REDUCTION-OXIDATION
TITRATIONS
Review on Redox Reactions
Oxidation, reduction, oxidizing and
reducing agents
Ce4+ + Fe2+ → Ce3+ + Fe3+
The vertical axis in oxidation/reduction titration
curves is generally an electrode potential instead
of logarithmic functions.
Equivalence Point Potentials
At the equivalence point, the conc.
cannot be obtained from the
stoichiometric reaction. Fortunately,
equivalence-point potentials are
readily obtained by taking advantage
of the fact that the two reactant
species have known concentration
ratios at chemical equivalence.
Derivation of Redox Titration Curves
a) initial potential
b) potential after initial addition
c) Equivalence-point potential
d) Potential after the excess addition
Oxidation-Reduction Indicators
Two types of indicators:
1. general redox indicators
2. specific indicators
1. General Redox Indicator
- substances that change color
upon being oxidized or reduced. The
color change is independent of the
chemical nature of the analyte and
titrant and depend instead upon the
changes in the electrode potential of
the system that occur as the titration
progresses.
a. Iron(II) complexes of ortho-phenanthrolines
- a class of organic compounds known as
phenanthroline that form stable complexes with
iron(II) and certain other ions.
- color change is from pale blue to red
b. Diphenylamine and its derivatives
c. Iodine solutions
- widely used in oxidation/reduction reactions
involving iodine as an oxidant or iodide ion as
the reductant.
2. Specific Indicator
a. Starch indicator
- the best known specific indicator which forms a
dark blue complex with triiodide ion, I3-.
- color change is from colorless to dark blue
b. KSCN
- disappearance of red color with Fe3+ solutions
with titanium sulfate
- the analyte in an oxidation/reduction
titration must be in a single oxidation state
at the outset, however, steps that precede
the titration frequently convert the analyte
to a mixture of oxidation state.
- Ex. When Fe is dissolved, two forms of Fe
are produced
a. Auxiliary Reducing Reagents
- a number of metals are good reducing agents
and have been used for prereduction of analytes
included among these are Zn, Al, Cd, Pb, Ni, Cu,
and Ag (in the presence of chloride ion).
- sticks or coils of the metals can be immersed
directly in the analyte solution. After reduction is
judged complete, the solid is removed manually and
rinsed with water. It is necessary to filter the
solution to remove granular or powdered forms of
the metal. An alternative to filtration is the use of
reductor.
Two types of reductor can be employed:
1. Jones reductor – has a diameter of about 20
cm and holds a 40-50 cm column of
amalgamated zinc.
2. Walden reductor – granular metallic silver held
in a narrow glass column is the reductant.
Walden reductor is more selective than Jones
reductor.
b. Auxiliary Oxidizing Reagents
i. Sodium bismuthate (NaBiO3)
- powerful oxidizing agent capable of converting
manganese(II) quantitatively to permanganate
ion
- a sparingly soluble salt but its exact composition
is uncertain
- oxidations are performed by suspending the
bismuthate in the analyte solution and boiling
for a brief period
- the half-reaction for the reduction of sodium
bismuthate can be written as;
NaBiO3(s) + 4H+ + 2e- BiO+ + Na+ + 2 H2O
ii. Ammonium peroxydisulfate (NH4)2S2O8
- powerful oxidizing agent that converts Cr(III) to
dichromate, Ce(III) to Ce(IV), and Mn(II) to
permanganate in acidic solutions.
- the half-reaction is
S2O82- + 2e- 2SO42- E°=2.01 V
- the oxidations are catalyzed by traces of silver
ion
- the excess reagent is readily decomposed by a
brief period of boiling:
2S2O8 2- + 2H2O 4SO42- + O2(g) + 4 H+
iii. Sodium peroxide and hydrogen peroxide
- a convenient oxidizing agent either as a
solid sodium salt or as a dilute solution of
the acid
- the half-reaction for hydrogen peroxide in
acidic solution
H2O2 + 2H+ + 2e- 2H2O
after oxidation is complete, the solution is
freed of excess reagent by boiling:
2H2O2 2H2O + O2(g)
Application of Standard Reductants
Standard solutions of most reducing agents
tend to react with atmospheric oxygen. For this
reason, reductants are seldom used for the
direct titrations of oxidizing analytes; indirect
methods are used.
