Ch.

Redox Determination of Iron

Assigned Reading: R.B. Fischer and D.G. Peters, Quantitative Chemical Analysis, Saunders,
Philadelphia, 1968, pp.12-18, 51-65,536-546; this reference is on reserve in the Chemistry
Library.
Introduction
Iron is one of the most frequently encountered elements in industrial analyses.
Therefore, its accurate determination is of great practical importance. A volumetric
determination of iron consists of these steps:
1. dissolution of the sample
2. quantitative conversion of iron (III) to iron (II) with a suitable
reducing agent
3. removal of the excess reducing agent
4. addition of special reagents to aid in detection of the endpoint and to
ensure that the proper reaction occurs during the subsequent
titration
5. titration of iron (II) to iron (III) with a suitable oxidizing agent
Principles
Dissolution of the Sample
Major components of an iron sample are often iron (II) and iron (III) compounds
that are insoluble in water. These can be dissolved in hot concentrated hydrochloric
acid. Silica, which is present in most natural iron samples, does not dissolve in hot
concentrated hydrochloric acid and may be observed as a white solid material floating
on the surface of the solution; silica will not interfere with the iron determination.
Reduction of Iron (III) to Iron (II)
After the sample is dissolved, the iron will exist mainly as iron (III). Titration
with a standard oxidizing agent requires that all the iron exist as iron (II). A quantitative
reduction of iron (III) to iron (II) can be performed by addition of tin (II) to the hot
hydrochloric acid solution of the sample:
2Fe3+ + SnCl42- + 2Cl-

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2 Fe2+ + SnCl62-

ChapterEight

Tin (II) possesses these advantages as a reductant in this system:

1.

It reduces iron (III) to iron (II) quantitatively and rapidly

2.

It possesses a certain degree of selectivity for iron (III), because it is

not so strong a reducing agent that it reduces other species in
solution

3.

An excess is easily destroyed with HgCl2 so that tin (II) will not
interfere with the redox titration

Due to the presence of chloride complexes of iron (III), the sample solution is
yellow, whereas iron (II) species are colorless. Therefore, tin (II) solution should be
added dropwise to the hot sample solution until the yellow color just disappears. One
drop excess should be added to ensure complete reduction of iron (III).
Removal of Excess Reducing Agent
Excess tin (II) must be destroyed as it will interfere with the redox titration. This
is accomplished by addition of a HgCl2 solution:
SnCl42- + 2HgCl42-

SnCl62- + Hg2Cl2(s) + 4Cl-

If the amount of tin (II) added is in great excess, the following reaction will also occur:
SnCl42- + HgCl42-

SnCl62- + Hg (l) + 2Cl-

Elemental mercury is produced in a colloidal form and will react with the
standard oxidizing agent, thereby ruining the determination. Mercurous chloride
(Hg2Cl2) is a white precipitate that will not interfere with the titration. If the precipitate
is gray or black, elemental mercury is present, and the sample must be discarded.
Addition of Special Reagents; Titration
Special reagents are sometimes added before a redox titration to:
1.

Act as an indicator

2.

Change a half-reaction potential to enhance the sharpness of an

endpoint

3.

Suppress the formation of certain colored complexes in solution

In an acid medium, the reaction between iron (II) and dichromate ion (the oxidizing
agent) is:
6Fe2+ + Cr2O72- + 14H+

6Fe3+ + 2Cr3+ + 7H2O

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RedoxDeterminationofIron

Standard potentials for the half-reactions are:

