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TITLE

Synthesis of KwFex(C2O4)y(H2O)z

AIM

Preparation of iron (II) oxalate

THEORY
Transition metal complexes are ions or compounds formed between transition metal
ions (Lewis Acids) and a variety of organic and inorganic anions or neutral molecules,
called ligands (Lewis bases).
The iron (II) ion d6, [Fe (H2O)6]2+ gives many crystalline salts. Mohr's salt,
Fe(NH4)2(SO4)2is reasonably stable towards air and loss of water, and is commonly
used to prepare standard solutions of Fe2+ for volumetric analysis and as a calibration
substance in magnetic measurements.

Oxalate complexes are coordination compounds produced by reacting oxalic acid with a
transition metal. Nearly all compounds of transition elements are coordination
compounds with the central metal a Lewis acid and the atoms or molecules attached to
it Lewis bases. These Lewis bases are called ligands, and the metal and molecules
bound to it are called the Coordination Sphere. When writing a chemical formula, the
coordination sphere is denoted by brackets such as [Cu(C2O4)2(H2O)2] for the cupric
oxalate complex. For these oxalate complexes, the copper (Cu) is the transition metal
acting as a Lewis acid and the oxalate ion (C2O4)2- complexes with water (H2O) to form
the Lewis base. Once the oxalate complex has been synthesized, it will then be
analyzed using spectroscopy and titration. Infrared spectroscopy will help to determine
whether the produced product is the intended oxalate complex while UV-visible
spectroscopy or a titration with potassium permanganate (KMnO4) helps to determine
the amount of metal in the oxalate complex.
Iron (II) oxalate is decomposed by heat to give iron (II) oxide, carbon dioxide and carbon
monoxide.

Iron (II) oxalate mechanismIts name is potassium trisoxalatoferrate (III) trihydrate


with the molecular formula K3Fe(C2O4)3.3H2O.
Reaction for the synthesis

3K+ + Fe2+ + 3C2O42- + 3H2O + 1/2 H2O2 K3Fe(C2O4)3.3H2O

This reaction can further be broken down into the following reactions:

The iron (II) oxalate dihydrate, Fe(C2O4). 2 H2O is mixed with basic potassium oxalate
solution and an orange intermediate complex of Fe (II) and an oxalate forms,
K2Fe(C2O4)2.2H2O

Fe(C2O4). 2 H2O + 2K+ + C2O42- K2Fe(C2O4)2.2H2O orange solid

K2Fe(C2O4)2.2H2O is oxidized to Fe(III) with hydrogen peroxide (H2O2) forming a brown


precipitate of iron(III) hydroxide(a base).

K2Fe(C2O4)2.2H2O + 1/2 H2O2 2K+ + 2C2O42- + Fe3+ + OH- and

Fe3+ + 3OH- Fe(OH)3 (brown solid)


Upon the addition of more oxalic acid, H2C2O4, the iron(III) hydroxide dissolves. The
Fe(III) in solution with oxalate undergoes complex ion formation yielding Fe(C2O4)33-
which gives the solution a clear lime green color.

3H+ + Fe(OH)3 3H2O + Fe3+ and

Fe3+ + 3C2O42- Fe(C2O4)33- (clear lime green solution)

The ionic product, the K+ salt of the complex ion, is very water soluble but only slightly
soluble in ethanol. Addition of ethanol followed by cooling, allows the product to
crystallize.

3K+ + Fe(C2O4 )33- + 3H2O K3Fe(C2O4)3. 3H2O(s)

Chemical reaction of oxalate: Oxalate is an excellent ligand for metal ions, where it
usually binds as a bidentate ligand. The affinity of divalent metal ions is sometimes
reflected in their tendency to form insoluble precipitates. Thus oxalic acid combines with
potassium to form crystals of the corresponding oxalate.
To determine the oxalate ion, a sample of known mass of K 3Fe(C2O4)3. 3H2O is titrated
with standardized potassium permanganate:

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


Procedure:

 Measured 1.0004g Fe(NH4)2(SO4)2.6H2O. Transferred to a 200ml test tube


 3ml of deionized water and 5-7 drops 6M H2SO4 added. Swirled mixture to
dissolve the salt.

 5ml of 1M H2C2O4 was added to the above solution. A yellow precipitate


(FeC2O4) formed.

 Approximately added 5-7 drops of 6M H2SO4, thereafter placed test tube in a


boiling water bath, to digest the precipitate.

 20mL of deionized water was boiled.

 Test tube was cooled. Precipitate settled, decanted and discarded the
supernatant.

 The precipitate was washed with 2-3ml hot deionised water. The precipitate was
washed twice.