The two most common indirect methods
are based upon:
a. Iron(II) solutions
- readily prepared from iron(II) ammonium
sulfate Mohr’s salt) or from closely related
iron(II) ethylenediamine sulfate (Oesper’s salt)
- air oxidation of iron(II) takes place rapidly in
neutral solutions but is inhibited in the
presence of acid with the most stable
preparations being 0.5 M in H2SO4.
b. Sodium thiosulfate
- moderately strong reducing agent that has
been widely used to determine oxidizing
agents by indirect procedure that involves
iodine as an intermediate
- with iodine, thiosulfate ion is oxidize
quantitatively to tetrathionate ion, the half-
reaction being
2S2O32- S4O62- + 2e-
- the end point is the disappearance of the
iodine color (for colorless analyte)
Stability of sodium thiosulfate solutions
Thiosulfate ions tend to decompose to give
sulfur and hydrogen sulfite ion but are
resistant to air oxidation:
S2O32- + H+ HSO3- + S(s)
Variables that influence the rate of
reaction include:
a) pH
b) presence of microorganisms
c) concentration of the solution
d) presence of copper(II)
e) exposure to sunlight
Standardization of Thiosulfate solutions
Potassium iodate is an excellent primary
standard for thiosulfate solutions. The
reaction for the standard mixture in a strong
acid is
IO3- + 5I- + 6H+ 3I2 + 2H2O
The liberated iodine is then titrated with
the thiosulfate solution. The stoichiometry of
the reaction is;
1 mol IO3- = 3 mol I2 = 6 mol S2O32-
Application of Standard Oxidants
a. The strong oxidants – potassium
permanganate and cerium(IV)
MnO4- + 8H+ + 5e- Mn 2+ + 4H2O
Ce4+ + e- Ce3+
The choice among the two depends upon:
1. the strength of the analyte as a reducing agent,
2. the rate of reaction between oxidant and
analyte,
3. the stability of the standard oxidant solutions,
4. the availability of indicator
End points
The intense purple color of potassium
permanganate solution is sufficient to serve as
an indicator for most titrations. The
permanganate ions react slowly with the large
conc. of manganese(II) ions present at the
end point.
2MnO4- + 3 Mn2+ + 2H2O 5MnO2(s) + 4H+
Solutions of cerium(IV) are yellow-orange
but the color is not intense enough to act as
an indicator in titrations. The most widely used
indicator is the iron(II) complex of 1,10-
phenanthroline or one of its derivatives.
Preparation and Stability of Standard Solution
Permanganate solutions when prepared properly,
are stable because decomposition reaction is slow.
It is catalyzed by light, heat, acids, bases,
manganese(II) and manganese dioxide.
Standardized permanganate solutions should be
stored in the dark but still reacts according to the
equation;
4 MnO4- + 2 H2O → 4 MnO2(s) + 3O2 (g) + 4OH-
a. Sodium Oxalate
- used to standardize permanganate and
cerium(IV) solutions. In acidic solution, the
oxalate is converted to the undissociated acid.
2MnO4- + 5H2C2O4 + 6H+ → 2Mn2+ + 10CO2(g) +
8H2O
Autocatalysis – when the product of a reaction
catalyzes the reaction
The same oxidation products are formed with
cerium(IV).
b. Potassium Dichromate
- dichromate ion is reduced to green chromium(III)
ion.
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O
- carried out in solutions that are 1 M in HCl or
H2SO4
- indefinitely stable , can be boiled without
decomposition and do not react with HCl.
- available commercially and at modest cost
The Preparation, Properties and Uses of
Dichromate Solutions
- reagent of potassium dichromate is pure
- it has an orange color and not intense for use
as an end point detection
- diphenylamine sulfonic is an excellent
indicator for this titration.
The oxidized form of the indicator is violet,
and the reduced form is essentially colorless;
thus the color change observed at the end
point in a direct titration is from green of
chromium(III) to violet.
