AAST College of Pharmacy

First year - Second semester

Basic Analytical Techniques (PPS 116)

Reduction-Oxidation (Redox) Titrations

Prof. Tarek S. Belal

Pharmaceutical Analytical Chemistry Department

Faculty of Pharmacy – Alexandria University

 Reduction-Oxidation (Redox) Reactions
 These are reactions involving transfer of electrons from one species
to another.

 Oxidation
Loss of electrons by a species and increase in oxidation number.
Fe2+  e– + Fe3+ (Oxidation half-reaction)
Ferric Ferrous
(Iron II) (Iron III)

 Reduction
Gain of electrons by a species and decrease in oxidation number.
Ce4+ + e–  Ce3+ (Reduction half-reaction)
Ceric Cerous
(Cerium IV) (Cerium III)
 Oxidizing agent (oxidant)

It is an electron acceptor. The oxidizing agent takes electron(s) from

another substance, therefore it is itself reduced, e.g. Ce4+

 Reducing agent (reductant)

It is an electron donor. The reducing agent donates electron(s) to

another substance, therefore it is itself oxidized, e.g. Fe2+

Fe2+ + Ce4+  Fe3+ + Ce3+

 Electrons are neither created nor destroyed during a redox reaction,

they are transferred from the species being oxidized to that being
reduced.
 Cu + 2Ag+  Cu2+ + 2Ag
Copper wire is placed in a solution of silver nitrate (AgNO3). After some time,
silver metal deposits on the surface of the wire and the solution turns blue.
Copper metal is a reducing agent while silver ions are oxidizing agent.
 Oxidation Numbers
 Oxidation number (or oxidation state) of an atom in a substance is the actual
charge of the atom if it exists as a monoatomic ion, or a hypothetical charge
assigned to the atom in the substance.

Examples: Mg2+ = +2 C in CO32– = +4

 Because any compound is electrically neutral, the sum of charges on its atoms
must be zero. The sum of oxidation numbers (hypothetical charges) of the atoms
in a polyatomic ion equals the charge on the ion.

 Oxygen is −2 in most of its compounds except H2O2 (O = −1) and OF2 (O = +2)

 Hydrogen is +1 in most of its compounds except in compounds with metals

where the oxidation number of H = −1 (Hydride ion). Examples: NaH , CaH2

 Metals of group IA = +1 , and metals of group IIA = +2

 Example: calculate oxidation number of Cl in HClO4
+1 + Cl + (4 x −2) = 0 therefore Cl = +7

 Example: calculate oxidation number of Cr in Cr2O72–

2Cr + (7 x −2) = −2 therefore Cr = +6

 Calculate the oxidation number of nitrogen in each of the following

compounds:
NH3 N 2H 4 NH2OH
NaN3 N 2O NO
HNO2 NO2 HNO3
 Detection of the End Point in Redox
Titrations

 Indicators used are classified into:

1- Self-indicators

2- Specific indicators

3- General redox indicators

 Self-Indicators
 Some colored titrants serve as self-indicators. A useful
property of potassium permanganate (KMnO4) solution is
its intense purple color, which is sufficient to serve as an
indicator for most titrations.

 MnO4– + 8H+ + 5e–  Mn2+ + 4H2O

Purple colorless

 The end point is detected by first drop excess of MnO4–

which gives the solution a faint pink color.
 Specific Indicators

 Starch is the indicator of choice for redox titrations

involving iodine. Starch forms with I2 a reversible intense
blue complex.
 Chlorinated hydrocarbons (Chloroform CHCl3 and carbon
tetrachloride CCl4) are used as specific indicators in
titrations involving iodine. These are good solvents for I2.
Iodine dissolves in the chlorinated hydrocarbons giving
reddish-violet solutions.
 General (True) Redox Indicators
Indicator Oxidized Form Reduced Form

Ferroin Pale blue Red

Diphenylamine sulphonic acid Red violet Colorless

Diphenylamine Violet Colorless

Methylene blue Blue Colorless

These are highly colored dyes that are weak reducing or

oxidizing agents. They are oxidized or reduced at the end
point therefore they show the color change.
 Ferroin

