EXPERIMENT III

Determination of Iron in Iron Oxide, (Fe2O3), Using Dichromate Method

Chemical Overview

This is a direct titration using K2Cr2O7, a primary standard, as the titrant. As

such the analysis is especially sensitive to the determination of the end point.

Reactions:

(1) Fe2O3 + 6 H+ → 2 Fe3+ + 3 H2O

(2) Sn+2 + 2 Fe3+ → Sn+4 + 2 Fe2+

(3) Sn+2 + 2Hg2+ + 2Cl- → Hg2Cl2(s) + Sn+4

(4) Sn+2 + Hg2+ → Hg0(s) + Sn+4

(5) K2Cr2O7 + 6Fe2+ + 14H+ → 2Cr3+ + 6Fe3+ + 7H2O

HCl reacts with Fe2O3 to generate Fe+3 (iron III). Stannous chloride (SnCl2) is
added, to a slight excess, converting iron III, Fe+3 to iron II, Fe+2. The reaction mixture
now contains Fe+2, Sn4+, and Sn2+. (The iron II is relatively unstable and subject to air
oxidation). Since Sn2+ is subject to oxidation by K2Cr2O7, the Sn+2 must first be
converted to Sn+4 state before the titration is started. Mercuric chloride (HgCl2), a mild
oxidizing agent, is added to the solution which converts the excess Sn2+ to the Sn4+
state while leaving iron II unreacted and forms Hg2Cl2, a milky white precipitate as a
product. This step also tests if:
1) Too large an excess of Sn II was added (reaction (4) takes place) and Hg0
(black precipitate) forms. This sample must be discarded as Hg0 can be oxidized by
K2Cr2O7.
2) Insufficient Sn II has been added, which results in no Hg2Cl2 (a white
precipitate) forming. This indicates that all of the Fe3+ was not converted to the Fe2+
state. This sample must also be discarded.

Purpose

1. Test of procedual skills learned in Experiments I and II. Since this experiment
uses a primary standard solution directly, both your weighing techniques and how
precisely you detect your end point will effect your results.
2. To learn the subtleties of redox reaction which allow selective reaction in a
solution containing several different ions.

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Terms: Direct titration, oxidation, reduction, primary standard.

Procedure Overview

I. Prepare Potassium Dichromate

II. Dissolution of iron ore
You may stop analysis at this point. Cover samples with plastic wrap and
store. Each sample is treated individually from this point on as Iron (II) is
easily oxidized by air.
III. Prereduction of Iron (III)
IV. Titration of Iron (II)

Procedure

I. Preparation of Potassium Dichromate (K2Cr2O7)

Equipment: unribbed watch glass

600 ml beaker
500 ml volumetric flask

1) On a clean, dry, preweighed unribbed watch glass, weigh 2.452X grams ± 0.1
gram of primary standard potassium dichromate (That is, weigh between 2.352X and
2.552X grams.) Record the weight to four decimal places.

2) Quantitatively rinse the watch glass into the 500 ml beaker.

3) Transfer the diluted dichromate to a 500 ml volumetric flask.

Quantitatively rinse the beaker. Dilute to mark.

4) Calculate the molarity of solution: Note that if the weight is not exactly 2.452
grams, the normality will not be exactly 0.1000. You are calculating molarity.

Formula:

1 mole K2 Cr 2 O7
grams K 2 Cr 2 O7 × × Purity
M.Wt. K 2 Cr2 O 7
Molarity K2 Cr 2 O7 =
Volume in liters

II. Dissolution of iron ore (Fe2O3 → 2 Fe3+)

Equipment: 4-500 ml conical flasks

4 ribbed watch glasses (Speedyvaps)

1) Weigh 0.35XX gram ( ± 0.1 gram) samples of the iron oxide unknown into 4
flasks. You may have to discard the other three samples and adjust the grams of
unknown used if the first titration uses more or less than 35 ml ± 5 ml. This is a
time saver gamble. If your first reduction of iron III fails you have back up unknown
samples prepared. However because the amount of iron varies in different unknowns,
the milliliters of titrant, potassium dichromate, used per unknown sample may fall out

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side the range of 30 to 40 milliliter. If this occurs, you will need to scrap the remaining
weighed unknowns and adjust your sample weights according to the ml/wt. ratio of
your first titration.

