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CHEM 301 LECTURE

Unit 10. REDOX TITRATION


I. Principle: reduction-oxidation between the titrant and the analyte
oxidation:
loss of electron
reduction:
gain of electron
oxidizing agent:
oxidizes another substance, undergoes reduction
reducing agent:
reduces another substance, undergoes oxidation
II. Indicators for Redox Titration
Iron(II) orthophenanthrolines

1,10-phenanthrolines or orthophenanthrolines

form stable complexes with iron(II) and certain other ions

2+

orthophenanthrolines form a covalent bond with the iron(II), yields a complex called ferroin, (phen)3Fe
the complex undergoes a reversible redox reaction:
3+
2+
(phen)3Fe + e- (phen)3Fe
pale blue

red

reacts rapidly and reversibly


pronounced color changed
stable solution and readily prepared
the oxidized form of ferroin is inert towards strong oxidizing agents

Starch/Iodine Solutions

colorless in the presence of excess iodide ion

blue in the presence of excess iodine


Potassium thiocyanate

used in the titration of iron(III)

red color of iron(III)-thiocyanate complex disappears at the end point

III. Auxiliary Oxidizing and Reducing Reagents

the analyte for titration must be in a single oxidation state


if the analyte is to be titrated with a standard reductant, it has to be pretreated with an auxiliary oxidizing reagent
if the analyte is to be titrated with a standard oxidant, it has to be pretreated with an auxiliary reducing reagent

the prereductant or preoxidant must:

react quantitatively with the analyte

readily removable after treatment

must not interfere with the titrant

Auxiliary Reducing Reagents

metals used as auxiliary reducing agents: zinc, lead, aluminum, cadmium, nickel, silver, copper
the solid is removed manually by filtration
alternative: use reductor set-up

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CHEM 301 LECTURE


Auxiliary Oxidizing Reagents
sodium bismuthate
the bismuthate is suspended in the analyte and boiled for a brief period
RHR:

NaBiO3 + 4H + 2e BiO + Na + 2H2O

ammonium peroxydisulfate
strong oxidizing agent
3+

2-

in acidic condition, oxidizes: Cr to CrO4


3+
5+
Ce to Ce
2+
Mn to MnO4
sodium peroxide or hydrogen peroxide

H2O2 + 2H + 2e 2H2O

excess peroxide is removed by boiling

IV. Standard Reducing Agents


Iron(II) solutions

prepared from iron(II) ammonium sulfate

or from iron(II) ethylenediamine sulphate

solutions are stable for no more than one day

Fe(NH4)2(SO4)2.6H2O Mohrs salt


FeC2H4(NH3)2(SO4)2.H2O Oespers salt

Sodium thiosulfate

moderately strong reducing agent

used in indirect methods involving iodine

an unmeasured excess of KI is added and the liberated I2 is titrated with the standard thiosulfate
+
OCl + 2I + 2H Cl + I2 + H2O
22I2 + 2S2O3 2I + S4O6
factors that affect stability of the thiosulfate standard:
2+

decomposition in acidic medium


S2O3 + H HSO3 + S

concentration of the solution

presence of copper(II) ions

exposure to light

presence of bacteria that metabolize thiosulfate to sulfite and sulfate ions, and sulfur
Example:
A 0.2134-g bleaching powder sample was analyzed for its calcium hypochlorite (142.98 g/mol) content. The powder was
dissolved in water, and a large excess of KI was added, acidifying with HCl. The liberated iodine required 32.16 mL of a 0.08653
M Na2S2O3 solution to decolorize the starch-iodine complex. Calculate the percentage of Ca(ClO)2 in the sample.

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CHEM 301 LECTURE


V. Standard Oxidizing Reagents
Strong Oxidants: Potassium Permanganate and Cerium (IV)

KMnO4
solutions in sulfuric acid require
require occasional restandardization
cannot be used for HCl solutions of
analytes
requires a primary standard like
sodium oxalate in acidic medium

Cerium(IV)
solutions in sulfuric acid are indefinitely stable

do not oxidize chloride ion; can be used for HCl


solutions of analytes

primary-standard-grade cerium ammonium


nitrate is available for preparing standard
solutions directly
sodium oxalate can also be used for
standardization
cerium(IV) solution is yellow-orange but not
intense enough; use of 1,10-phenanthroline as
indicator is required
more expensive

the intense color of the permanganate


ion does not require any indicator

cheaper

form precipitates of basic salts in solutions with


less than 0.1 M in strong acid

Preparation of potassium permanganate:


permanganate oxidizes water:

4MnO4 + 2H2O 4MnO2 + 3O2 + 4OH

2+

although the decomposition is slow, it is catalyzed by light, heat, acids, bases, Mn and MnO2

KMnO4 reacts with organic matter and dust that may be present in the water that was used to dissolve it
the reaction produces manganese dioxide
heating and storing for a day allows the permanganate to react completely with the impurities
MnO2 is removed by filtration before titration
paper cannot be used for filtration, an inert material like asbestos in glass wool is used
the solution is stored in an amber bottle

Example:
In the standardization of a KMnO4 solution, 0.1148 g of Na2C2O4 (134.0 g/mol) was dissolved in 100 mL of water. After adding
acid, the solution required 23.85 mL of the KMnO4 solution to reach the end point. What is the concentration in M of the
KMnO4 solution?

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CHEM 301 LECTURE


Example:
A 3.0 mL sample of H2O2 (34.00 g/mol) was dissolved and 20.0 mL of water and required 11.85 mL of a 0.02645 M KMnO4
solution to reach the end point. If commercial agua oxigenada contains 3 % (20 volumes) H2O2, is the sample fresh or expired?

Potassium Dichromate

dichromate titrations are generally carried out in solutions that are about 1 M in HCl or H2SO4

indefinitely stable

can be boiled without decomposition

do not react with HCl

reagent-grade potassium dichromate is available for direct preparation of standard solution

the orange color of the dichromate is not intense enough for end point detection

diphenylamine sulfonic acid is used as an indicator; the oxidized form is violet, the reduced form is colorless
Example:
A 5.00-mL sample of lambanog was diluted to 1.000 L in a volumetric flask. The ethanol in a 25.00-mL aliquot was distilled into
50.00 mL of 0.02000 M K K2Cr2O7 and oxidized to acetic acid with heating:
2-

3+

3C2H5OH + 2Cr2O7 16H 4Cr

+ 3CH3COOH + 11H2O

2+

2+

After cooling, 20.00 mL of 0.1253 M Fe was pipetted into the flask. The excess Fe was then titrated with 7.46 mL of the
standard K2Cr2O7. Calculate the percentage (w/v) of ethanol (46.07 g/mol) in the liquor.

Iodine

a weak oxidizing agent used for determination of strong reductants


have limited application
lacks stability due to volatilization of I2and requires restandardization
iodine is not very soluble in water; is dissolved in concentrated KI solution

END!!
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