SnCl2)
Sn4++ 2e-↔ Sn2+
Eliminated by adding HgCl2
These reducing agents are packaged in a
column through which the sample is passed
5. Practical aspects and applications.
a) Titrations with permanganate (KMnO4)
1. The oxidation half-reaction is conditioned by the pH
It is a strong oxidant in strong acid medium (the most used reaction)
MnO4 - + 8 H+ + 5e-  Mn+2 + 4 H2O Eo = 1.51 V
In weakly acidic, neutral or slightly alkaline medium, it is reduced to Mn (IV)
MnO4 - + 4H+ + 3e-  MnO2 + 2 H2O Eo = 1.68 V
In strong alkaline medium, it is reduced to manganate
MnO4 - + e-  MnO4 –2 Eo = 0.67 V
2. The permanganate serve as its own indicator.
3. KMnO4 is not a primary standard, it can be standardized against:
Sodium oxalate (Na2C2O4), Oxalic acid (H2C2O4.2H2O).
4. The reactions of KMnO4 are slow. Titrations are performed with warm solutions
and are catalyzed by Mn2+
Applications: Determination of Fe +2, H2O2, NO2-, HSO3- and H3AsO3
Fe +2 → Fe 3+ + 1e - // H2O2 → O2 + 2H+ +2e- // NO2- + H2O → NO3- + 2H+ + 2e-
5. Practical aspects and applications.

b) Titrations with potassium dichromate

1. It is a strong oxidant in acidic medium:
Cr2O7-2 + 14H+ + 6e-  2 Cr(III) + 7 H2O Eo =1.33 V
2. It is a primary standard
Limitations:
• Less powerful oxidizing agent than permanganate
• Its reactions are slow
• It does not act as an autoindicator. Diphenylamine sulphonic acid or
diphenylbenzidine sulfonic acid are used as indicators
Applications: determinations of organic compounds. E.g .ethanol present in
alcoholic beverages. Determination of the "Chemical Oxygen Demand“
5. Practical aspects and applications.

c) Titrations with Ce+4

Its solutions are stable indefinitely. It is an oxidant in acid medium, whose redox
potential depends on the concentration and type of acid:
Ce+4 + e -  Ce+3 In HCl: 1.28 V
Ammonium hexanitratocerate (IV), (NH4)2Ce(NO3)6,is the primary standard
Applications:
• It can be used in place of KMnO4.
• It is not an autoindicator. Ferroin can be used as indicator.
• Analysis of organic compounds: Malonic acid, Alcohols, Aldehydes, Ketones,
carboxylic acids.
5. Practical aspects and applications.

d) Titrations with Iodine

1. The I2 / I- pair can act as a reducing or as an oxidizing agent, indistinctly

I2 + Red ↔ 2 I- + Oxd. I 2 + 2 e - ↔ 2 I- Eº = 0.54 V
2. I2 is only slightly soluble in water but its solubility is enhanced by complexation
with iodide, forming the triiodide complex (I3-)
I 2 + I- ↔ I 3 - I3- + 2e- ↔ 3I- (for convenience, it is written I2)
3. An exccellent way to prepare standard I3- is to add a known quantity of the
primary standard potassium iodate (KIO3) to a small excess of KI in a strong acid
solution (pH≈1)
5. Practical aspects and applications.

d) Titrations with Iodine

5. Titrations that use iodine are classified in :
• Direct methods (Iodimetry). I2 + 2 e- ↔ 2I-
When a reducing analyte is titrated with iodine. The final point is observed by the
appearance of the first excess of I2.

