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REDUCTION-OXIDATION

TITRATION
Volumetric method of analysis which relies on
oxidation or reduction of analyte.
Initial Step in Redox Titration
The first step is to dissolve the sample which can
result in a mixed oxidation state.
Example: Dissolution of Fe results to
mixture of Fe+2 and Fe+3

The analyte must be in a single oxidation state


at the start of the titration.

This can be achieved by using a pre-oxidation or


pre-reduction step prior to analysis.
Auxillary Reducing Agents
ACTIVE METALS - Ni, Zn, Al, Cd, Pb, Cu, Ag (in the
presence of Cl)
Usage depends on the reduction potential of the metal
relative to that of the analyte.
The metal may be mixed directly with analyte solution
and removed mechanically or by filtration.

JONES REDUCTOR uses amalgated Zn as reducing


agent
Zn(Hg) Zn2+ + Hg + 2e-
Amalgam prevents - Zn + 2H+ Zn2+ + H2(g)
Auxillary Reducing Agents
WALDEN REDUCTOR uses granular Ag
Ag (with HCl) AgCl(s) + e-
Ag is not easily oxidized; Cl- encourages oxidation of Ag.
Auxillary Oxidizing Agents
Sodium bismuthate, NaBiO3
very powerful oxidizing agent
converts Mn2+ to MnO4-
not very soluble so excess reagent can be
removed after filtration
make a suspension with the sample and boil it
Auxillary Oxidizing Agents
Ammonium peroxydisulfate, (NH4)2S2O8
In acid, converts Cr3+ to Cr2O72- , Mn2+ to MnO4-,
Ce3+ to Ce4+
excess reagent is removed by adding a trace of
silver and boiling; this decomposes the reagent
according to the chemical equation below:

Ag+
2S2O82- + 2H2O 4SO42- + O2(g) + 4H+
Auxillary Oxidizing Agents
Peroxide
not as strong as the other examples
must be used in acidic solutions

H2O2 + 2H+ +2e- 2H2O

Excess reagent can be removed by boiling


PERMANGANATE METHOD
Titrant: Potassium Permanganate (KMnO4)
powerful oxidizing agent
can be used to determine Fe2+, Sn2+, Hg22+, NO2-,
C2O42-, SO32-
indicator: MnO4-, serves as its own indicator
because it is colored
primary standard: Na2C2O4, As2O3
PERMANGANATE METHOD
Disadvantages:
most significant disadvantage: tendency to
decompose
decomposition can be catalyzed by light, acid, heat,
bases, Mn2+ and MnO2

MnO4- Mn2+ (acidic medium)


MnO4- MnO2 (neutral)
MnO4- MnO42- (basic medium)
PERMANGANATE METHOD
DIRECT METHOD - used in the presence of an acid in
the direct titration of oxidizable cations and anions.

INDIRECT METHOD - determination of reducible


substances
Analyte + xss reducing agent products
KMnO4 + reducing agent products
Dichromate Process
Titrant: Potassium dichromate (K2Cr2O7)
Reduced to Cr+3 in strongly acidic solution;
Cr2O72 + 14H+ + 6e 2Cr+3 + 7H2O
Standard solutions can be prepared directly
Standard solutions are indefinitely stable
Principal use: volumetric titration of iron (II)
Indicator: Diphenylaminesulfonic acid
reduced form colorless
oxidized form violet
Disadvantage: slowness of reactions with reducing
Sample Problem
A 0.7120 g of iron ore was brought into solution
and passed through a Jones reductor. Titration of
Fe(II) produced required 39.21mL of 0.02086M
KMnO4. Express the results of analysis in terms of
(a) percent Fe and (b) percent Fe2O3.
5Fe+2 + MnO4 +8H+ 5Fe+3 + Mn+2 + 4H2O
Sample Problem
A 4.971g sample containing the mineral tellurite was
dissolved and then treated with 50.00mL of 0.03114M
K2Cr2O7:
3TeO2 + Cr2O72 + 8H+ 3H2TeO4 + 2Cr+3 + H2O
When the reaction is complete, the excess Cr2O72
required a 10.05mL back-titration with Fe+2. Calculate
the percentage of TeO2 in the sample.
6Fe+2 + Cr2O72 + 14H+ 6Fe+3 + 2Cr+3 + 7H2O
IODINE METHODS
Iodine is a weak oxidizing agent but reacts rapidly and
there is an available indicator.

Two methods:
Iodimetry I2 is the titrant
Iodometry the substance is made to liberate iodine and
the iodine liberated is titrated by thiosulfate
I2 + 2S2O32- 2I- + S4O62-
IODIMETRY
The titrant is I2 and the analyte is a reducing agent
I2 is slightly soluble in water (0.00134 mol/L at 25oC) but
soluble in solutions containing I-
I2 + I- I3-

indicator: starch forms a deep intense blue complex


with I2
primary standard: As2O3, anhydrous Na2S2O3 or
BaS2O3.H2O
IODIMETRY
Iodine titrations are usually performed in, neutral, mildly
alkaline or weakly acidic solution.
If the solution is strongly acidic:
starch indicator is hydrolyzed/ decomposed in
strong acid, thus endpoint detection is affected
the reducing power of several reducing agents
are decreased in strongly acidic solutions but
are increased in neutral solution
e.g. H3AsO3 + I2 +H2O H3AsO4 + 2I- + 2H+
IODIMETRY
If the solution is strongly basic:
I2 will disproportionate to hypoiodite and iodide

I2 + 2OH- IO- + I- + H2O

Why standardize iodine solutions?


Iodine solutions should be standardized because iodine
is volatile & commercial iodine is not sufficiently pure.
IODOMETRY
the method makes use of the fact that practically all
oxidizing agents oxidize iodide in dilute acid solutions to
free iodine. The liberated iodine can then be titrated
with thiosulfate solutions.
endpoint is detected with starch (disappearance of blue
color)
the starch is not added at the beginning of titration
when iodine concentration is high
the starch indicator is added just before the endpoint
when dilute iodine color becomes pale yellow.
IODOMETRY
Sodium thiosulfate, Na2S2O3
moderately strong reducing agent
widely used to determine oxidizing agents
OA + I- xss I2 + reduced form of analyte
I2 + S2O32- I- + S4O62-
variables that may influence the decomposition of
thiosulfate solutions
pH, microorganism, presence of Cu2+ ions, exposure to
sunlight
acidic solutions increases decomposition rate
thiobacteria may metabolize S2O32- to SO42-, SO32- or S
Sample Problem
A 0.1017-g sample of KBrO3 was dissolved in dilute HCl
and treated with an unmeasured excess of KI. The
liberated iodine required 39.75 mL of a sodium
thiosulfate solution. Calculate the molar concentration
of the Na2S2O3.
Sample Problem
The tetraethyl lead [Pb(C2H5)4] in a 25.00-mL sample of
aviation gasoline was shaken with 15.00 mL of 0.02095
M I2. The reaction is
Pb(C2H5)4 + I2 Pb(C2H5)3I + C2H5I
After the reaction was complete, the unused I2 was
titrated with 6.09 mL of 0.03465 M Na2S2O3. Calculate
the weight (in milligrams) of Pb(C2H5)4 (323.4 g/mol) in
each liter of the gasoline.