 It is a complex of iron (II) with 1,10-phenanthroline

(orthophenanthroline).
 Three molecules of 1,10-phenanthroline combine with
one Fe2+. It is formulated as (phen)3Fe2+

N
2+
Fe
N

3
 The complexed iron in ferroin undergoes a reversible
redox reaction
(phen)3Fe3+ + e– ↔ (phen)3Fe2+
Pale blue Red
 It is useful for many titrations with cerium (IV).
 It is considered as an ideal redox indicator:
 It reacts rapidly and reversibly.
 Its color change is sharp.
 Its solutions are stable and easily prepared.
 Diphenylamine sulfonic acid

• The sodium salt of this indicator is used to prepare aqueous solution.

• Indicator reaction:

Colorless Violet
Reduced form Oxidized form

• Color change is sharp from colorless to violet.

• Used in titrations with standard K2Cr2O7 solution.
 OXIDATION REDUCTION TITRATIONS
It is a type of titration based on a redox reaction between the analyte
and the titrant.

1- Potassium permanganate (KMnO4)

Properties:
 A strong oxidant with an intense violet color.
 Secondary standard.
Standard solution and stability:
 Aqueous solutions of MnO4− are not entirely stable because MnO4−
ions tend to oxidize water:
4MnO4− + 2H2O  4MnO2 (s) + 3O2 (g) + 4OH−
 This decomposition reaction is catalyzed by light, heat and acids.
 Potassium permanganate should be stored in dark glass bottles and
kept away from high temperature.
Standardization:
 It is standardized against standard oxalic acid.

70⁰ C
2MnO4− + 5H2C2O4 + 6H+  2Mn2+ + 10CO2 + 8H2O
Purple colorless

End point detection:

Self indicator: The intense purple color of MnO4− serves as
indicator
Reduction half-reactions of permanganate in different media:
Strong acidic solutions (pH ≤ 1)
 MnO4− + 8H+ + 5e–  Mn2+ + 4H2O
Purple manganese (II)
(colorless)
 Change in oxidation state of Mn: +7 to +2
 EqW for redox reactions = MW / n
where n = number of electrons transferred per one mole of
substance.

Neutral, weak acid or weak alkaline solutions

 MnO4− + 2H2O + 3e–  MnO2 (s) + 4OH–
Manganese dioxide
(brown ppt)
 Change in oxidation state of Mn: +7 to +4

Strong alkaline solutions (1-2 M NaOH)

 MnO4− + e–  MnO42 −
manganate (green)
 Change in oxidation state of Mn: +7 to +6
 Applications in acidic solutions (0.1M to 1M H2SO4)
Direct Titrations
 HCl cannot be used. Why?
 The acid used for acidification is H2SO4 and not HCl because MnO4–
oxidizes Cl– in acid medium.
2MnO4− + 10Cl− + 16H+  2Mn2+ + 5Cl2 + 8H2O

[1] Determination of Fe2+ salts e.g. FeSO4

 MnO4− + 5Fe2+ + 8H+  Mn2+ + 5Fe3+ + 4H2O
 H2SO4 and H3PO4 are added in the titration flask.
 H3PO4 complexes Fe3+ to form Fe(HPO4)+ which is colorless, thus
prevents formation of yellow FeCl4– complex. This leads to sharp
end point color change.
H3PO4 + Fe3+  Fe (HPO4)+
colorless
[2] Determination of H2O2
Official assay method in USP 2015 and BP 2016.
H2O2 ↔ O2 (g) + 2H+ + 2e−
5H2O2 + 2MnO4− + 6H+  2Mn2+ + 5O2 + 8H2O

[3] Determination of oxalic acid H2C2O4

70⁰ C
2MnO4− + 5H2C2O4 + 6H+  2Mn2+ + 10CO2 + 8H2O

[4] Determination of nitrite salts (NaNO2)