 2ml of 2M K2C2O4 was added to the solid precipitate, FeC2O4,

 The solution was warmed mixture for 10mins in a hot water bath with constant
swirling.

 8ml H2O2 was slowly added to the solution in the test tube. A brown solid was
formed.
 The reaction mixture was heated in the water bath for about 5 minutes.

 2ml of 1M H2C2O4 was added dropwise. A yellow green solution appeared.

 5ml of ethanol was added to the solution. Green crystals were formed.

 The solution was heated in the water bath to dissolve the crystals.

 The test tube was wrapped in aluminum foil and stored.

 A week later large emerald green crystals were present in the test tube

 The crystals were filtered, washed with acetone and air-dried crystals. Mass=
0.6580g

3B
 Weighed out 3 samples of the coordination compound into 3 Erlenmeyer flasks.

 Added 30ml deionised water and 5ml of 6M H2SO4. Dissolved sample.

 Heated each solution and titrated with standardized KMnO4.

Properties of reagents:

Reagent Molecular Melting Point Density Description


Weight (C) (g/cm3)
(g/mol)
Oxalic Acid 126.07 101
dihydrate
Potassium 184.215 2.217 Hygroscopic
oxalate
monohydrate
Ammonium 392.13 100 1.864 Light/air
iron (II) sensitive
sulfate
hexahydrate
KmnO4 158.0 Strong
oxidant

Safety precautions
It is advisable to wear safety goggles, safety shoes, cloves and protective clothing
during the whole duration of the experiment due to the use of toxic and corrosive
substances like oxalic acid and sulphuric acid and these should be used under the fume
hood.

Experiment 3A
Aim: Synthesis of KwFex (C2O4) y (H2O) z

Results:
Mass of Fe (NH4)2(SO4)2.6H2O weighed: 1.0094g

Mass of crystals + watch glass + filter paper: 14.2015g


Mass of watch glass + filter paper: 13.1906g
Mass of crystals: 1.0109g

Calculations
Fe (NH4) (SO4)2.6H2O + H2C2O4  FeC2O4 (s) + H2SO4 + (NH4)2SO4 + 6H2O (l)
FeC2O4 + K2C2O4 + H2O2  Fe (OH) 3

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

Calculating the Limiting Reagent


Moles of Fe (NH4) (SO4)2.6H2O:

𝑚𝑎𝑠𝑠
Moles of Fe (NH4) (SO4)2.6H2O =
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

1.0004 𝑔
=
392.02 𝑔/𝑚𝑜𝑙
= 2.552 x 10-3 moles of Fe (NH4) (SO4)2.6H2O

Moles of H2C2O4:

𝑚𝑎𝑠𝑠
Density of H2C2O4 =
𝑣𝑜𝑙𝑢𝑚𝑒
Mass of H2C2O4 = Density x Volume
= (1.653 g/ml) (5ml)
= 8.265 g of H2C2O4
𝑚𝑎𝑠𝑠
Moles of H2C2O4 =
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

8.265𝑔
=
90.13 𝑔/𝑚𝑜𝑙
= 0.09170 moles of H2C2O4

The limiting reagent is Fe (NH4) (SO4)2.6H2O

Theoretical mass of K3 [Fe (C2O4)3]. 3H2O:

3K2C2O4 + 2Fe (OH) 3 + 3H2C2O  2K3 [Fe (C2O4)3].3H2O + 3H2O

1.0004 g Fe (NH4)2(SO4). 6H2O x 1 mol Fe (NH4)2(SO4). 6H2O

392.02 g Fe (NH4)2(SO4). 6H2O


Mole ratio of Fe (NH4)2(SO4). 6H2O to FeC2O4 is 1:1

1 𝑚𝑜𝑙 𝐹𝑒2+ 2 𝑚𝑜𝑙 𝐹𝑒3+ 1 𝑚𝑜𝑙 𝐹𝑒(𝑂𝐻)3


= 2.552x10-3 mol FeC2O4 x 1 𝑚𝑜𝑙 𝐹𝑒𝐶2𝑂4 x 2 𝑚𝑜𝑙 𝐹𝑒2+
x 1 𝑚𝑜𝑙 𝐹𝑒3+

2 mol K3 [Fe (C2O4)3].3H2O


= 2.552x10-3 mol Fe(OH)3 x 2 𝑚𝑜𝑙 𝐹𝑒(𝑂𝐻)3

= 2.552x10-3 mol K3[Fe(C2O4)3.3H2O

𝑚𝑎𝑠𝑠
Moles of K3 [Fe (C2O4)3].3H2O =
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

