MODULE 3

VOLUMETRIC ANALYSIS: OXIDATION-REDUCTION

Table of Contents:
Module 3 : Volumetric Analysis: Reduction-Oxidation

Unit 1: Volumetric Analysis: Permanganometry

Unit 2: Volumetric Analysis: Iodometry

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 UNIT 1: VOLUMETRIC ANALYSIS: PERMANGANOMETRY
ENGAGE AND EXPLORE

Permanganometry is a type of volumetric analysis (titration) that makes use of redox

reactions rather than acid base chemistry. The titrant is a solution of potassium

permanganate which is colored. The end point is detected by slight persistent pink that

indicates excess permanganate ion.

Permanganometry is one of the techniques used in chemical quantitative analysis. It is a

redox titration that involves the use of permanganates to measure the amount of analyte

present in unknown chemical samples. It involves two steps, namely the titration of the

analyte with potassium permanganate solution and then the standardization of

potassium permanganate solution with standard sodium oxalate solution. The titration

involves volumetric manipulations to prepare the analyte solutions.

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 EXPERIMENT NO. 9 PREPARATION OF
PERMANGANATE AND FERROUS AMMONIUM SULFATE SOLUTIONS

Objectives:
1. To prepare solutions to be used in redox titrations.
2. To be able to determine approximate concentration of a permanganate and ferrous
solution.
ENGAGE AND EXPLORE: Theoretical Discussion

In this redox reaction, Fe2+ is converted into Fe3+ and MnO4- (dark purple) is converted into
Mn2+. The change in the oxidation state of manganese in MnO4- to Mn2+ causes a change in
color. When the reaction is complete, and excess mno4- is added to the reaction mixture, the
solution turns pink and the titration is done.

Fe2+ + MnO4- (dark purple) → Fe3+ + Mn2+

(Fe2+ from FeSO4) (MnO4- from 0.02M KMnO4)

Potassium permanganate is a very powerful oxidizing agent. The intense coloring power of
permanganate wherein no indicator is needed, makes potassium permanganate a frequently
used oxidizing titrant in volumetric analysis. The permanganate process can also be applied
to the determination of certain oxidizing agent by the indirect method. In this case, a
measured amount of a reducing agent is added to the substance to be determined and after
reaction is complete, the excess reducing agent is determined by titration with standard
permanganate.

Permanganate in the presence of acid is always reduced to a manganous salt, and the
oxidation number of the manganese changes by five units (from +7 to +2). One- fifth of the
gram-equivalent molecular weight of potassium permanganate, therefore constitutes a norm
solution as an oxidizing agent.

Ferrous ion is oxidized in acid solution to ferric ion, involving a one-unit change in oxidation
number from +2 to +3. The gram-molecular weight of FeSO4•7H2O or of
FeSO4•(NH4)2SO4•6H2O, therefore constitutes 1 gram-equivalent weight of each of these two
commonly used ferrous compounds, and this amount, when dissolved in 1 liter of solution gives
a 1.000N solution in each case. Tenth-normal concentration are ordinarily used for both
permanganate and ferrous solutions.

EXPLAIN AND ELABORATE

Materials and Reagents:
Materials:
Weigh bottle (s) 10mL Pipet Funnel
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 100mL Graduated cylinder 1000mL Beaker Pipettol
500mL Container bottle Crucible Stirring rod
1L Volumetric flask buret clamp Dessicator
500mL Volumetric flask Wash bottle

Reagents:
 Distilled water, carbon dioxide (CO2) free: Prepared either (1) by boiling for 20 min
and cooling with soda-lime protection or (2) by bubbling air, freed from CO2 by
passing through a tower of soda lime, through water for 12 hr.
 KMnO4
 FeSO4 ∙ (NH4 )2 SO4 ∙ 6H2O
 6N H2SO4

