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Synthesis and Analysis of

Aadil Khan |21416042


Transition metal ions react with charged or neutral ligands, L, (e.g. Cl– or H2O) to form complex
ions. Iron in the +3 oxidation state can form octahedral complexes with up to 6 unidentate
ligands surrounding a central metal ion (Figure 1). The ligands act as Lewis bases, donating at
least one pair of electrons to the Fe3+ ion. Oxalate ion, C2O42–, acts as a chelating bidentate
ligand, donating 2 electron pairs from 2 oxygen atoms to the transition metal center, Fe3+ (Figure
2). During the first week of this experiment a coordination compound with the formula
KxFey(C2O4)z·nH2O will be synthesized. A coordination compound typically contains a complex ion
(with ligands bound to a central metal cation), counter ions, and, sometimes, waters of hydration.
During the second week the empirical formula of the coordination compound will be determined
(i.e., the values of x, y, z, and n) by redox titration and gravimetric analysis.

Figure 1. Octahedral Fe3+ complex surrounded Figure 2. Octahedral Fe3+ complex with 1
by unidentate ligands, L (e.g., Cl–, NO2–, H2O, bidentate oxalate ligand, C2O42–, which donates

or NH3). Each L donates 1 e- lone pair forming 2 e- lone pairs to form 2 bonds.

a bond to Fe3+.
1) AIM
To synthesis and analyse KwFex(C2O4)y(H2O)z for oxalate and iron(III).


Part A: Synthesis of KwFex(C2O4)y(H2O)z

 1g of Fe(NH4)2(SO4)2. 6(H2O was weighed and transferred into a 200 mm test tube. Thereafter, 3
mL of deionized water and several drops of 6 M sulphuric acid was added to the sample and the
resulting mixture was swirled to dissolve the salt.
 5 mL of 1 M oxalic acid was measured using a graduated cylinder and transferred to the sample
solution. A yellow iron oxalate precipitate formed at this step.
 Several drops of 6M sulphuric acid was added to the sample solution to digest the precipitate.
The reaction mixture was then placed in a boiling water bath for ≅ 10 min with occasional
 The reaction mixture was cooled to allow the precipitate to settle. And Once reaction mixture was
cooled, the supernatant was decanted and discarded into the “waste acids container”.
 The precipitate was washed three times with 2-3 mL of hot deionized water. (washings were
discarded into the “waste acids container”).
 2-3 mL of 2 M K2C2O4 was added to the precipitate and the mixture was warmed to ≅ 40 °C in a
water bath.
 Slowly and with constant swirling, 8 mL of 6 % H2O2 was added to the mixture ensuring that the
temperature of the solution did not exceed 60 °C. A brownish solid formed at this step.
 Thereafter, the reaction mixture was heated for several minutes in a boiling water bath. The test
tube was then removed from the water bath and 2 mL of oxalic acid was added dropwise. A
yellow-green solution containing the coordination compound formed at this step.
 5 mL of 95 % ethanol was added to the solution and green crystals formed immediately. The
test tube was then stoppered and wrapped in aluminium foil and stored for a week.
Part B: Analysis for oxalate in KwFex(C2O4)y(H2O)z
 A sodium oxalate solution was prepared and used to standardize a 0.01 M KMnO4 solution.
 0.01 g of the green crystals were weighed and transferred into a 125 mL Erlenmeyer flask. 30
mL of deionized water and 5 mL of 6 M sulphuric acid was added to the sample. The sample
mixture was then swirled to dissolve the sample.
 Step 3 was repeated twice to obtain triplicate samples for analysis.
 The first sample solution was heated to ≅ 60 °C and then titrated with KMnO4 solution to a
pale pink colour endpoint that persisted for at least 30 seconds.

Table 2: Composition of standard tris-Bipyridyliron (II) solutions

Vol. of stock standard tris-Bipyridyliron (II) Vol. of deionized water/

Standard test solution
solution / mL mL
1 1 9
2 2 8
3 3 7
4 4 5
5 7 3

 The spectrophotometer was calibrated at a wavelength of 520 nm and % Transmittance of each

test solution was measured.