Fe3+ + eCr2O72- + 14 H+ + 6e-

Fe2+

EO = +0.70 V

2 Cr3+ + 7 H2O

EO = +1.33 V

However, in a 1 M hydrochloric acid medium, the formal potential (EO) for the
dichromate-chromic ion couple is +1.00 V. Note that, under the latter conditions, E is
only +0.30V. To enhance
E, a mixture of phosphoric acid and sulfuric acid is added
to the sample prior to the titration. This lowers the potential of the iron (III)-iron(II)
couple to +0.61 V. Phosphoric acid forms complexes with iron (III), lowering the
concentration of simple Fe3+ ions and decreasing the potential of the iron (III)-iron (II)
couple. Because the new E is +0.39V, the endpoint coincides more closely with the
theoretical equivalence point.
A redox indicator must also be added at this stage. A redox indicator is a
compound that changes color over a potential range of interest due to a reductionoxidation process. Since dichromate cannot serve as its own indicator, the dichromatechromic ion system requires a redox indicator. Chromic ion is green and the dichromate
ion is orange, so the endpoint is masked.
An important family of redox indicators is derived from diphenylamine, a
colorless compound which is oxidized by dichromate to diphenylbenzidine

Diphenylamine (colorless)

Diphenylbenzidine (colorless)

And then to diphenylbenzidine violet:

Diphenylbenzidine violet (violet)

Diphenylbenzidine violet has a deep purple color that is easily seen at the endpoint, even
in the presence of green chromium (III) ions. Note that the diphenylbenzidine-

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diphenylbenzidine violet system is reversible, yielding good indicator behavior.

Dipheylbenzidine violet produced locally in the vicinity of added dichromate will revert
back to the colorless diphenylbenzidine until the true endpoint is reached.
Barium diphenylamine sulfonate will be employed as the indicator since it is more
soluble in water than diphenylamine; the color change for diphenylbenzidine sulfonate is
at E=+087V, which is very close to the endpoint potential for the titration.
Potassium dichromate is an excellent oxidizing agent for iron (II) since:
1.
2.
3.

Dichromate and iron (II) react quantitatively and with a known

stoichiometry
The reaction is sufficiently fast to be practical for a titration and
The E is large enough to produce a well-defined endpoint

Potassium dichromate is a primary standard; it can be purchased as a high-purity solid.

Standard solutions of potassium dichromate can be prepared from a weighed quantity of
the dried solid and need not be standardized; the prepared solutions are very stable.
Procedure
Preparation of a Standard Potassium Dichromate Solution
Transfer approximately 2.45g of reagent-grade potassium dichromate to a clean,
dry weighing bottle. Using a beaker-and-watch-glass arrangement, dry the solid in an
oven at 110OC for one hour. Cool the potassium dichromate in its weighing bottle for at
least 30 minutes in a desiccator. Obtain the weight of the weighing bottle and its
contents to the nearest milligram, transfer the potassium dichromate to a clean beaker,
and reweigh the empty weighing bottle to the nearest milligram in order to determine the
weight of the potassium dichromate by difference.
Dissolve the potassium dichromate by adding a small volume of distilled water
to the beaker. Transfer the solution quantitatively, with the aid of a glass funnel and
stirring rod, to a clean 500-mL volumetric flask.
Note: To ensure that the potassium dichromate solution is transferred
quantitatively, let the solution drain as completely as possible from the beaker into
the funnel. Then place a small volume of distilled water into the beaker, rinse all
the inside surface that had contacted the solution, and add the rinse solution to the
volumetric flask. Two or three repetitions should be sufficient if each drainage has
been as complete as possible and the solution has not beaded on the surface of the
funnel due to improper cleaning.
Add distilled water to the volumetric flask to bring the solution up to the calibration
mark, stopper the flask, and mix the solution thoroughly.