Methodology:
A. Preparation of KMnO4
1. Dissolve 1.25 g of KMnO4 in 375 mL of distilled water in a 1000 mL beaker.
2. Warm and stir the solution until the crystals dissolve.
3. Keep warm over a small flame or in a steam bath for 30 minutes or more.
4. Cover the solution with a watch glass and allow to stand until cool, preferably
overnight.
5. Filter the permanganate using a glass wool.
6. Store the filtrate into an amber-colored reagent bottle.
7. Calculate the normality.
B. Preparation of Ferrous ammonium sulfate (FAS)
1. Pulverize 10.00 grams of ferrous ammonium sulfate, FeSO4 ∙ (NH4 )2 SO4 ∙ 6H2O.
2. Moisten with 7.5 mL of 6N H2SO4 (to prevent hydrolysis).
3. Transfer to a 250 mL volumetric flask and add enough water up to the mark.
4. Shake vigorously to insure uniformity.
5. Calculate the normality of the solution.
EVALUATE

Define the following

1. Oxidation
2. Reduction
3. Oxidizing agent
4. Reducing agent

Solve the problem.

What is the normality of KMnO4 if 20.00 mL of it is used to oxidize 0.2100 g of potassium
acid oxalate, KHC2O4•2H2O?
Data and Results:
N of KMnO4

N of FeSO4

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Computations:

Discussion:

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 EXPERIMENT NO. 10 DETERMINATION OF CONCENTRATION RATIO BETWEEN
POTASSIUM PERMANGANATE AND FERROUS AMMONIUM SULFATE

Objectives:
1. To determine, by means of titration, the concentration ratio between KMnO 4 and
FeSO4 ∙ (NH4)2 SO4 ∙ 6H2O.

ENGAGE AND EXPLORE: Theoretical Discussion

In the analyses given here, the ferrous sulfate solution is used only to back-titrate a solution in
which the end point has been overstepped. The concentration of an ferrous or permanganate
can be used to calculate the Normality of the other solution prepared if the ratio existing
between them has been determined. The concentration ratio can be determined by the
quantitative relation between the amounts of ferrous and permanganate used after titration.

EXPLAIN AND ELABORATE

Materials and Reagents:
Materials:
Buret, 50 mL Analytical balance
Volumetric pipet, 40 mL Volumetric flask, 250 mL
Weigh bottle (s) 10mL Pipet Funnel
100mL Graduated cylinder 1000mL Beaker Pipettol
Stirring rod buret clamp Dessicator
Wash bottle
Reagents:
 Prepared permanganate and ferrous solutions

Methodology:
1. Fill the burets separately with the potassium permanganate and ferrous ammonium
sulfate solutions observing the usual precautions.
2. Run out into a 250-mL Erlenmeyer flask about 7.5 mL of the ferrous ammonium sulfate
solution. Dilute to 25 mL and add 2.5 mL of 6N H2SO4.
3. Titrate with the potassium permanganate until a faint pink color is obtained which
persists even after swirling the solution for 15 seconds.
4. Calculate to 4 significant figures the value of each mL of the ferrous solution in terms of
the number of mL of the permanganate solution
EVALUATE
From the following data obtained, calculate up to 4 significant figures the value of each mL
of the ferrous ammonium sulfate solution in terms of the number of mL of the potassium
permanganate solution.

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Data and Results:
I II
Final reading FAS
Initial reading FAS

Final reading KMnO4

Initial reading KMnO4

1 mL KMnO4 ≎ mL FAS ≎ mL FAS

1mL FAS ≎ mL KMnO4 ≎ mL KMnO4

Mean Values: 1 mL KMnO4 = ______ mL FAS

1 mL FAS = ______mL KMnO4
Computations:

Discussion:

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 EXPERIMENT NO. 11 STANDARDIZATION OF POTASSIUM PERMANGANATE
SOLUTION

Objectives:
1. To determine a more accurate concentration of potassium permanganate using a
primary standard.
2. To calculate the concentration of ferrous solution using the concentration ratio.

ENGAGE AND EXPLORE: Theoretical Discussion

Potassium permanganate, KMnO4, is a strong oxidizing agent. Permanganate, MnO4-, is an
intense dark purple color. Reduction of purple permanganate ion to the colorless Mn+2 ion,
the solution will turn from dark purple to a faint pink color at the equivalence point. No
additional indicator is needed for this titration. The reduction of permanganate requires strong
acidic conditions.