2) Add 10 - 15 ml of 12 M. Hydrochloric acid (HCl) to each flask. Swirl to mix,

cover with ribbed watch glasses.

3) On the heaters in hood, evaporate solution to about 5 ml. There may be

precipitation of iron salts due to concentration.

4) Dilute each solution to 15 ml with distilled water. This will usually dissolve any
precipitated salts.

Samples may be covered with plastic wrap and stored at this point.
From here on do each solution individually to completion.

III. Prereduction of Iron (III) to Iron (II)

Equipment: 2 small beakers

eye dropper
100 ml graduated cylinder
10 ml graduated cylinder

1) In the hood, heat flask #1 with the Iron (III) solution to boiling. While the
solution is heating, prepare the chemicals for the prereduction step.

2) Preparation of chemicals: put small amounts of 0.5 M. Stannous chloride and

0.25 M. Mercuric chloride into beakers.

Measure 10 ml of Mercuric chloride into 10 ml graduated cylinder

Measure 50 ml of distilled water into 100 ml graduated cylinder

3) Remove the flask (boiling) from heat.

4) DROPWISE, add 0.5 M. Stannous chloride until the yellow iron solution is
reduced to light green ( Iron (II) ). You may not be able to detect the light green color of
the iron (II) unless your initial solution was very concentrated. The solution may simply
go from yellow to colorless or very faint green. Do not add more than 2 drops excess.

5) Cool to room temperature.

6) Add 50 ml of distilled water, stir rapidly (or swirl flask).

7) Using a 10 ml graduated cylinder, add all at once 10 ml 0.25 M Mercuric

chloride. Mercuric chloride is added all at once to avoid reducing the mercuric ion to
mercury metal.

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 8) Wait 3 minutes. If your reduction was carried out properly, the precipitate in
the flask will appear to be "silky white" at this point. The actual appearance depends on
the amount of excess stannous chloride added. Too much causes greying of the
precipitate and the loss of the silky appearance. A white precipitate should form, but
may appear cloudy. If no precipitate at all forms, there was no excess stannous
chloride, discard the sample. If the precipitate is dark grey or black, mercury metal
is present, discard the sample. While waiting the 3 minutes, clean and fill buret with
K2Cr2O7.

IV. Titration of Iron (II)

1) Prepare:

a) Using 100 ml graduated cylinder to measure,.prepare 200 ml of distilled

water in a beaker.

b) Wear Safety Goggles.1:5 Sulfuric acid (H2SO4) is prepared by first

adding 8 ml distilled water to a 10 ml graduated cylinder followed by then, adding 2 ml
concentrated H2SO4.

c) Add 5 ml of 85% Phosphoric acid to a separate graduated cylinder.

d) Sodium or barium diphenylamine sulfonate is all prepared in a dropper

bottle.

2) Immediately after 3 minutes if a white precipitate forms:

Add in rapid sequence:

200 ml of distilled water

10 ml of 1:5 H2SO4
5 ml of 85% Phosphoric acid
8 drops of Na or Ba diphenylamine sulfonate
Swirl flask to mix

3) Place the flask on a magnetic stirrer and put a clean stirring bar in the
solution. Titrate slowly with potassium dichromate solution. The end point is a color
change from blue-green to grey to purple. At the grey point proceed titrating dropwise
to purple. After the endpoint is reached the color may revert back to grey or blue-green
if the solution stands for a while.

4) Remember, if the amount of potassium dichromate used to titrate is not about

35 ml, discard the 3 remaining iron sample solutions and adjust the unknown sample
weight so that you will be using about 35 ml of potassium dichromate in the titration.

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 5) Repeat steps from III. Prereduction of Iron (III) with the 3 remaining samples,
if titration of first was about 35 ml.

Repeat from the beginning if you are adjusting weight of unknown.

6) Calculations:

a) Percentage of iron in sample:

Formula:

6 mole Fe
Vol.(L)K 2 Cr 2 O 7 × M K 2 Cr 2 O 7 × × At. Wt. Fe × 100%
1 mole K 2 Cr 2 O7
% Fe =
gms unknown

b) Find the mean %Fe.

c) Find the mean deviation.

d) Fine the RMD in ppt.

Notes

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Notes

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Notes

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Notes

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