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RedoxDeterminationofIron

Note: Since beading of solution on the inside of the neck of the volumetric flask will
make it impossible to obtain an accurate adjustment of volume, initially clean the
flask thoroughly and check for beading of the distilled water used to rinse the flask.
From the weight of potassium dichromate used, calculate the concentration of the
solution. Be sure to label the volumetric flask containing your standard solution.
Preparation of the Sample Solution
Transfer approximately 2.0 to 2.5g of the iron-containing sample to a clean, dry
weighing bottle. Dry the sample in an oven at 100OC for one hour. Weigh accurately,
to the nearest tenth milligram, portions of the dried sample into each of the three 500mL Erlenmeyer flasks; each sample should contain enough iron to require
approximately 30 to 35 mL of the potassium dichromate titrant. Add 10mL of distilled
water and 10mL of concentrated (12 M) hydrochloric acid to each flask and heat each
mixture gently over a burner in a ventilation hood to dissolve the sample. A residue of
white or gray-white silica can be ignored.
Note: From this point on, take each of the sample solutions separately and
immediately all the way through the final titration before returning to adjust the
oxidation state of iron in the second, and then the third, sample solution.
Adjustment of the Oxidation State of Iron
Heat the sample solution to boiling over a burner in a ventilation hood and add
0.5 M SnCl2 solution drop by drop, while swirling the flask, until the yellow color of
iron (III) just disappears. Then add one or two drops more of the SnCl2 solution. Cool
the solution to a temperature below 25OC and add all at once 10 mL of 0.18 M mercuric
chloride solution. A silky white precipitate should form. If it is gray or black or if no
precipitate forms, an incorrect amount SnCl2 solution was used and the sample must
discarded. After two or three minutes, but not longer, add 150 mL of distilled water and
proceed immediately to the addition of special reagents and the titration.
Addition of Special Reagents; Titration
Add 10 mL of the sulfuric acid-phosphoric acid solution and 8 drops of barium
diphenylamine sulfonate indicator solution. Titrate the solution with standard0.0167 M
potassium dichromate to an endpoint marked by the sudden appearance of a deep violet
color throughout the solution.
Completion of Analysis
With the second and third sample solutions, in turn, repeat the steps of the
procedure involving oxidation-state adjustment, addition of special reagents, and final
titration. From the experimental data, calculate the percentage of iron in each of the
original samples. If the results differ significantly, repeat the analysis with additional
samples of the unknown.
Report all the individual results. If any results are considered invalid, state
clearly the basis for that conclusion and report the average percent of iron as calculated

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ChapterEight

from the titrations deemed to be valid. Also report the standard deviation and the
percent relative range, defined as:
% relative range = ____(100)_(high value low value)______
(average value)
Questions and Problems
1.
a. A standard dichromate solution is prepared by dissolution of 3.143
grams of potassium dichromate in 1.005 liters of water. This is used to titrate a
0.4719 g sample of ferrous sulfate monohydrate, FeSO4 H2O. If the titration
required 43.35 mL of the dichromate solution, calculate the purity of the ferrous
sulfate monohydrate.
b. Suppose that the dichromate solution had been prepared by dissolution
of 3.143 g of sodium dichromate dehydrate in 1.004 liters of water. What
volume of the dichromate solution would have been required to titrate the 0.4719
g sample of ferrous sulfate monohydrate?
2.
Five students carried out the same analytical procedure on five different
samples containing traces of iron; results are given below. Assuming an absence
of systematic errors, calculate the standard deviation (a) of the procedure and (b)
of the mean of three measurements on a single sample. Iron concentrations (in
ppm): student 1, sample C, 44, 47, 48; student 2, sample A, 37, 38, 39, 41, 42;
student 3, sample D, 51, 55, 56, 58; student 4, sample E, 35, 37, 39, 41; student
5, sample B, 46, 49, 52, 54.
3.
An iron determination by a gravimetric procedure yielded an average of
46.03% Fe for six trials; and four trials done according to a volumetric procedure
gave an average of 46.19% Fe, the standard deviation being 0.08% Fe in each
case. Use 95% confidence limits to decide if there is a significant difference in
the results obtained from the two methods.
4.
In a certain semi-micro volumetric determination of iron, the data
obtained with their standard deviations were as follows: initial buret reading,
0.23 mL, s=0.03 mL; final buret reading, 8.82 mL, s=0.02 mL; sample weight,
45.0 mg, s=0.3mg. From these data, find the relative standard deviation (defined
as sX/X) of the final result obtained using the equation below; the atomic weights
used to calculate the equivalent weight are known to within 1 part in 104:
% X = (titrant volume) (equivalent weight) (100)
(sample weight)

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