In this experiment, permanganate will be reduced by oxalate, C2O42- in acidic conditions.

Oxalate reacts very slowly at room temperature so the solutions are titrated hot to make the
procedure practical. The unbalance redox reaction is shown below.

MnO4- + C2O42- → Mn2+ + CO2 (acidic solution)

In this experiment, a potassium permanganate solution will be standardized against a sample

of potassium oxalate. Once the exact normality (eq/l) of the permanganate solution is
determined, it can be used as a standard oxidizing solution. In part ii of this experiment, the
standard permanganate solution will be used to find the concentration of iron(II) in a ferrous
solution (g/l). The unbalanced redox reaction is shown below.

MnO4- + Fe2+ → Mn2+ + Fe3+ (acidic solution)

Since the number of gram milliequivalents of a given solid (x) is found by dividing its weight in
grams by its equivalent weight (mewt):

number of mex = gramsx / mewtx

And the number of milliequivalents of a substance in a solution (s) is the product of the number
of milliliters and normality:
number of mes = mL s x Ns
Hence,
number of mex = number of mes

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EXPLAIN AND ELABORATE

Materials and Reagents:

Materials:
Weighing paper Buret 500 ml Florence flask
Ring stand Rubber stopper Analytical balance
Buret clamp Hot plate or Bunsen burner 250 ml Erlenmeyer flask

Reagents:
 Solid KMNO4 Na2C2O4 6N H2SO4
 Distilled H2O

Methodology:
1. Weigh out using a weighing bottle about 0.05 g of Na2C2O4 which has been previously
dried for 2 hours at 105oC.
2. Transfer the Na2C2O4 into an Erlenmeyer flask and add 50 mL of distilled water and 7.5
mL of 6N H2SO4.
3. Using the thermometer as a stirring rod, warm the mixture until the oxalate has dissolved
and the temperature has been brought to to 80 – 90 oC.
4. Fill the burette with the prepared KMnO4.
5. Titrate slowly sodium oxalate solution with the potassium permanganate in the burette
stirring constantly, and keep the solution above 70oC at all times.
6. Add the potassium permanganate dropwise when near the endpoint allowing each
drop to decolorize before adding the next.
7. Take as the endpoint the faintest visible shade of pink that remains even after allowing
the solution to stand for 15 seconds.
8. From the data obtained calculate the normality of the potassium permanganate as an
oxidizing agent.
EVALUATE

Give the name and chemical formula of four (4) primary standards used for standardization
of KMnO4.

Solve the problem.

What is the normality of a solution of KMnO4 if 48.00 mL will oxidize 0.5000g of sodium
oxalate?

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Data and Results
I II

Weight of Na2C2O4
Final reading KMnO4
Initial reading KMnO4

Final reading FAS

Initial reading FAS
Value of FAS used in terms of KMnO4
Net volume of KMnO4

Normality of KMnO4
Computations:

Discussion:

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 UNIT 2: IODOMETRY

ENGAGE AND EXPLORE

Titration is the process used to determine the volume of one solution that will react with a

carefully measured volume of another solution. It is a quantitative technique based on the

mole relationships in a chemical reaction. Since molar concentration data are used, it is

considered to be a type of volumetric analysis. An acid-base titration is a quantitative analysis

of acids and bases; through this process, an acid or base of known concentration neutralizes

an acid or base of unknown concentration.

The titration progress can be monitored by visual indicators, pH electrodes, or both. The

reaction’s equivalence point is the point at which the titrant has exactly neutralized the acid

or base in the unknown analyte; if you know the volume and concentration of the titrant at

the equivalence point, you can calculate the concentration of a base or acid in the unknown

solution.

