EXPERIMENT 3

THE PREPARATION OF POTASSIUM TRIS (OXALATO) FERRATE (III)

TRIHYDRATE

PURPOSE
To prepare a special type of compound called a coordination compound in the laboratory.

INTRODUCTION

The compound to be prepared is K3[Fe(C2O4)3].3H2O. its correct name is potassium tris

(oxalate) ferrate (III) trihydrate. The components of this compound are K +, Fe3+, C2O42- and
H2O. the ion C2O42- is called the oxalate ion, and since there are three C 2O42- in the formula
above, and iron is in the 3+ state (indicated by the Roman numeral (III), the complex ion in
the square brackets has a 3- charge, and thus three K+ are required to balance the charge.

During this laboratory period, K3[Fe(C2O4)3].3H2O will be prepared. Ferrous ammonium

sulfate, Fe(NH4)2(SO4)2.6H2O, is dissolved in a slightly acid solution, excess oxalic acid,
H2C2O4, is added, and the following reaction takes place.

Fe(NH4)2(SO4)2.6H2O + H2C2O4 = FeC2O4(s) + H2SO4 + (NH4)2SO4 + 6H2O(l) Eq.1

FeC2O4 is a finely divided precipitate and tends to be colloidal. However heating the solution
causes it to coagulate and facilitates separating the precipitate from the solution.

Potassium oxalate is added to the FeC2O4 precipitate which produces a slightly basic solution
for the oxidation of the ferrous ion to the ferric ion by hydrogen peroxide, H 2O2. The
following reaction takes place:

2Fe2+ = 2Fe3+ + 2e (2e lost)

H2O + HO2- + 2e = 3OH- ____________ (2e gained)
H2O + HO2- + 2Fe2+ = 2Fe3+ + 3OH- (net reaction) Eq. 2

The OH- ion concentration of the solution is high enough so that some of the Fe 3+ reacts with
OH- to form ferric hydroxide(brown precipitate as follows:

Fe3+ + 3OH- = Fe(OH)3 (s) Eq.3

With the addition of more H2C2O4, the Fe(OH)3 dissolves and the soluble complex
K3[Fe(C2O4)3].3H2O is formed according to :

3K2C2O4 + 2Fe(OH)3 (s) + 3H2C2O4 = 2K3[Fe(C2O4)3].3H2O + 3H2O Eq. 4

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Alcohol is added to the solution to cause the complex iron salt to precipitate since it is less
soluble in alcohol than in water. The complexity of the series of reactions described in
equations 1 - 4 may be greatly simplified by following the Fe 2+/ Fe3+ ion throughout. One
discovers that for every mole of Fe(NH4)2(SO4)2].6H2O used as starting material, one mole of
K3[Fe(C2O4)3].3H2O will be obtained as the final product.

Fe(NH4)2 (SO4)2.6H2O + H2C2O4 = FeC2O4 (s) + …etc (see Eq1) (Fe2+=Fe2+)

FeC2O4 + K2C2O4 + H2O2 = Fe(OH)3 (s) + …etc (see Eq 2 &3) (Fe2+=Fe3+)

Fe(OH)3 + H2O2 + K2C2O4 = K3[Fe(C2O4)3].3H2O + ...etc (see Eq 4) (Fe2+=Fe3+)

PROCEDURE

1. Add a solution of 2.5 g of oxalic acid dehydrate in 25 mL of water to a well-stirred

solution of 5 g of ferrous ammonium sulfate in 20 cm 3 of warm water containing 1 mL of
dilute sulfuric acid in the beaker. Slowly heat the mixture to boiling (beware of bumping)
then allow the yellow precipitate to settle. Decant the supernatant. Add 15 mL of hot water
to the solid. Decant the supernatant and add 10 mL hot water.

2. Add 3.5 g solid potassium oxalate monohydrate to the yellow precipitate and heat to
approximately 40oC. Add slowly, using a dropper, while the temperature is at 40 oC,
immediately add 10 mL of 6 % H2O2 drop wise and stir continuously. Periodically check
the temperature of the solution and make sure that it is at least 40 oC (but not >50oC) during
the addition of H2O2 (some brown Fe(OH)3 may precipitate at this time).

