Topic VI

Reduction-Oxidation
Titrimetry

2nd Semester 2020-2021

 REDUCTION-OXIDATION
TITRATION CURVE
Redox Titration Curves
• The vertical axis in oxidation/reduction titration curves is
generally an electrode potential instead of logarithmic
functions.

Equivalence Point Potentials (p. 344 Skoog)

• 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 conc. 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
REDUCTION-OXIDATION
TITRATION CURVE
 REDUCTION-OXIDATION
TITRATION CURVE
1. General Redox Indicator
➢ substances that change color upon beig 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 Orthophenanthrolines

• known as phenanthroline that form stable complexes with iron(II) and
certain other ions.
b. Diphenylamine and its Derivatives
c. Iodine Solutions
• widely used in oxiddddation/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.
 AUXILLIARY REDUCING AND
OXIDIZING AGENTS
Auxilliary Reducing and Oxidizing Agents
➢ 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.

a. Auxilliary Reducing Reagents

= a number of metals are good reducing agents and have been
used for preredction 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.
 AUXILLIARY OXIDIZING AGENTS
b. Auxilliary Oxidizing Reagents

1. 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
 AUXILLIARY OXIDIZING AGENTS
b. Auxilliary Oxidizing Reagents

2. Ammonium Peroxydisulfate
• 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 + 2H2O 4SO42- + O2(g) + 4 H+
 AUXILLIARY OXIDIZING AGENTS

b. Auxilliary Oxidizing Reagents

3. 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 sol’n
H2O2 + 2H+ + 2e- 2H2O E°=1.78 V
• after oxidation is complete, the solution is freed of excess
reagent by boiling:
2H2O2 2H2O + O2(g)
 Titrant: Titrant:
Strong Reductant Strong Oxidant

Upon addition of Upon addition of

the titrant, analyte the titrant, analyte
is reduced is oxidized
Analyte must be in Analyte must be in
the oxidized state; the reduced state;
sample solution is sample solution is
added with auxilliary added with auxilliary
oxidizing agent; all reducing agent; all
Fe in Fe3+ state Fe in Fe2+ state

Sample solution: Contains Fe (analyte) Sample solution: Contains Fe (analyte)

(mixture of Fe2+ and Fe3+) (mixture of Fe2+ and Fe3+)
NPPETEROS Chem 28 Lecture
 APPLICATION OF STANDARD
REDUCTANTS
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
form 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 beig 0.5 M in H2SO4.
 APPLICATION OF STANDARD
REDUCTANTS
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 tend to decompose to give sulfur and
hydrogen sulfite ion: S2O32- + H+ HSO3- + S(s)
APPLICATION OF STANDARD
REDUCTANTS
 APPLICATION OF STANDARD
REDUCTANTS
Variables that influence the rate of thiosulfate reaction include
1. pH
2. presence of microorganisms
3. concentration of the solution
4. presence of copper (II)
5. exposure to sunlight

Standardization of Thiosulfate solutions

• Potassium iodide 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-
Standardization:
calculate the concentration PRACTICE EXERCISE 1
A solution of sodium thiosulfate was standardized by dissolving
0.1210 g KIO3 (214.00 g/mol) in water, adding a large excess of KI,
and acidifying with HCl. The liberated iodine required 41.64 mL of
the thiosulfate solution to decolorize the blue starch/iodine
complex. Calculate the molarity of Na2S2O3. Ans: 0.08147 M
IO3- + 5I- + 6H+ 3I2 + 2H2O
1 mol IO3- = 3 mol I2 = 6 mol S2O32-
 COMMON OXIDANTS USED AS
STANDARD SOLUTIONS
Reduction Standard Standardize with Indicator
Product Potential, V
KMnO4 Mn2+ 1.51 Na2C2O4, Fe, As2O3 MnO4-
KBrO3 Br- 1.44 KBrO3 -Naphthoflavone
Ce4+ Ce 3+ 1.44 Na2Cr2O7, Fe, As2O3 1,10-phenanthroline iron(II)
K2Cr2O7 Cr3+ 1.33 K2Cr2O7, Fe diphenylamine sulfonic acid
I2 I- 0.536 BaS2O3•H2O, Na2S2O3 starch

a. The strong Oxidants – Potassium Permanganate and Cerium(IV)