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 EXPERIMENT NO. 12 DETERMINATION OF IRON IN LIMONITE

Objectives:
To calculate the iron content of limonite and express it in terms of % Fe and % Fe 2O3

ENGAGE AND EXPLORE: Theoretical Discussion

An application of permanganate process is the determination of Iron in Limonite. It consists
of three essential steps: (1) dissolving the iron compounds present in the ore; (2) bringing
the iron to the ferrous state; and (3) titration the ferrous ions to the ferric state with standard
permanganate. Limonite is a common iron ore, a hydrated oxide of iron and its essential
composition is expressed by the formula Fe2O3•xH2O.

Hydrochloric acid is the best single solvent for Limonite and similar iron ores because of the
ability of chloride ions to tie up the iron to form iron complex. However, chloride ions are
capable of reducing permanganate therefore HCl gas is removed by evaporating to
fumes with H2SO4 subsequent to the dissolving of the ore. The other procedure is to titrate
the iron in cold, dilute solution in the presence of a large amount of MnSO4. The presence
of manganous ions causes the permanganate to oxidize the ferrous ions without acting
appreciably on the HCl.

The product of the number of milliliters of the titrating solution used mL s and the normality
of the solution N s represents the number of gram-milliequivalents in the solution used. This
is the same as the number of gram milliequivalent of pure substance neutralized. If the
number of gram-milliequivalents of substance x is multiplied by the value in grams of one
milliequivalent weight (mewt), the product is the number of grams of substance present in
the sample. The percentage purity of the sample is then simply 100 times the weight of
pure substance divided by the weight of sample taken for analysis:

EXPLAIN AND ELABORATE

Materials and Reagents:

Materials:
Buret, 50 mL Analytical balance
Volumetric pipet, 40 mL Volumetric flask, 250 mL
Weigh bottle (s) 10mL Pipet Funnel
100mL Graduated cylinder 1000mL Beaker Pipettol
Stirring rod buret clamp Dessicator
Wash bottle
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 Reagents:
 Prepared permanganate and ferrous solutions
 Limonite
 HCl (12N and 6N)
 HgCl2
 SnCl2

Methodology:
1. Weigh accurately 2 samples of about 0.075 to 0.1 g each of limonite into a 400 mL
beaker.
2. Add 5 mL of 6N HCl to the ore in the beakers and heat to just below boiling, with the
beakers covered with a watch glass. Preferably heat on a steam bath or on an electric
hot plate.
3. Continue to heat for 30 minutes or until the residue is white indicating the presence of
nothing but siliceous material.
4. If dark particles remain after 30 min, add 1.25 mL of 12N HCl and heat for 20 minutes
longer.
5. Heat the acid solution nearly to boiling.
6. Add dropwise a solution of SnCl 2 until the ferric ions have just been reduced to ferrous
ions, as indicated by the disappearance of the yellow .Do not add more than a drop or
2 in excess and keep the solution hot during the entire reduction.
7. Cool completely, and without much delay add rapidly 7.5 mL of HgCl 2 solution. A white
silky precipitate should form.
8. Allow the solution to stand for 5 minutes, dilute to about 100 mL with cold water, add
6.25 mL of MnSO4 titrating solution.
9. Titrate the cold solution at once with standard permanganate to a pink color
that remains for 15 seconds or more while the solution is stirred.
10. From the data, express the analysis in terms of % Fe and % Fe2O3 in limonite.

EVALUATE
a. Name three (3) other types of samples that can be analyzed in a permanganate
process.
b. Solve the problem.
A 0.5000g sample of limonite required 50.00 mL of KMnO4 (1.000 mL KMnO4 ≎
0.005317g Fe) for complete titration. Determine the percentage of Fe in the sample.