3. Heat to boiling, and add a solution of 2 g of oxalic acid dihydrate in 30 mL of water in

portions, add 20 mL initially, then if the brown precipitate still remains, add more solution
little by little until it all dissolves. Boil the clear solution for 5 minutes and filter through a
Buchner funnel with well fitting paper and add 95% ethanol (30 mL) slowly to the
supernatant and leave to crystallize (keep until next week in a dark place).

NEXT WEEK

4. Filter and wash the crystals on the Buchner with a 1:1 ethanol/water mixture and finally
with acetone, (beware fire again). Dry in the air and weigh. Record the crystal actual
weight. The complex is photosensitive and should not be exposed to light unnecessarily.
Store in a sample bottle wrapped in foil.

RESULT AND DISCUSSION

Record the weight of crystal and calculate the percent yield. Show your work.

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 EXPERIMENT 4

DETERMINATION OF THE OXALATE CONTENT OF POTASSIUM

TRISOXALATOFERRATE (III) TRIHYDRATE

PURPOSE
The purpose of this experiment is to standardize the potassium permanganate solution and to
determine the percentage by weight of oxalate in the complex.

PROCEDURE

A. Standardization of potassium permanganate solution.

1. Weigh two 0.1 g samples of the dried Na2C2O4 into conical flask.

2. Dissolve each in about 50 mL of 1 M H 2SO4. Heat each solution to 60oC and titrate with
the KMnO4 solution. Titrate until the first persistent pink color. Repeat at least once.

Weight of sodium oxalate (g)

Burette reading I II

Final

Initial
B. Dete rminatio
n of Volume of KMnO4 (mL) the
oxalate
content of potassium trisoxalatoferrate (III) trihydrate

1. Weigh accurately about 0.2 g of the potassium trisoxalatoferrate (III) complex prepared
previously (experiment 3).

2. Dissolve the sample with 50 mL of 1 M sulfuric acid in a conical flask. Heat the solution
to 60oC and titrate slowly with the potassium permanganate solution provided. Continue
until the warm solution retains a slight pink coloration after standing for about 30 sec.

Weight of pyrolusite ore (g)

Burette reading I II

Final

Initial
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Volume of KMnO4(mL)
RESULT AND DISCUSSION

1. Calculate the exact molarity of the permanganate solution.

Titration reaction:

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

2. Calculate the percentage by weight of oxalate in the complex, compare this with the
theoretical value and thus obtain the percentage purity of the complex.

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 EXPERIMENT 5

PREPARATION AND ISOLATION OF A COMPOUND

A STOICHIOMETRIC STUDY

PURPOSE
To prepare a special type of compound called a coordination compound in the laboratory and
to calculate the % yield of a reaction.

INTRODUCTION
One of the important aspects of any chemical research is the preparation of new compounds.
This process is called synthesis. In this experiment you will synthesize a special kind of
compound called a coordination compound. A coordination compound consists of a metal ion
which is chemically bonded to one or more atoms or groups of atoms by coordinate covalent
bonds. The metal ion contains one or more empty orbitals which can receive pair(s) of
electron and the atom or group of atoms bonded to the metal ion (ligands) contain one or more
pairs of electrons which can be donated to the metal ion. When a covalent bond (a bond
formed by sharing of one or more pairs of electrons) contains a pair of electrons which comes
from only one atom in the bond it is called a coordination covalent bond.

The compound which will be prepared in this experiment is tetraamminecopper(II) sulfate

monohydrate, a coordination compound which also a hydrate. A hydrate is a compound which
contains loosely bound water (called water of hydration) in its structure.

The equation for the overall reaction is:

CuSO4 + 4NH3 + H2O [Cu(NH3)4]SO4.H2O

The synthesis will be carried out in three steps:

(1) The anhydrous copper (II) sulfate CuSO4 will be dissolved in water.

CuSO4(s) Cu2+ (aq) + SO42- (aq)

(2) The dissolved copper (II) ion (in step one) will be reacted with ammonia to form the
complex ion [Cu(NH3)4]2+.

Cu2+ (aq) + 4NH3 (aq) + SO42- (aq) [Cu(NH3)4]2+ (aq) + SO42- (aq)

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 (3) The final product will be precipitate with ethanol in which it is soluble.