2MnO4− + 5NO2− + 6H+  2Mn2+ + 5NO3− + 3H2O
 2- Cerium (IV) or ceric (Ce4+)
Properties
 Strong oxidizing agent.
 Salts: ceric ammonium nitrate, (NH4)2Ce(NO3)6 or ceric sulfate,
Ce(SO4)2
 Primary standard.
 Ceric solutions in sulfuric acid do not oxidize Cl− ions and can
be used to titrate samples in HCl solutions.
Reduction half-reaction
 Ce4+ + e−  Ce3+
 EqW = MW / 1
Standard solutions and stability
 Ceric salt is dissolved in sulfuric acid (at least 0.1 M) to
prevent precipitation of basic salts. Ceric solution
hydrolyzes to form ceric hydroxide if the solution is not
acidic.
 Solution in sulfuric acid is remarkably stable over
prolonged periods. They need not be protected from light
or heat.
End point detection
 Ferroin indicator: (red to blue).
 Solutions of Ce4+ are yellow-orange. They are not intense
enough to act as self-indicator.
 Applications
Direct Titrations
[1] Determination of Fe2+ salts (e.g. Ferrous fumarate , FeSO4)
Official assay method in USP 2015 and BP 2016.
Fe2+ + Ce4+  Fe3+ + Ce3+
[2] Determination of H2O2
2Ce4+ + H2O2  2Ce3+ + O2 (g) + 2H+
[3] Determination of H2C2O4
2Ce4+ + H2C2O4  2Ce3+ + 2CO2 + 2H+
[4] Determination of menadione (Vitamin K3)
Official assay method in USP 2015 and BP 2016.

EqW = MW / 2
 Back Titrations

Determination of Glycerol

 Excess standard Ce4+ is added and heated with glycerol sample.

C3H8O3 + 8Ce4+ + 3H2O  3HCOOH + 8Ce3+ + 8H+

3C = –2 3C = +2 x 3 = +6

 EqW of glycerol = MW / 8

 Excess unused Ce4+ is titrated against standard H2C2O4 or

standard iron (II) using ferroin indicator.

2Ce4+ + H2C2O4  2Ce3+ + 2CO2 + 2H+

 Color change: blue (oxidized) to red (reduced).
 3- Potassium dichromate (K2Cr2O7)

Properties
 Slightly weaker oxidizing agent than MnO4− and Ce4+
 Its reactions are slow with some reducing compounds.
 Primary standard.
 Potassium dichromate solutions are stable, can be boiled
without decomposition.
 It does not oxidize Cl− ions into Cl2
 Titrations are carried out in acidic solution that are about 1 M
in hydrochloric or sulfuric acid.
 In basic solution, Cr2O72− is converted to yellow chromate ion
(CrO42−) whose oxidizing power is nil.
Reduction half-reaction
Cr2O72− + 14H+ + 6e−  2Cr3+ + 7H2O
Orange Green
2Cr = +6 x 2 = +12 +3 x 2 = +6
For 1 mole of Cr2O72−, number of electrons gained = 6
EqW = MW / 6

End point detection

 Diphenylamine sulfonic acid
EP is marked by change in color from colorless to violet.

 Ferroin
EP is marked by change in color from red to pale blue.
 Applications
Direct Titrations

Determination of Fe2+ salts

6Fe2+ + Cr2O72− + 14H+  6Fe3+ + 2Cr3+ + 7H2O

 A mixture of sulfuric / phosphoric acid is added in this titration.

 H2SO4 For acidification

 H3PO4 It complexes Fe3+ to Fe(HPO4)+ , accordingly it

decolorizes its yellow color  sharp end point

 Indicator: diphenylamine sulfonic acid: color changes from

colorless to violet.
 Back Titrations

[1] Determination of Glycerol

 Add excess standard Cr2O72− (heat / conc sulfuric acid).

3C3H8O3 + 7Cr2O72− + 56H+  9CO2 + 14Cr3+ + 40H2O

9C = -2 x 3 = -6 9C = +4 x 9 = +36

-6 to +36 = loss of 42 e−

Number of electrons lost for 1 molecule of glycerol = 42/3 = 14 e−

 EqW of glycerol = MW / 14

 Back titration of un-reacted Cr2O72− by iodometric titration.