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Data and Results

I II

Weight of sample

Final Rdg KMnO4

Initial Rdg KMNO4

%Fe

%Fe2O3
Computations:

Discussion:

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 EXPERIMENT NO. 13
DETERMINATION OF THE OXIDIZING POWER OF PYROLUSITE

Objectives:
To calculate the oxidizing power of the pyrolusite in terms of % MnO2

ENGAGE
Materials AND EXPLORE
and Reagents:
Materials:
Weighing bottles Analytical balance
100mL, 1000mL beaker Volumetric flask, 250 mL
Funnel 10mL Pipet Funnel
100mL Graduated cylinder Stirring rod Pipettol
Buret clamp Buret Dessicator

Methodology:

1. Weigh out duplicate samples about 0.05g or pyrolusite

2. Weigh duplicate samples about 0.09g of pure Na2C2O4 into the beakers containing the
pyrolusite samples
3. Pour into each beaker 6.25mL of distilled water and 12.50mL of 6N H2SO4. Cover the
beaker and warm gently until the evolution of CO2 ceases and the residue is free from
black particles
4. Dilute to 62.50mL
5. Heat to a temperature just below boiling and while hot titrate the excess oxalate with
the standard permanganate
6. From the data obtained, calculate the oxidizing power of the pyrolusite in terms of %
MnO2
EVALUATE

Data and Results

I II

Weight of sample
Na2C2O4
Weight of sample

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 Final Rdg KMnO4

Initial Rdg KMNO4

% MnO2

Computations:

Discussion:

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 IODOMETRY

The term “iodometry” describes the type of titration that uses a standardised sodium

thiosulfate solution as the titrant, one of the few stable reducing agents where oxidation

of air is concerned. Iodometry is used to determine the concentration of oxidising agents

through an indirect process involving iodine as the intermediary. In the presence of iodine,

the thiosulphate ions oxidise quantitatively to the tetrathionate ions.

To determine the concentration of the oxidising agents, an unknown excess of potassium

iodide solution is added to the weakly acid solution. The iodine, which is stoichiometrically

released after reduction of the analyte, is then titrated with a standard sodium

thiosulphate solution (Na2S2O3).

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 EXPERIMENT NO. 14 PREPARATION OF POTASSIUM IODATE, SODIUM
THIOSULFATE AND STARCH SOLUTION

Objectives:

1. To prepare solutions to be used in iodometry

2. To be able to calculate the approximate normal concentration of iodine and
thiosulfate solutions
ENGAGE AND EXPLORE: Theoretical Discussion

Redox reaction can also be a basis of titration. In the oxidation process of volumetric
analysis, standard solution of oxidizing agents and reducing agents take the place of the
acid and alkali solutions of the neutralization process. Redox reactions are a combination
of two reactions; oxidation and reduction reaction. The oxidation reaction involves
increase in the oxidation state whereas in a reduction, the oxidation number of reactant
molecules reduces by certain numbers. The substance that oxidized is known as reducing
agent. On the contrary, the substance that reduces is known as an oxidizing agent in the
redox reaction.

One important combination is the iodine and sodium Thiosulfate solutions. The two
iodimetric titrating solutions must be prepared very carefully. Iodine does not dissolve
appreciably in water but does dissolve in a solution of potassium iodide, forming KI 3. An
iodine solution reacts with water to form HI under the influence of sunlight, and even at
room temperatures the iodine tends to volatilize from solution. It should therefore be
protected from light and heat. Sodium Thiosulfate is rarely sold as pure but can be purified
by recrystallization. Certain microorganisms that may present in water are able to
decompose Thiosulfate (into sulfate and sulfur) sufficiently to cause a gradual change in
normality. Boiling the water in which Thiosulfate is dissolved serves to destroy this bacteria.
Bacterial action is also retarded by adding a small amount of mild alkali (Na 2CO3) to the
solution, but this tends to accelerate the oxidation of Thiosulfate by the air.
Iodine is a moderately weak oxidizing agent; it is reduced to form the iodide anion, as
follows:

I2(aq) + 2e → 2I(aq)

The above redox reaction is completely reversible, and so the iodide anion is a moderately
weak reducing agent that will react with oxidizing analytes to produce iodine. Titrations
involving iodine have evolved for the analysis of a number of oxidizing and reducing
agents. In iodimetric titrations, the analyte (a reducing agent) reacts with iodine to
produce iodide:
Aox + I2 → Ared + 2I

where Aox and Ared are the oxidized and reduced forms, respectively, of the analyte.
The iodine may then be titrated to determine the analyte concentration in the sample.
The nearly universal titrant for iodine is thiosulfate; they react quantitatively as follows:
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 2S2O32 + I2 → (S4O6)2 + 2I

The fundamental reaction is represented by

I2 + 2Na2S2O3 → 2NaI + Na2S4O6

In both cases starch is used as an indicator. Starch forms with I 3- (tri-iodide ion) a dark blue
complex, visible with very tiny amounts of I3- present. Starch solution hydrolyze slowly in the
presence of acid to form decomposition products which do not give a blue color with
iodine.