Applications of Potassium Dichromate
Solutions
The principal use of dichromate is for the
volumetric titration of iron(II) based upon the
reaction;
Cr2O72- + 6Fe2+ + 4H+ 2Cr3+ + 6Fe3+ + 7H2O
-titration is in the presence of moderate conc. of
HCl
The reaction of dichromate has been widely used
for the indirect determination of a variety of
oxidizing agents. This method has been applied to
the determination of nitrate, chlorate,
permanganate, and dichromate ions as well as
organic peroxides and several oxidizing agents.
c. Iodine
- solutions of iodine are weak oxidizing agents
that are used for the determination of strong
reductants.
I3- + 2e- 3I-
- advantageous of the use of iodine solutions
although it has low potential is that it imparts a
degree of selectivity that makes possible the
determination of strong reducing agents in the
presence of weak ones.
- an important advantage of iodine is the
availability of sensitive or reversible indicator for
the titrations.
- iodine solutions lack stability and must be
restandardized regularly.
The Preparation and Properties of Iodine
Solutions
- not very soluble in water; it is ordinarily
dissolved in moderately concentrated solutions of KI
and the reaction is
I2(s) + I- I3-
- the volatility of iodine solute makes the iodine
solutions lack stability; iodine slowly attacks most
organic materials; cork and rubber stoppers are
never used to close containers of reagent.
- air oxidation of iodide ions can cause changes in
the molarity of an iodine solution:
4I- + O2(g) + 4H+ 2I- + 2H2O
- this reaction causes molarity of iodine solution to
increase. Air oxidation is promoted by acids, heat
and light.
The Standardization and Application of
Iodine Solutions
- can be standardized against anhydrous
sodium thiosulfate or barium thiosulfate
monohydrate, both which are available
commercially.
Problem.
The purity of a hydrazine, N2H4, sample is determined
by titration with iodine. A sample of the oily liquid
weighing 1.4286 g is dissolved in water and diluted to a
liter in a volumetric flask. A 50.00-mL aliquot is taken
with a pipet and titrated with standard I2 solution,
requiring 42.41 mL. The iodine was standardized against
0.4123 g primary standard, As2O3, by dissolving the
As2O3 in a small amount of NaOH solution, adjusting the
pH to 8, and titrating, requiring 40.28 mL of iodine
solution. What is the %purity by weight of the
hydrazine?
Standardization reaction:
As2O3 + 6OH- → 2AsO33- + 3H2O
AsO33- + 3H+ → H3AsO3
H3AsO3 + I2 + H2O → H3AsO4 + 2I- + 2H+
Analysis reaction:
N2H4 + 2I2 → N2 + 4H+ + 4I-
1. Potassium bromate
- used for the determination of organic
compounds that contain olefinic and certain types of
aromatic functional groups
a. Potassium Bromate as a Source of Bromine
- available for commercial uses and can be used
to prepare standard solutions that are stable
indefinitely.
- widely used as a stable source of bromine
standard bromine solutions lack stability
BrO3- + 5Br + 6H+ 3Br2 + 3 H2O
an excess potassium iodide is introduced to
determine the excess bromine, the reaction
occurring is
2I- + Br2 + 6H+ 3Br2 + 3H2O
the liberated iodine is then titrated with standard
sodium thiosulfate.
bromine is incorporated into an organic molecule
either by substitution or by addition.
2. Periodic acid
reacts selectively with organic compounds having
hydroxyl, carbonyl, or amine groups on adjacent
carbon atoms.
the reaction of periodic acid to iodate ion is best
described by the half-reaction
H5IO6 + H+ + 2e- IO3- + 3H2O
The Preparation and Properties of Periodic
Acid Solutions
paraperiodic acid is available for the preparation
of standard solutions; it is a crystalline, readily
soluble, hygroscopic solid.
another is sodium metaperiodate, NaIO4, which
is soluble in water, sodium paraperiodate,
Na5IO6, is not sufficiently soluble but converted
to soluble metaperiodate by recrystallization
from concentrated nitric acid.
periodate solutions vary in stability, depending
on their mode of preparation.
