Oxidation-Reduction Titrations

 applicable to a variety of a A + b T --In c Products

both inorganic and
organic substances Analyte Titrant Products
OA RA RP + OP
 popularity may exceed RA OA RP + OP
that of acid-base titrations
 availability of many
titrants & standards, each
with properties that make
it especially suitable for
specific applications
 Pretreatment
Analytes  use of auxiliary reagents
 Auxiliary Oxidizing Agents
 Auxiliary Reducing Agents
must be  must react quantitatively
in a single with the analyte
oxidation  excess of the reagent must be
state readily removable because
such excesses will inevitably
interfere by consuming
standard solution
 Analytes

Pre-Oxidation

 higher oxidation 1. NaBiO3

state 2. (NH4)2S2O8
3. Na2O2
 employs the use 4. H2O2
of auxiliary
oxidants
 Analytes

Pre-Reduction

 lower oxidation 1. metals - Zn, Al, Cd,

state Pb, Ni, Cu, Ag

 employs the use 2. alternative to

of auxiliary filtration is the
reductants use of a reductor
Reductors
1. Jones –
amalgamated
zinc

2. Walden –
granular
metallic silver
 tends to react
1. Iron (II) Solutions
with  readily prepared from Mohr’s salt –
Fe(NH4)2(SO4)2 . 6H2O or from the closely
atmospheric related Oesper’s salt – FeC2H4(NH3)2(SO4)2 .
oxygen 4H2O
 seldom used  numerous oxidizing agents are conveniently
determined by treatment of the analyte
for direct
solution with a measured excess of standard
titration of iron (II) followed by immediate titration of
oxidizing the excess with a standard solution of
analytes potassium dichromate or cerium (IV)

 indirect
methods are
used instead
Titrants : Reductants
2. Sodium Thiosulfate
 a moderately strong
reducing agent that has
been widely used to
determine oxidizing
agents by an indirect
procedure that involves
iodine as an intermediate
 resistant to air-oxidation,
they do tend to
decompose to give sulfur
and hydrogen sulfite ion
 potassium iodate is an
excellent primary
standard
1 mol IO3 1- = 3 mol I2
= 6 mol S2O3 2-
 other primary standards:
potassium dichromate,
potassium bromate,
potassium hydrogen
iodate, potassium
ferricyanide and metallic
copper
 Titrants : Oxidants

Choice depends on:

 strength of the analyte  cost

as a reducing agent
 availability of a
 rate of reaction between satisfactory indicator
oxidant and analyte

 stability of the standard

oxidant solutions
 Titrants : Common Oxidants

1. Potassium Permanganate (KMnO4)

 useful property is its  not entirely stable; should

intense purple color, be stored in the dark
which is sufficient to serve
as an indicator for most  widely used primary
titrations standard : sodium oxalate

 second reason for

popularity is their modest
cost
 Titrants : Common Oxidants

2. Cerium (IV)
 oxidizing strength  primary-standard- grade salt
comparable to of the reagent is available,
permanganate solutions thus making possible the
direct preparation of
 solutions of cerium (IV) in
standard solutions
sulfuric acid are stable
indefinitely  iron (II) complex of 1,10-
phenanthroline or one of its
 solutions are yellow-orange,
substituted derivatives are
but the color is not intense
widely used as indicator
enough to act as an indicator
during titration
in titrations
 Titrants : Common Oxidants
3. Potassium Dichromate (K2Cr2O7)
 solutions are indefinitely
stable, can be boiled without
decomposition and do not
react with HCl
 primary-standard reagent is
available commercially and
at a modest cost
 its orange color is not
intense enough for use in
end-point detection
 disadvantages of potassium
dichromate are its lower
electrode potential and the
slowness of its reaction with
certain reducing agents
 diphenylamine sulfonic acid
is an excellent indicator
 reaction of dichromate with
iron (II) has been widely
used for the indirect
determination of a variety of
oxidizing agents
 Titrants : Common Oxidants
4. Iodine (I2)
 weak oxidizing agent used
for the determination of
strong reductants
 have relatively limited
application because of their
significantly smaller
electrode potential
 imparts a degree of
selectivity (e.g. determination
of strong reducing agents in the
presence of weak ones)
 an important advantage is
the availability of a sensitive
and reversible indicator for
titrations
 lacks stability and must be
re-standardized regularly
 can be standardized against
anhydrous sodium
thiosulfate or barium
thiosulfate monohydrate
Titrants : Common Oxidants
Reagent Reduction Standard Standardized
Formula Product Potential, V with

KMnO4 Mn2+ 1.51 Na2C2O4, Fe,

As2O3
KBrO3 Br1- 1.44 KBrO3
Ce4+ Ce3+ 1.44 Na2C2O4, Fe,
As2O3
K2Cr2O7 Cr3+ 1.33 K2Cr2O7, Fe
I2 I1- 0.536 Ba2S2O3, .
H2O,
Na2S2O3
 1. Potassium Bromate
 used for the determination of organic
used compounds that contain olefinic and
primarily for certain types of aromatic functional groups
determining  primary-standard grade is available from
certain commercial sources and can be used
special directly to prepare standard solutions that
groups of are stable indefinitely
compounds  is a convenient and widely used stable
source of bromine