EXPLAIN AND ELABORATE

Materials and Reagents:

Materials:
Weigh bottle (s) 10mL Pipet Funnel
100mL Graduated cylinder 1000mL Beaker Pipettol
500mL Container bottle Crucible Stirring rod
1L Volumetric flask Tong Dessicator
500mL Volumetric flask Wash bottle

Reagents:
 KI solution
 Iodine crystals
 distilled water
 Na2S2O3.5H2O
 Na2CO3
 Starch

Methodology:

Preparation of Starch Solution:

(Enough for 100 titrations, assign group to prepare the solution for the whole class, unused
portion should be refrigerated every after class)

1. Weigh 1g of starch and dissolve in about 15 mL of distilled water

2. Dilute to 500 mL with boiling water and heat until the mixture is clear
3. Cool. Transfer in a tightly stoppered bottle. (Use 2 to 3 mL as indicator).

Preparation of Potassium Iodate Solution:

1. Dry about 6g of potassium iodate at 110C for at least 1h and cool in a dessicator.

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 2. Weigh (to the nearest 0.1mg) about 1.1g of dry potassium iodate and transfer into a
250 mL volumetric flask; use a powder funnel to ensure quantitative transfer of the
solid.
3. Dissolve the KIO3 in about 100mL of distilled water.
4. Dilute to the mark and shake.

Preparation of Sodium Thiosulfate:

1. Boil about IL of distilled water for 10 to 15 minutes
2. Allow the water to cool to room temperature.

3. To 50mL of the CO2 free distilled water, add about 6.25g Na2S2O3.5H2O and 0.1g of
Na2CO3.
4. Stir until the solid has been dissolved.
5. Transfer the solution to a clean 250 mL volumetric flask and dilute to the mark
6. Store in a dark place

EVALUATE

Answer the following questions.

1. Why should starch solution be freshly prepared?
2. What is titration? And how it is applied in the procedure?

Data and Results

N I2
N NA2S2O3

Computations:

Discussion:

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 EXPERIMENT NO. 15
STANDARDIZATION OF SODIUM THIOSULFATE
Objectives:

1. To determine the concentration of sodium thiosulfate using a primary standard by

means of direct standardization.

ENGAGE AND EXPLORE: Theoretical Discussion

Commercial iodine is usually not sufficiently pure and is too volatile to permit its use as
standard for Thiosulfate solutions or for the direct preparation of a standard solution of
iodine.

Substances that can be obtained sufficiently pure to serve for the standardization of
Sodium Thiosulfate are potassium bromate, potassium Iodate, potassium biiodate,
potassium dichromate and metallic copper. All these substances in acid solution will
liberate iodine from an excess of KI, and the liberated iodine can be titrated with the
Thiosulfate solution. Potassium dichromate crystals are satisfactory for the standardization
of Thiosulfate, but the deep green color of the resulting chronic ions makes it a little more
difficult to estimate the iodo-starch end point.

Iodine/triiodide solutions are unstable for a variety of reasons. First of all, aqueous iodine
exerts a significant vapor pressure. Also, under acidic conditions iodide is slowly air-
oxidized to produce iodine. Finally, under alkaline conditions, iodine will disproportionate
to produce iodide and iodate, as follows:

3I2 + 6OH IO3 + 5I + 3H2O

Thus, iodine solutions are generally most stable at neutral pH values. Iodine titrant solutions
must be standardized fairly frequently against a standard arsenate solution. The reaction:

H3AsO3 + I2 + H2O H3AsO4 + 2I- + 2H+

in a strongly acidic solution, arsenate is quantitatively reduced by iodide to arsenate, with

the liberation of iodine; in a solution that is kept neutral during the reaction, arsenite is
quantitatively oxidized by iodine to arsenate. This is in keeping with the principle of mass
action whereby the equilibrium is displaced by a change in the concentration of
hydrogen ion. The former reaction is frequently used in qualitative analysis; the latter
reaction is used as the basis for the iodimetric determination of arsenate and for the
following method of standardizing iodine against As2O3. By making use of both these
reactions, it is possible to determine arsenate and arsenate in the same sample.