The Standardization of Periodate
Solutions
can be standardized by buffering aliquots of
the reagent with standard borax or sodium
hydrogen carbonate to ensure they remain
slightly alkaline. An excess iodide is introduced
in the formation of a mol of iodine for each
mole of periodate
H4IO6- + 2I- IO3 + I2 + OH- + H2O
3. Karl Fischer reagent
widely employed for the determination of
water in a variety of organic or inorganic
samples
relatively specific for water
The Reaction and Stoichiometry
composed iodine, sulfur dioxide, pyridine and
methanol
stoichiometry involves the consumption of 1
mole of iodine, 1 mole of sulfur dioxide, and
3 moles of pyridine for each mole of water.
Titer
-mg analyte that is chemically equivalent
to 1 m L of titrant
Example.
If K2Cr2O7 has a titer of 1.267 mg Fe; then
1 mL K2Cr2O7 will react with 1.267 mg Fe.
1. sample of K2Cr2O7 (294.19 g/mol) contains 5.442
g/L. What is its titer in terms of mg Fe3O4?
Cr2O72- + 6Fe2+ + 14H+ → 2Cr3++ 6Fe3+ + 7H2O
2. Express the titer of a 0.0500M KMnO4 solution in
mg Fe2O3 (159.7 g/mol) per mL KMnO4.
MnO4- + 5Fe2+ + 8H+ → Mn 2+ + 5Fe3+ + 4H2O
3. Given the ff. data:
Calculate %Fe (55.85 g/mol) in a sample of
limonite ore.
Standardization data of the solution:
1.000 mL KMnO4 = 0.005317 g Fe
1.000 mL FeSO4 = 0.009200 g FeO (71.85g/mol)
Analysis data:
Mass of sample = 0.5000 g
V of KMnO4 used = 50.00 mL
Back-titration data:
V of FeSO4 used = 6.00 mL
Reaction:
MnO4- + 5Fe2+ + 8H+ → Mn 2+ + 5Fe3+ + 4H2O
An 8.13-g sample of an ant-control
preparation was decomposed wet-ashing with
H2SO4 and HNO3 . The As in the residue was
reduced to As3+ with N2H4 . After removal of the
excess reducing agent, the As(III) required 23.77
mL titration with 0.02425 M I2 in a faintly
alkaline medium. Express the results of this
analysis in terms of %As2O3 (197.85 g/mol) in
the original sample.
H3AsO3 + I2 + H2O → H3AsO4 + 2I- + 3H+
20
A piece of brass weighing 220 mg was
dissolved and prepared for an iodometric
titration. Excess KI was added and the
liberated I2 required 26.9 mL of 0.0847 M
Na2S2O3 to reach the starch endpoint.
Calculate %Cu (63.5 g/mol) in the brass.
2Cu2+ + 4I- → 2 CuI(s) + I2
I2 + 2S2O32- → 2I- + S4O62-
21
1. Treatment of hydroxylamine, H2NOH, with an
excess of Fe3+ results in the formation of N2O and an
equivalent amount of Fe2+;
2H2NOH + 4Fe3+ → N2O + Fe2+ + 4H+ + H2O
Calculate the molar concentration of H2NOH
solution if the Fe2+ produced by the treatment of a
50.00 mL aliquot required 23.61 mL of 0.02170M
K2Cr2O7.
Cr2O72- + 6Fe2+ + 14H+ → 2Cr3+ + 6Fe3+ + 7H2O
2. Under suitable conditions, thiourea, CS(NH2)2
(76.13 g/mol) is oxidized to sulfate by bromate;
3 CS(NH2)2 + 4BrO3- + 3H2O → 3CO(NH2)2 +
3SO42- + 4Br- + 6H+
A 0.0715 g sample of a material was found to
consume 14.1 mL of 0.00833M KBrO3. What was the
% purity of the thiourea sample?
3. A 4.971 g sample containing the mineral tellurite was
dissolved and then treated with 50.00 mL of 0.03114 M
K2Cr2O7;
3TeO2 + Cr2O72- + 8H+ → 3H2TeO4 + 2Cr3+ + H2O
Upon completion of the reaction, the excess required a
10.05-mL back-titration with 0.1135 M Fe2+.
6Fe2+ + Cr2O72- + 14H+ → 2Cr3+ + 6Fe3+ + 7 H2O
Calculate %TeO2 (159.6 g/mol) in the sample.