Specialized Oxidants
 Specialized Oxidants
2. Periodic Acid
 reacts selectively with organic
compounds having hydroxyl,
carbonyl or amine groups on
adjacent carbon atoms
 organic compounds containing
aldehyde, ketone or alcohol
groups on adjacent carbon
atoms are rapidly oxidized by
periodic acid (e.g. primary &
secondary alpha-
hydroxylamine)
3. Karl Fischer Reagent
 widely employed for the
determination of water in a
variety of organic and
inorganic samples
 is composed of iodine, sulfur
dioxide, pyridine and
methanol
 Indicators

1. General or True REDOX Indicators

 substances that change color
upon being oxidized or
reduced  Iron (II) complexes of
1,10-Phenanthroline
 largely independent of the
chemical nature of the  Diphenylamine and its
analyte and titrant Derivatives
 depend instead upon  Starch/Iodine Solutions
changes in the electrode
potential of the system that
occur as the titration
progresses
 Indicators
2. Specific REDOX Indicators
 Starch
 forms a dark blue
complex with triiodide
ions
 complex signals the end
point in titrations in which
iodine is either produced
or consumed
 Potassium Thiocyanate
 employed in the titration
of iron (III) with solutions
of titanium (III) sulfate
 end point involves the
disappearance of the red
color of the iron
(III)/thiocyanate complex
due to the decrease in the
iron (III) concentration at
the equivalence point
 Applications

1. Diazotization Titrations
 useful for the analysis of
 titration with HNO2 used in
sulfonamide antibiotics and
the assay of benzocaine,
aminobenzoic acid-derived
dapsone, primaquine,
local anesthetics
procaine, sulfacetamide,
 titration is carried with sulfadoxine, sulfamethizole,
acidified NaNO2, causing the sulfapyridine and
primary aromatic amine sulfathiazole
functional group is
converted to a diazonium
salt
 Applications

2. Iodine Titrations
 Iodimetric Method  Iodometric Method
 titrant is I2  sample is made to liberate
 direct titration I2
 back titration  titrant is Na2S2O3
 detected using starch  indirect titration
indicator
 assay of ascorbic acid,
sodium stilbigluconate,
dimercaprol injection and
acetarsol
 Exercise 15

A 5.00-mL sample of brandy was diluted to 1.000-L in

a volumetric flask. The ethanol (C2H5OH) in a 25.00-
mL aliquot of the diluted solution was distilled into
50.00-mL of 0.02000-M K2Cr2O7 and oxidized to
acetic acid with heating. The reaction is:
3 C2H5OH + 2 Cr2O7 2- + 16 H 1+ 
4 Cr 3+ + 3 CH3COOH + 11 H2O
After cooling, 20.00-mL of 0.1253-M Fe 2+ were
pipetted into the flask. The excess Fe 2+ was then
titrated with 7.46-mL of the standard K2Cr2O7 to a
diphenylamine sulfonic acid end point. Calculate the
percent (w/v) C2H5OH in the brandy.
Molar Mass: C2H5OH = 46.07
 Exercise 15
A 0.2981-g sample of an antibiotic powder
containing sulfanilamide was dissolved in HCl
and the solution diluted to 100.0-mL. A 20.00-
mL aliquot was transferred to a flask and
followed by 25.00-mL of 0.01767-M KBrO3. An
excess of KBr was added to form Br2 and the flask
was stoppered. After 10 minutes, during which
time the Br2 brominated the sulfanilamide, an
excess of KI was added. The liberated iodine was
titrated with 12.92-mL of 0.1215-M sodium
thiosulfate. Calculate the percent
NH2C6H4SO2NH2 in the powder.
Molar Mass: NH2C6H4SO2NH2 = 172.21
Reactions for the Analysis of Sulfanilamide
1. BrO3 1- + 5 Br 1- + 6 H 1+  3 Br2 + 3 H2O
2. NH2C6H4SO2NH2 + 2 Br2 
NH2C6H2 Br2SO2NH2 + 2 H 1+ + 2 Br 1-
3. Br2 + 2 I 1-  2 Br 1- + I2 (excess KI)

4. I2 + 2 S2O3 2-  S4O6 2- + 2 I 1-
 Exercise 15

A 10.0-mL aliquot (density – 1.50 g/mL) of a

fluorohydrocarbon, thought to be contaminated
with water, was dissolved in 50-mL of anhydrous
methanol and titrated with a Karl Fischer Iodine
Reagent, requiring 22.4-mL to reach the end
point.
A 10.0-mL aliquot of a sample prepared by
dissolving 1.00-mL of distilled water in 500-mL
of anhydrous methanol required 26.7-mL of the
same titrant to reach the endpoint.
Calculate the percentage of H2O in the
fluorohydrocarbon solvent.
Molar Mass: H2O = 18.02