Determination of Arsenic (As) H3AsO3 + H2O ↔ H3AsO4 + 2H+ + 2 e-

Antimony Determination (Sb) H3SbO3 + H2O ↔ H3SbO4 + 2H+ + 2 e-

Determination of ascorbic acid (Vitamin C) C6H8O6 ↔ C6H6O6 + 2H+ +2e-

Determination in organic compounds with sulfhydryl groups 2(R-SH), H2S ↔ RSSR,

S + 2H++2e-
5. Practical aspects and applications.

d) Titrations with Iodine

• Indirect methods (Iodometry). 2I- ↔ I2 + 2 e-
When an oxidizing analyte is added to excess I- to produce iodine, which is then
titrated with standardized thiosulfate solution. The final point is the disappearance
of the I2 that is titrated.
Determination of the content of hypochlorite in a bleach: ClO- + 2H+ +2e- ↔ Cl-+
H2O
Main reaction: ClO- + I- excess ↔ I2 + Cl-
Titration reaction: I2 generated + S2O32- ↔ I- + S4O62-

Thiosulfate is not a primary standard. It is usually standardized against I2 formed

with:
• K2Cr2O7 + KI
• KIO3 + KI
• KBrO3 + KI
 5. Practical aspects and applications.

Titrations with Permanganate (KMnO4)

25 mL of a hydrogen peroxide solution were taken and diluted with distilled water
to 250 mL, using a volumetric flask. 25 mL of this latter solution is taken, acidified
with H2SO4 and titrated with 0.02500 M KMnO4 solution. Knowing that 40.32 mL of
the permanganate solution are necessary to oxidize all the H2O2, calculate the
concentration of hydrogen peroxide in the initial solution, expressing the result in
g/L.

40.32 mL
25 mL 0.02500 M de KMnO4

25 mL
+
¿¿ H2O2 ?? H2SO4

2 (MnO4 - + 8 H+ + 5e- → Mn+2 + 4 H2O)

5 ( H2O2 → O2 + 2H+ +2e- )
2MnO4 - + 6 H+ + 5H2O2 → 2Mn+2 + 8H2O + 5O2
5. Practical aspects and applications.

Titrations with Cerio

25.00 mL of a glycerin solution, C3H5(OH)3, is treated with 20 mL of 0.230 M solution of Ce
(IV) in 4 M HClO4. The reaction that takes place is as follows:
HOCH2-CHOH-CH2OH + 8Ce4+ + 3H2O → 3HCOOH + 8H+ + 8Ce3+
Once the reaction has ended, the excess Ce (IV) is titrated with 0.100 M Fe2+ solution.
Knowing that 8.70 mL of this solution are required to reach the turn of the indicator,
calculate:
a.- The Molarity of glycerin in the sample
b.- The grams of glycerin present in the 25 mL of the initial solution.

25 mL 8,70 mL HOCH2-CHOH-CH2OH + 3H2O → 3HCOOH + 8H+ + 8 e-

+ 0.1 M Fe+2 8 (Ce4+ + 1e- → Ce3+ )
HClO4
+ Ce4+ + 1e- → Ce3+ HOCH2-CHOH-CH2OH + 8Ce4+ + 3H2O → 3HCOOH + 8H+ + 8Ce3+
20 mL 0.230 M Ce(IV) Fe2+ → Fe3+ + 1e-

Ce4+ + Fe2+ → Ce3+ + Fe3+

5. Practical aspects and applications.

Titration with dicromate (K2Cr2O7)

A 5.00 mL portion of a wine was diluted to 100 mL in a volumetric flask. The ethanol was
distilled from a 20 mL aliquot and collected in 100 mL of 0.05151 M K2Cr2O7. Heating the
reaction of oxidation of ethanol to acetic acid by reaction with potassium dichromate was
completed.
C2H5OH + Cr2O72- + H+ → Cr3+ CH3-COOH + H2O
The excess of potassium dichromate was then titrated with 14.42 mL of a standard solution of
Fe (II) 0.02497 M. Calculate the %w/v ethanol in the wine.

14,42 mL 3 (C2H5OH + H2O → CH3-COOH + 4H+ + 4e- )

5 mL 20 mL 0.02497 M Fe+2
2(Cr2O72- + 14 H+ + 6e-→ 2Cr3+ + 7H2O )
100 mL 3C2H5OH + 2Cr2O72- + 16H+ → 4Cr3+ + 3CH3-COOH + 11H2O
100 mL K2Cr2O7 0.05151 M
Cr2O72- + 14 H+ + 6e-→ 2Cr3+ + 7H2O
6(Fe2+ → Fe3+ + 1e- )

Cr2O72- + 14 H+ + 6Fe2+ → 2Cr3+ + 6Fe3+ 7H2O