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EXPLAIN AND ELABORATE

Materials and Reagents:

Materials:
10mL Pipet Pipettol 250mL Erlenmeyer flask(s)
Weighing bottles Buret clamp Acid/base buret
Iron stand
Reagents:
 KIO3
 3M sulfuric acid
 6N HCl
 Prepared Iodine and Thiosulfate solutions

Methodology:
1. Pipet 50mL aliquot of standard iodate solution into 250mL conical flasks.
2. Introduce 2g of iodate free KI, and swirl the flask to hasten the reaction.
3. Add 2mL of 6M HCl, and immediately titrate with prepared sodium thiosulfate solution
until the solution becomes pale straw yellow.
4. Introduce 5mL of starch solution, and titrate with constant swirling to the disappearance
of the blue color
5. Record readings
6. Make another trial following procedure 1 to 5
7. Calculate the concentration of sodium thiosulfate.

EVALUATE

Answer the following questions.

If 50.0 mL of Thiosulfate solution are required to titrate the I 2 liberated from an excess of
KI by 0.3000 grams of potassium Iodate, calculate

(a) normality of the thiosulfate solution

(b) value of each milliliter of Thiosulfate solution in terms of grams of I 2.

Data and Results

I II

Volume sample

Initial Rdg Na2S2.5H2O

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 Final Rdg Na2S2O3.5H2O

N Na2S2O3.5H2O

Average N Na2S2O3.5H2O

Computations:

Discussion:

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 EXPERIMENT NO. 16
PREPARATION OF IODINE SOLUTIONS

Objectives:
1. To be able to calculate the approximate normal concentration of iodine solutions

ENGAGE AND EXPLORE: Theoretical Discussion

Iodine crystals are not directly soluble in water, which is why most water-based iodine

solutions call for potassium iodide as an ingredient. Iodine is soluble in potassium iodide

solutions. As a general rule, start with approximately one-fourth of the final volume of water

and add the required amount of potassium iodide. Once the potassium iodide has

dissolved, add the iodine crystals. Stir until completely dissolved and bring the solution up

to its final volume. Generally, the more concentrated the potassium iodide solution, the

more readily the iodine crystals will dissolve. Iodine solutions should be prepared in a fume

hood.

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EXPLAIN AND ELABORATE

Materials and Reagents:

Materials:
 Weighing bottle(s)
 Pipetol
 Watch glass (es)
 Stirring rod
 500mL volumetric flask
 10mL pipet (s)
 1000mL beaker
 100mL beaker
 Funnel

Methodology:

1. Weigh about 10g of KI and transfer into a 100mL beaker.

2. Add to it 3.35g of I2 (CAUTION: HIGHLY CORROSIVE) and 10mL of water.
3. Stir for several minutes (or until the solid I2 dissolves).
4. Introduce an additional 20 mL of water and stir again for several minutes.
5. Carefully decant the bulk of the liquid into 250mL volumetric flask containing some
distilled water and dilute to the mark. (It is essential that any undissolved iodine
remains in the beaker).

EVALUATE
Data and Results

N I2

Computations:

Discussion:

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 EXPERIMENT NO. 17
STANDARDIZATION OF IODINE SOLUTION

Objectives:

1. To determine the concentration of iodine solution using a primary standard by means

of direct standardization.