Mn O4- + 8H+ + 5e- Mn 2+ + 4H2O
Ce4+ + e- Ce3+

The choice among the two depends upon

• the strength of the analyte as a reducing agent,
• the rate of reaction between oxidant and analye,
• the stability of the standard oxidant solutions,
• the cost
• the availability of indicator.
 APPLICATION OF OXIDANTS
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.0
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.
APPLICATION OF OXIDANTS
APPLICATION OF OXIDANTS
Determine mass of PRACTICE EXERCISE 1
titrant/solution
Describe how would you prepare 2.0 L of an approximately 0.010 M
solution of KMnO4 (158.03 g/mol). Ans: 3.16 g KMnO4
 PRIMARY STANDARDS

Name Formula
Cerium(IV) ammonium nitrate Ce(NO3)4•2NH4NO3
Cerium(IV) ammonium sulfate Ce(SO4)2•2(NH4 )2SO4•2H2O
Cerium(IV) hydroxide Ce(OH)4
Cerium(IV) hydrogen sulfate Ce(HSO4)4

Primary Standards for KMnO4 and Ce4+

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
The same oxidation products are formed with Cerium(IV).
Determine mass of primary
standard (standardization) EXAMPLE 1
You wish to standardize the 0.010 M KMnO4 solution against primary
standard sodium oxalate (134.00 g/mol). If you want to use between
30 and 45 mL of the reagent for the standardization, what range of
masses of primary standard should you weigh?
Ans: 0.10 - 0.15 g primary standard

2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2(g) + 8H2O

Standardization:
calculate the concentration PRACTICE EXERCISE 3
Exactly 33.31 mL of the KMnO4 solution were required to titrate a
0.1278 g sample of primary standard Na2C2O4. (134.00 g/mol) What
was the molarity and normality of KMnO4 reagent. Ans: 0.01145 M
2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2(g) + 8H2O
Determine mass of sample
(from % purity) EXAMPLE 2
Aqueous solutions containing approximately 3% (w/w) H2O2 are sold
in drug stores as a disinfectant. Propose a method for determining
the peroxide content if you want to use between 30-45 mL of
0.01145 KMnO4 solution. The reaction is:
5H2O2 + 2MnO4- + 6H+ → 5O2 + 2Mn2+ + 8H2O
Ans: 0.97 – 1.5 g sample
 APPLICATION OF OXIDANTS
2. Potassium Dichromate
• dichromate ion is reduced to green chromium(III) ion.
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O E° = 1.33V
• carried out in solutions that are 1 M in HCl or H2SO4
where E° is 1.0 to 1.1 V.
• indefinitely stable , can be boiled w/o decomposition and do
not react with HCl.
• primary standard reagent is available commercially and at
modest cost.
• the disadvantage of potassium dichromate over cerium(IV)
and permanganate ion is its lower electrode potential and the
slowness of its reaction with certain reducing agents.
 APPLICATION OF OXIDANTS
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 sulfunic 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 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.
% Purity with back-titration EXAMPLE 3
A 5.00 mL sample of brandy was diluted to 1.00 L in a volumetric
flask. The ethanol (C2H5OH) in 25.00 mL aliquot of the diluted solution
was distilled into 50.00 mL of 0.0200 M K2Cr2O7 and oxidized to
acetic acid with heating. The reaction is
3C2H5OH +2Cr2O72- +6H+ 4Cr3+ +3CH3COOH +11H2O
After cooling, 20.00 mL of 0.1253 M Fe2+ were pipetted into the flask.
The excess Fe2+ was then tritated with 7.46 mL of the standard
K2Cr2O7 to a diphenylamine sulfonic end point.
Cr2O72- + 6Fe2+ + 4H+ 2Cr3+ + 6FE3+ + 7H2O
Calculate the percent (w/v) C2H5OH (46.07 g/mol) in the brandy.
Ans: 40.4 % (w/v) C2H5OH
 APPLICATION OF OXIDANTS
3. Iodine
• solutions of iodine are weak oxidizing agents that are used for
the determination of strong reductants.
I3- + 2e- 3I- E° = 0.536 V
• 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.
 APPLICATION OF OXIDANTS
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- K=7.1 x 102
• 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 oxidationof 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.
 APPLICATION OF OXIDANTS
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- K=7.1 x 102
• 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 oxidationof 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.
References
 D.A. Skoog, D.M. West, F.J. Holler, and S.R. Crouch,
Fundamentals of Analytical Chemistry, 9th ed., Thomson
Learning Asia, Singapore, 2014.
 Supplemental Notes

 Web references