[2] Determination of Ethanol
 Add excess standard Cr2O72− (heat / 2M sulfuric acid).

3CH3CH2OH + 2Cr2O72− + 16H+  3CH3COOH + 4Cr3+ + 11H2O

Ethanol Acetic acid

6C = -4 x 3 = -12 6C = 0 x 3 = 0

-12 to 0 = loss of 12 e−

Number of electrons lost for 1 molecule of ethanol = 12/3 = 4 e−

 EqW of ethanol = MW / 4

 Back titration of un-reacted Cr2O72− by iodometric titration.

 4- Standard iodine solution (I2 or I3−)
Properties
 It is a weak oxidizing agent used for determination of
strong reductants.
 Iodine is slightly soluble in water.
 It is dissolved in aqueous KI solution giving the triiodide
ion:
I2 (s) + I− (aq)  I3− (aq)
Triiodide ion is very soluble in water, brown color.
Stability
 Iodine solutions lack stability (WHY?)
Volatility of iodine: loss of iodine from an open vessel occurs in
a relatively short time.
 Air oxidation of iodide ion  increases concentration of iodine
solution
4 I− + O2 (g) + 4H+  2 I2 + 2H2O
This reaction is promoted by acids, light and heat.
 Iodine slowly attacks most organic materials. Therefore, cork
or rubber stoppers are never used to close its containers.
 To keep stability of standard iodine solution:
It should be stored in closed dark glass stoppered bottles, kept
from elevated temp.
Standardization

 Using previously standardized sodium thiosulfate Na2S2O3

I2 + 2S2O32−  S4O62− + 2 I−

Tetrathionate

Reduction half-reaction

I2 + 2e−  2 I−

Change in oxidation state of iodine : 0 to -1 x 2

EqW = MW / 2
 Titrations involving iodine
 Iodimetry: Direct method. Used for analysis of reducing compounds.
 Iodometry: Indirect method. Used for analysis of oxidizing compounds.

Applications of Iodimetric Titrations

Direct Titrations
End point detection:
 Starch is used as indicator. It is added at the beginning of the titration.
The first drop excess of I2 at the equivalence point causes the solution
to turn blue.
 Aqueous starch suspension decomposes within few days because of
bacterial action. Decomposition products give irreversible reddish
color with I2 which masks the true end point.
 To avoid this drawback, starch solution should be freshly prepared.
[1] Determination of Na2S2O3
Official assay method in USP 2015 and BP 2016.
2S2O32− + I2  S4O62− + 2 I− (EqW of S2O32− = MW / 1)

[2] Determination of Ascorbic acid (Vitamin C)

Official assay method in USP 2015 and BP 2016.

I2

Ascorbic acid Dehydroascorbic acid

EqW = MW / 2
 Back Titrations
[1] Determination of aldehydes and aldoses
 Formaldehyde HCHO
 Glucose (aldehydic reducing sugar)
 Sucrose (non reducing sugar which gives equivalent amount of
glucose after acid hydrolysis)
I2 + 2OH−  IO− + I− + H2O
Hypoiodite
(stronger oxidizing agent)

RCHO + IO− + OH−  RCOO− + I− + H2O

IO− + I− + 2H+  I2 + H 2O
Excess Acidification
unreacted

I2 + 2S2O32−  2 I− + S4O62−

 Starch is used as indicator

[2] Determination of compounds containing thiol (–SH) group
Official assay methods for several compounds in USP 2015 and BP
2016.
- Cysteine
- Acetylcysteine EqW = MW / 1
- Captopril
- Dimercaprol
These compounds can be titrated using back iodimetry. Starch
is used as indicator in most of these methods.
2R-SH + I2  R-S-S-R + 2 I− + 2H+

I2 + 2S2O32−  2 I− + S4O62−
Excess
unreacted
 Iodometric Titrations
 Used for analyzing oxidizing species

 General procedure: Add excess I− (KI) to a solution of analyte. I2 is

produced in an amount equivalent to the analyte. Liberated I2 is
titrated against standard Na2S2O3

 Na2S2O3 is a universal titrant for I2 in neutral or acidic solutions.