ENGAGE AND EXPLORE: Theoretical Discussion

If a standard iodine solution is used as a titrant for an oxidizable analyte, the technique is
iodimetry. If an excess of iodide is used to quantitatively reduce a chemical species while
simultaneously forming iodine, and if the iodine is subsequently titrated with thiosulfate, the
technique is iodometry. Iodometry is an example of an indirect determination since a
product of a preliminary reaction is titrated. The use of iodine as a titrant suffers from two
major disadvantages. First, iodine is not particularly soluble in water, and second, iodine is
somewhat volatile. Consequently, there is an escape of significant amounts of dissolved
iodine from the solution. Both of these disadvantages are overcome by adding iodide (I –)
to iodine (I2) solutions. In the presence of iodide, iodine reacts to form triiodide (I 3–) which
is highly soluble and not volatile.

The major chemical species present in these solutions is triiodide. The reduction of triiodide
to iodide is analogous to the reduction of iodine. Triiodide reacts with thiosulfate to yield
iodide and tetrathionate. Dilute triiodide solutions are yellow, more concentrated solutions
are brown, and even more concentrated solutions are violet. Iodide solutions are colorless.
If all of the other solution components are colorless, it is possible to detect the endpoint of
titrations involving triiodide without the use of an indicator. Endpoint detection is
considerably easier, however, with an indicator. The indicator that is usually chosen for
titrations involving iodine (triiodide) is starch. Starch forms a dark blue complex with iodine.
The endpoint in iodometry corresponds to a sudden color change to blue. Likewise the
endpoint in iodometry corresponds to a sudden loss of blue color due to the complex.
Potato starch, rather than corn starch, is preferred for making the indicator solution since
the color change due to the starch complex at the end point is sharper. In iodometry the
starch is added only after the color due to triiodide has begun to fade, i.e., near the
endpoint, because starch can be destroyed in the presence of excess triiodide.

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EXPLAIN AND ELABORATE

Materials and Reagents:

Materials:
 10mL pipet
 Weighing bottle(s)
 Iron stand
 Pipetol
 Buret clamp
 250mL Erlenmeyer flask(s)
 Acid/base buret

Methodology:
1. Transfer 25.0 mL aliquot of the prepared iodine solution to a 250mL conical flask.
2. Dilute to about 50mL.
3. Introduce approximately 1mL 3M H2SO4 and titrate immediately with standard sodium
thiosulfate solution until the solution becomes a faint straw yellow.
4. Add about 5mL of starch solution and complete the titration to the disappearance of
the blue color.
5. Record readings.
6. Calculate the concentration of iodine solution.

EVALUATE

Answer the following questions.

If 50.0 mL of Thiosulfate solution are required to titrate the I 2 liberated from an excess of
KI by 0.3000 grams of potassium Iodate, calculate

(a) normality of the thiosulfate solution

(b) value of each milliliter of Thiosulfate solution in terms of grams of I 2.

Data and Results

I II

Volume sample

Initial Rdg Na2S2.5H2O

Final Rdg Na2S2O3.5H2O

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 N Iodine solution

Average N Iodine
Solution

Computations:

Discussion:

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References:

Brown T.E., LeMay E.H. (2014). Chemistry the Central Science 13th Edition : Prentice Hall

Carr J.D. and Hage D.S. (2011). Analytical chemistry and quantitative analysis: Prentice Hall.

Christian G.D. (2013). Analytical Chemistry 7th Edition : John Wiley & Sons

Fifield F.W. (2000). Principles and Practice of Analytical Chemistry 5TH Edition : John Wiley &
Sons.

Gilreath, E. S. (1954). Qualitative Analysis Using Semimicro Methods. New York: McGraw-Hill
Book Company, Inc.

Hamilton L.F, Simpson, S.G. (1947). Calculations of analytical chemistry: McGraw-Hill.

Harris D.C. (2007). Quantitative Chemical Analysis 7th Edition : W.H. Freeman and Company
N.Y.

Scoog, D. A., West, D., Holler, J., & Crouch, S. R. (2014). Fundamentals of Analytical Chemistry
9th ed. Belmont: Cengage Learning.

Skoog D.A. (2013). Fundamentals of Analytical Chemistry 9th Edition: Cengage Learning

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