Mass of K3 [Fe (C2O4)3].3H2O = 2.552x10-3 mol x 491.21 g /mol

= 1.2535 grams of K3 [Fe (C2O4)3].3H2O

Percentage yield of K3 [Fe (C2O4)3].3H2O:

𝐴𝑐𝑡𝑢𝑎𝑙 𝑀𝑎𝑠𝑠
% Yield = x 100%
𝑇ℎ𝑒𝑜𝑟𝑒𝑐𝑡𝑖𝑐𝑎𝑙 𝑚𝑎𝑠𝑠

0.6580
= x 100 %
1.2535

=52.50%
Experiment 3B

Aim: Analysis of oxalate in KwFex (C2O4) y (H2O) z

Introduction

In this experiment, KMnO4 will be standardize with H2C2O4 , after standardization potassium
permanganate will be titrated with the unknown complex sample to determine the % of Oxalate ion
presented in the complex KwFex (C2O4) y (H2O) z.
KMnO4 in titration reduces errors brought about by the use of chemical indicators since excess
permanganate can already determine the end point of titration. In this case, Permanganate serves as a
self-indicator, which under acidic conditions, becomes pale pink by the presence of Mn2+. In addition,
Mn2+serves as auto catalyst, which is directly proportional to the speed of the reaction, causing an
increase in the speed with an increase in the concentration of Mn2+

The reaction of permanganate with oxalate involves an oxidation-reduction reaction (Redox)


with half reactions given by:

Reduction half reaction: MnO42- + 8H + 5 e-  Mn2+ + 4H2O


Oxidation half reaction: C2O42-  2CO2 + 2 e-
Overall Reaction: 2MnO42- + 16H+ + 5 C2O42-  2Mn2+ (aq) + 8H2O (l) + 10 CO2 (g)

INTRODUCTION
This experiment is continuing from experiment 3A, here the oxalate content in the
potassium trisoxalatoferrate(III) trihydrate (complex prepared in part 3A) is determined
using a standard solution of potassium permanganate. Potassium permanganate
(KMnO4) is a useful REDOX titrant because it is its own indicator. The intense purple
colour of the permanganate ion (MnO4-) changes to the very pale pink (almost
colourless) of Manganese(II) ion as the MnO4- is reduced.

MnO4- can be reduced in a variety of ways depending on the reaction conditions,


especially pH. In neutral solution one of the main products is hydrated manganese(IV)
oxide. This at first gives the solution of a brown colour and finally gives a brown
precipitate. Under alkaline conditions the permanganate ion is reduced to the green
manganate ion. Under acid conditions the permanganate ion is reduced further to the
very pale pink manganese(II) ion. For this titration, reduction to the manganese(II) ion is
required, so the titration must be done under acidic conditions. Permanganate ion
oxidizes oxalate ion to carbon dioxide gas in the following reaction.

In acid solution, potassium trisoxalatoferrate(III) provides iron(III) and oxalate ions.


Iron(III) is not oxidized by permanganate ion so the oxalate can be titrated directly.

However, oxalate ions react only slowly with permanganate ions at room temperature,
so the solution must be warmed to about 60oC in order for the reaction to be fast
enough to be useful in a titration.
RESULTS AND CALCULATION

STANDARDISING

Moles of H2C2O4:

H2C2O4.2H20
Mass weighed: 0.7875g

0.7875𝑔
Moles = = 6.25x10-3 moles of H2C2O4
126𝑔.𝑚𝑜𝑙

0.00625 𝑚𝑜𝑙
[H2C2O4.2H20] = = 0.025M
0.025𝐿

Sample no. Volume of KMnO4


(ml)
Initial Final Actual
1 0.00 19.60 19.60
2 0.00 19.60 19.60
3 0.00 19.50 19.50
Average Volume of KMnO4 Titrated: 19.57ml

2MnO4- + 5H2C2O4 + 6H+ -> 2Mn2+ + 10CO2 + 8H2O


𝐶1𝑉1 𝐶2𝑉2
= 𝑁2
𝑁1
(0.025𝑀)(20.00𝑚𝑙) 𝐶2(19.00𝑚𝑙)
=
5 2
C2 = 0.0102 M of KMnO4
MASSES OF SAMPLE KwFex (C2O4) y (H2O) Z WEIGHED FOR EACH TITRATION:

Sample 1: 0.1018 g
Sample 2: 0.1069 g
Sample 3: 0.1013 g

Sample no. Volume of KMNO4


(ml)

Initial Final Actual

1 0.10 24.75 24.65


2 0.00 25.85 25.85
3 0.00 24.60 24.60

Average: 25.03ml

2MnO4- + 5H2C2O4 + 6H+ -> 2Mn2+ + 10CO2 + 8H2O

Moles of permanganate used to titrate iron (iii) – oxalate complex:


𝑛
c=
𝑉
n=𝑐𝑥𝑉

1. (0.0102 M KMnO4)(24.65 x 10-3L KMnO4) = 2.5143 x 10-4 moles of KMnO4


2. (0.0102 M KMnO4)(24.85 x 10-3L KMnO4) = 2.6367 x 10-4 moles of KMnO4
3. (0.0102 M KMnO4)(24.58 x10-3L KMnO4) = 2.5092 x 10-4 moles of KMnO4

Moles of Oxalate Titrated by Permanganate:


2MnO4- + 5H2C2O4 + 6H+ -> 2Mn2+ + 10CO2 + 8H2O

1. (2.5143x10-4mol Mn04-) (5mol H2C2O4/ 2mol MnO4-) = 6.286 x10-4 moles of H2C2O4
2. (2.6367x10-4mol Mn04-) (5mol H2C2O4/ 2mol MnO4-) = 6.592 x 10-4 moles of H2C2O4
3. (2.5092x10-4mol Mn04-) (5mol H2C2O4/ 2mol MnO4-) = 6.273 x 10-4 moles of H2C2O4
Percentages of each Oxalate ion present in the sample KWFeX (C2O4) y (H2O) Z:

1. = 6.641 x10-4 mol x 88.00 g/mol C2O42-


= 0.05844 grams of C2O42-
0.05844 𝑔
= 0.1034 𝑔 𝑥 100
= 56.52 %

2. = 6.340 x 10-4 mol x 88.00 g/mol


= 0.05579 grams of C2O42
0.05579 𝑔
= 0.1066 𝑔 𝑥 100
= 56.20 %

3. = 6.452 x 10-4 mol x 88.00 g/mol


= 0.05678 grams of C2O42
0.05678 𝑔
= 0.1006 𝑔 𝑥 100
= 56.44 %

Using the data given in Question 2:

Calculation of the moles of Oxalate ion


5 𝑚𝑜𝑙 𝑜𝑓 𝐶 2 𝑂42− 26.1 𝑚𝑙 𝑜𝑓 𝐾𝑀𝑛𝑂4
= 𝑥 𝑥 0.010 𝑀
2 𝑚𝑜𝑙 𝑜𝑓 𝑀𝑛𝑂4− 1000 𝑚𝑙
= 6.5275 x 10⁻⁴ moles

Calculation of the percentage of Oxalate ions present in 0.100 g of sample:


= 6.5275x10-4mol x 88.00 g/mol
= 0.05506 grams of C2O42-
0.05506 𝑔
= 𝑥 100
0.100𝑔
= 55.07 %

DISCUSSION OF RESULTS
The experiment confirmed the presence of the oxalate ion by titration analysis .The
titration of the oxalate was performed using potassium permanganate as the oxidizing
agent, from the titration amount of oxalate present in a sample was determined.
As for spectroscopic method which involved the reagent being added to form a coloured
complex with analyte, the more intense the colour, the greater the quantity of analyte
present.
 The addition of 1M H2C2O4 to the Fe(NH4)2(SO4)2.6H2O solution should bring
about a yellow precipitate. My reaction took a while for the precipitate to settle,
not waiting for this to happen, I added 6M H2SO4 and placed it into the boiling
water bath. By adding the 6M H2SO4 It was digesting the precipitate, however by
not waiting I had no precipitate to digest. I wasted time and reagents in this way.
 The colour of the precipitates and solutions in this experiment is interesting. The
yellow precipitate of Fe(C2O4)2. 2 H2O, the brown precipitate of Fe(OH)3 and the
lime green solution of Fe(C2O4)33- and finally the emerald green crystals of the
desired precipitate, K3Fe(C2O4)3. 3H2O.
 Molecular Weight of K3Fe(C2O4)3. 3H2O = 491.2 g/mol
Oxalate ion in K3Fe(C2O4)3. 3H2O = 264g/mol
% oxalate ion = 53.75%
% Yield obtained = 55.07%
This variation could be due to missing the end point during titration. The
sample may have been over tritrated.

REFERENCES
1) Basic Inorganic Chemistry; F.A. Cotton; G. Wilkinson & P.L.Gaus; John
Wiley&Sons; 3rd edition; pagrs465-467
2) Modern Inorganic Chemistry; G.F. Liptrot; 4th edition; pages 58-61
1. http://chemfinder.cambridgesoft.com
2. http://academic.bowdoin.edu/courses/so2/chem109/laboratory/dissem