S4O62 + 2e−  2S2O32−

Example: Determination of K2Cr2O7

Cr2O72− + 6 I− (excess) + 14H+  2Cr3+ + 3 I2 + 7H2O

I2 + 2S2O32−  2 I− + S4O62−
Iodometric titrations are usually done in acidic medium (Why?)
 Acidity is important for some oxidizing agents because H+ ions
are involved in their half reactions.

Examples

Cr2O72− + 14H+ + 6e−  2Cr3+ + 7H2O

MnO4− + 8H+ + 5e−  Mn2+ + 4H2O

 Acidity promotes the reaction between the oxidizing analyte and

iodide → equilibrium is shifted to right (ensure complete reaction).
 End point detection
 Starch can be used as indicator. Starch should not be added at the
beginning of titration. Instead it is added just before the end point (I2 color
fades during titration till it becomes straw yellow). The end point is indicated
by the disappearance of blue starch-iodine color.
 WHY starch is added just before the end point?
Iodine-starch complex is ONLY slowly dissociated, and a false positive EP
would result if a large amount of iodine is adsorbed on starch (some of the
iodine remains bound to starch, even after the EP is reached, thus
introducing an error).
 Most iodometric titrations are performed in strong acidic solutions and starch
hydrolyzes in strong acid solution. So, starch cannot be used.
 CHCl3 or CCl4 are used as indicators and they are suitable for strong acidic
solutions. Iodine dissolves in these solvents giving reddish-violet color. EP is
marked by the disappearance of violet color in the organic solvent layer
(vigorous shaking during titration is required).
 Stability of Na2S2O3 standard solution

 Acidity: Sodium thiosulfate solutions tend to decompose in acidic

solutions to give sulfur and hydrogen sulfite ion:
S2O32− + H+  HSO3− + S (s)
To prevent this reaction, standard solution is prepared in freshly
boiled water to get rid of dissolved CO2 which makes the solution
acidic. Also pH is adjusted at 9-10 for optimum stability by adding
NaHCO3 or borax.

 Bacterial growth: Some bacteria metabolize S2O32− into SO32−,

SO42−, and S. To prevent this, boiling water is used as a solvent,
preservatives (e.g. sodium benzoate or CHCl3) may be added, and
the pH is adjusted by adding borax or NaHCO3 to about pH 9 which
inhibits bacterial action.
 Applications
[1] Determination of Cu2+ salts (e.g. CuSO4)
Official assay method in USP 2015 and BP 2016.
Cu2+ + e−  Cu+
 KI has 2 functions in determination of Cu2+ samples
1- To reduce Cu2+ to Cu+ 2- To precipitate Cu+ ion
2Cu2+ + 4 I-  Cu2I2 ↓ + I2
white ppt
cuprous iodide
 But the precipitated Cu2I2 adsorbs I2 on its surface, so we add NH4SCN
to precipitate the more insoluble Cu2(SCN)2 and liberate the adsorbed I2.
Cu2I2 + 2SCN–  Cu2(SCN)2 + 2 I–
white ppt
cuprous thiothyanate
 Titrate the liberated I2 against standard Na2S2O3 using starch indicator.
[2] Determination of other oxidizing samples
 Determination of Fe3+ salts (e.g. FeCl3)
2Fe3+ + 2 I−  2Fe2+ + I2
(Official assay method for FeCl3 in USP 2015 and BP 2016)

 2MnO4− + 10 I− + 16H+  2Mn2+ + 5 I2 + 8H2O

 Cr2O72− + 6 I− + 14H+  2Cr3+ + 3 I2 + 7H2O
 Cl2 + 2 I−  I2 + 2Cl−
 Br2 + 2 I−  I2 + 2Br−