Measurement of the amount of Iron in the coordination compound:

 0.1 g of the coordination compound synthesized in part A of the experiment was weighed and
transferred into a 100 mL volumetric flask. Without disturbing the precipitate, 5 mL of 6 M
sulphuric acid and 20 mL of 0.5 M CaCl2 was added to the sample solution. The solution was
swirled and diluted to the calibration mark and the then left to stand to allow the precipitate to
 To a 50 mL volumetric flask 15 mL of deionized water and 2 pinches of ascorbic acid was added.
Using a 10 mL graduated pipet, more than 2mL of the solution prepared in step 1 was dispensed
into the 50 mL volumetric flask. 20 mL of 0.0020 M bipyridyl solution was added and the solution
was diluted to the calibration mark with the buffer solution (pH ≅ 4.7).
 A set of test solutions were prepared in the same manner as the standard solutions in Part C1
step 4. The calibration of the spectrophotometer was repeated and % transmittance was
measured for the 5 test solutions.
The calculated yield of the salt was 79.80%. which is an effective yield. yield of 70.67% is
considered fair for the effectiveness on the synthesis of Iron(III) Oxalate Complex in Experiment
#4A. There are several reasons for the synthesis to have a lower yield: First, as stated in the
observation from Experiment #4A, it was suspected some loss of the Iron(II) ammonium
sulfate hydrated salt in the process of transferring. Also, the possible loss of precipitate
when washing or left in the stirring rod and glassware can attribute a smaller percent yield.
An observation worth mentioning was the appearance of the crystals synthesized. The
crystals were jasmine green small “rocks” with white powder on top. The white powder
could be an indication of a source of error. The solution might not have been mixed well
during the synthesis, resulting a possible product other than the one expected. This could
have greatly affected the results of the analysis of the Iron(III) Oxalate Complex, and it
might have attributed to the incorrect composition number in the empirical formula of the
The answer to the proposed questions are as follows
1 in calculations
2 Peroxide
3 FeC2O4 + K2C2O4 + H2O2  Fe (OH) 3

4 30 FeC2O4 + 27 H2O2 + 6 K2C2O4 + 4 H2O = 4 K3[Fe(C2O4)3]3H2O + 18 Fe(OH)3

5 An explanation for the ability of polar solvents to dissolve certain salts such as NaCl is that
water has a high dielectric constant (about 80) and is thus able to separate the Na+ cations from
the Cl- anions. (Roughly speaking, dielectric constant is the ability to “hide” charges by
polarization of the medium; in the case of polar solvents, this polarization mostly involves
orientation of the molecules

6 Its photosensitive and aluminium reflects sunlight, the top was sealed to prevent moisture from
entering and contaminating the formation of crystals
For the titration part(3B) the results were very precise. Although precision does not imply accuracy,
it does mean that the data of the experiment is fairly consistent. Possible errors that might deviate
from accuracy should be still considered. First, the possible loss of solid Iron(III) Oxalate Complex
when transferred can create a difference between the expected dissolved mass and the actual
dissolved mass, which can overestimate the weight % of the oxalate calculated and affect the later
calculations for the composition of the compound. Another possible error is the variation of
the color end point in the titration trials. Different ratios between the titrant and the analyte can
create solutions that might have overshot. For instance, as mentioned in the
observations in Experiment #4B, the end point from all 4 trials vary from having a faint
pink that disappeared in 30 seconds to a slight darker pink that is suspected to have
overshot ½ to 1 drop of titrant. These can cause deviation during calculations for weigh%
for oxalate from the actual value. Although, during volumetric analysis, splashes of titrant
left on the flask walls are usually a potential error to consider, in Experiment 3B,
however, the titrant is dark enough to notice any drops, therefore the potential error is
minimal to negligible. At last, all reagents and solutions are exposed to contamination that
might have affected the results.

Experiment 3A--‐B shows
a fairly accurate determination of the empirical formula through the results of a
wide variety of analysis suitable for different composites in compound, Iron(III)
Oxalate Complex. While some composites are suited for titrations, others are
suited for spectrophotometry, demonstrating a wide amount of options to
perform analytical chemistry. In the real world, analytical chemistry is often
used to analyze the composition of the atmosphere in factories and even to
monitor the level of toxic substances in facory workers to ensure their health.


1 http://www.guidechem.com/cas-516/516-03-0.html
2 http://chemister.ru/Database/properties-en.php?dbid=1&id=2084
3 Sigma-Aldrich Co., Iron(II) oxalate dihydrate. Retrieved on 2014-05-03.
4 Echigo, Takuya; Kimata, Mitsuyoshi (2008). "Single-crystal X-ray diffraction and spectroscopic studies on
humboldtine and lindbergite: weak Jahn–Teller effect of Fe2+ ion". Phys. Chem. Minerals. 35: 467–475.
5 Hermanek, Martin; Zboril, Radek; Mashlan, Miroslav; et al. (2006). "Thermal behaviour of iron(II)
oxalate dihydrate in the atmosphere of its conversion gases". J. Mater. Chem. 16: 1273–1280