[Cu(NH3)4]2+ (aq) + SO42- (aq) + H2O ethanol [Cu(NH3)4]SO4.H2O

The reaction equation for step (2) indicates that one mole of Cu2+, which comes from one mole
of CuSO4, reacts with four moles of NH3 (ammonia) to form one mole of the
tetraamminecopper (II) ion. One mole of coordination compound is produced in step (3) from
one mole of the tetraamminecopper (II) ion; therefore, in the overall reaction, one mole of
coordination compound is obtained for every one mole of copper (II) sulfate reacted. The
amount of ammonia required to react with any given amount of copper (II) sulfate can be
calculated from the equation in step (2).

The amount of coordination compound expected from a given mass of copper (II) sulfate can
be calculated and is called the theoretical yield. The actual mass of coordination compound
synthesized, called the actual yield is usually less than the theoretical yield. The efficiency of
the synthesis is expressed as a percent yield:

% yield = __Actual yield x 100

Theoretical yield

Careful work should produce a percent yield for this experiment between 80-90 %.

SAFETY DISPOSAL METHODS

Addition of ammonia should be performed under the hood. Disposal of the filtrate should be
done in the drains under the hood with lots of water running. The precipitate should be
disposed of in the labeled container under the hood.

PROCEDURE

Part I. Preparation of the compound.

1. Weigh accurately about 2.00 g of anhydrous copper (II) sulfate to the beaker. Record the
weight of the copper (II) sulfate on your report sheet.

2. Add 20 mL of distilled water to the beaker and stir to dissolve the copper (II) sulfate.
Leave the stirring rod in the solution. Note the color of the solution, which is due to the
copper (II) ion, on your report sheet.

3. Under the hood, add the required volume (as designated by the instructor) of concentrated
ammonia to the beaker and stir until any precipitate is completely dissolved. The first
addition of ammonia may cause a light blue precipitate of copper (II) hydroxide to form,
but this should dissolve to form the tetaamminecopper (II) ion upon further addition of
ammonia.

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 Note any color changes on your report sheet which occur during the addition of ammonia.
The color of the solution is due to the presence of tetraamminecopper (II) ion.

4. While stirring the solution in the beaker, add 20 mL of ethanol. Fill a container half full of
crushed ice, position the beaker containing your compound in the crushed ice, and allow
its contents to cool for about 10 minutes. Record your observations during the cooling on
your report sheet.

Part II. Isolation of the compound by vacuum filtration.

1. Set up a vacuum filtration flask as shown in the figure below.

2. Place a piece of filter paper into the Buchner funnel so that all the holes are covered.
Moisten the paper with water. Connect the vacuum tubing from the filter flask to the
vacuum outlet at your desk.

3. Turn the vacuum handle until it is in the completely open position. Press down on the
Buchner funnel to set the adapter in tightly and ensure a good vacuum.

4. Pour the cold solution in the beaker and the precipitate into the Buchner funnel. When all
the liquid has passed through, turn off the vacuum.

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5. Pour 5-8 mL of ethanol into the beaker and rinse any remaining precipitate into the
Buchner funnel. Stir CAREFULLY to avoid tearing the filter paper. Turn on the vacuum
again and pull the liquid through. Turn off the vacuum and wash the precipitate by adding
5 mL of acetone to the funnel, stirring carefully. Turn on the vacuum and pull the wash
liquid through. Repeat the washing one more time with a second 5 mL portion of acetone,
turning off the vacuum between washings. After the second washing, allow the suction to
continue for 2-3 minutes to speed the drying of the product.

6. Remove the product from the Buchner funnel with your spatula and place it on a glass
plate. Spread the product out on the plate and allow the product to dry overnight in the
oven.

7. Record the weight of the product on your report sheet.

RESULT AND DISCUSSION

Using the equations for the three-step synthesis of tetraamminecopper (II) sulfate
monohydrate, calculate the following. Show your work.

1. The number of moles of CuSO4 in 2.00 g of CuSO4.

2. The number of moles of Cu2+ in 2.00 g of CuSO4 (see equation 1).

3. The number of moles of NH3 required for complete reaction with all the Cu 2+ (see equation
2).

4. How many grams of [Cu(NH3)4SO4].H2O should be produced in the reaction of 2.00 g

anhydrous CuSO4 with an excess of NH3?

5. Calculate the % yield of your synthesis.

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