 Titrate the liberated I2 against standard Na2S2O3 using starch

or CCl4 indicator.
 Karl Fischer Titration
 Reagent
Iodine (I2) and sulfur dioxide (SO2) dissolved in pyridine (C5H5N) and excess
methanol (CH3OH).
 Application
Determination of water content in different samples (salts, acids, alcohols, esters,
ethers, anhydrides…).
 Reaction
Redox reaction of I2 and SO2 in presence of water.
I2 + SO2 + (H2O)  2HI + SO3
 Role of Methanol
SO3 is capable of consuming water:
SO3 + H2O  H2SO4
This reaction is undesirable and can be prevented by excess methanol (more
reactive than water).
SO3 + CH3OH  CH3SO4H
 Method
Direct titration. Back titration is also
applicable.
 End point detection
Color change from yellow (reaction
products) to the brown color of excess
reagent (pyridine-iodine complex).
Automated measurement is also
applied.
 Stoichiometry
1 mole of I2 and 1 mole of SO2 for each
mole of H2O.
I2 ≡ H2O
 5- Potassium iodate (KIO3)
Properties
 It is a primary standard strong oxidizing agent.
IO3− + 2Cl− + 6H+ + 4e−  ICl2− + 3H2O
 Its aqueous solutions are stable indefinitely.

Applications
Andrews method
 Used for determination of I− samples (e.g. KI).
 Carried out in strong acidic solutions > 3M HCl
(for stabilization of I+ as ICl or ICl2−)
I+ = iodinium ion ICl = iodine monochloride
 Indicators used are CCl4 or CHCl3. Vigorous shaking is required
especially near the EP.
Determination of I− salts (e.g. KI)
(Official assay method in USP 2015 and BP 2016)
 Two steps reaction:
Step 1: IO3− + 5 I− + 6H+  3 I2 + 3H2O
Colorless Brown
Step 2: IO3− + 2 I2 + 10Cl− + 6H+  5 ICl2− + 3H2O
Brown Yellow
 Overall reaction: IO3– + 2 I– + 6Cl– + 6H+  3 ICl2– + 3H2O
 Color change during titration:
Colorless (IO3− + I− ) to yellowish brown (I2 ) to dark brown (↑ I2) to
pale brown (↓ I2 , ↑ ICl2−) this is accompanied by fading of pink color
of CHCl3 layer. EP is detected by disappearance of last traces of I2
(CHCl3 layer is colorless).
 6- Potassium bromate (KBrO3)
Properties
 It is a primary standard strong oxidizing agent.
 Its aqueous solutions are stable indefinitely.
Applications
 Potassium bromate solution is used as a source of bromine (Br2). It is
used for determination of organic compounds that react with Br2.
Standard Br2 solutions cannot be used as such due to volatility and
toxicity of Br2
 A measured excess of standard bromate is added to the solution that
contains the sample plus an excess of KBr. On acidification, BrO3–/ Br–
mixture is quantitatively converted to Br2
BrO3− + 5Br− + 6H+  3Br2 + 3H2O
Measured
excess
 Reduction half reaction of Br2
Br2 + 2e−  2Br−
BrO3− ≡ 3Br2 ≡ 6e−
 Determination of phenol (back titration)
 Official assay method in USP 2015 and BP 2016.
 It is a redox substitution reaction (bromination of phenol).
 Sequence of reactions:
1- BrO3− + 5Br− + 6H+  3Br2 + 3H2O
OH OH
Br Br
2-
+ 3 Br2 + 3HBr

Br
3- Excess unreacted Br2 is titrated iodometrically.
Br2 + 2I–  I2 + 2Br–
I2 + 2S2O32–  S4O62– + 2I–
 Chloroform is used to dissolve product of the reaction
(tribromophenol) and it acts as indicator.

 C6H6O + 3Br2  C6H3OBr3 + 3HBr

6C+6–2 = 0 6C+3–2–3 = 0
6C = – 4 6C = + 2
 Phenol: loss of 6e−
 3Br2  6Br− : gain of 6e−
 C6H6O ≡ 3Br2 ≡ BrO3− ≡ 6e−
 EqW of phenol = MW / 6