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ID: 1205675
Experiment details: -
Number: 2
Introduction:
The acetylacetonate anion can then act as a ligand towards the oxovanadium cation to
produce VO(acac)2. This ligand bonds to the metal ion through both its oxygen atoms and,
hence, a six membered, weakly aromatic ring is produced:
Refluxing with pyridine causes further metal-ligand coordination and produces VO(acac)2Py.
IR spectroscopy is useful then in distinguishing between the vibrational energies of the dark
blue-green VO(acac)2 and greyish VO(acac)2Py.
Apparatus:
250 ml beaker
10 ml measuring cylinder
Glass rod
Heating mantle
Buchner funnel
FTIR spectrometer
Materials:
Vanadium(V) oxide
Absolute ethanol
Acetylacetone
Dichloromethane
Diethyl ether
Toluene
Pyridine
Procedure:
3. The mixture was refluxed by using heating mantle. The mixture was swirled while
heating to avoid any precipitate formed at the wall of the round bottom flask.
4. After an hour, the colour of mixture turned from green and blue.
5. A little ethanol was added to make the dark solution less viscous. The solution was
filtered through a cotton wool.
6. The filtrate was transferred to 250 ml beaker and was added with 3.5 ml
acetylacetone.
9. The product was recrystallized. The product was dissolved in minimum warm
chloroform.
10. The impurities were filtered and the filtrate was cooled in an ice bath.
11. About 10-20 ml diethyl ether was added until precipitate occurs.
12. The product was filtered, washed with cold ether and air dried. The yield was
recorded.
1. The half of the product from Part 1 was dissolved in about 20 ml toluene and was
refluxed for 30 minutes with a large excess (6 ml) of pyridine.
2. The resultant solution was concentrated to a smaller volume by distilling off the
toluene and pyridine.
3. The solution was cooled down and crystals were formed in ice bath.
Results:
Part 1:
Mass of V2O5 1.0019 g
Mass of petri dish 33.2020 g
Mass of VO(acac)2 with petri dish 34.7790 g
Mass of VO(acac)2 1.5770 g
Part 2:
Calculations:
Part 1:
mass
Mole of V2O5 =
molar mass
1.0019 g
=
181.88 g/mol
= 0.011 mol
= 2.92 g
actual mass
Percentage yield = * 100%
theoretical mass
1.5770 g
= * 100%
2.92 g
= 54.0 %
Part 2:
1VO(acac)2 + Py 1VO(acac)2Py
1.5770 g
Mole of VO(acac)2 = mole of VO(acac)2Py =
265.157 g /mol
= 2.047 g
0.6794 g
Percentage yield = * 100%
2.047 g
= 33.19 %
Discussion:
In the first part of the experiment, Vanadium pentoxide, V2O5 was refluxed with
concentrated H2SO4, water and ethanol for an hour, reduces V2O5 to (VO)2+. Orange V2O5
dissolves in the colourless solvents to form a dark green (VO)2+ solution.
1
V2O5 + 4H+ 2(VO)2+ + 2H2O + O2
2
The vanadium (II) ion, VO2+ was chelated with 2 acac anions to form blue-green
[VO(acac)2]. The mass recovered from recrystallization is 1.5770g with percentage yield of
54.0 %. This dark blue-green complex has a square-based pyramidal geometry and is able to
accommodate one more ligand as shown below:
bis(acetylacetonato)oxovanadium(IV)
Sodium carbonate, Na2CO3 was added in order to remove the excess H+ from the
ionisation of acacH and concentrated H2SO4 so as to drive the reaction to completion. By Le
Chateliers principle, with the removal of H+ ions, the equilibrium of the reaction is shifted to
favour the formation of the VO(acac)2 complex.
Pyridine adduct
In the second part, pyridine and the complex was mixed with toluene as the pyridine
is miscible in organic solvent. Pyridine has a lone pair of electrons on the N atom which can
be used to bind with the central vanadium ion to form a 6-coordinated complex. The overall
structure of the grey complex, VO(acac)2Py, is an octahedral. The mass of the complex
recovered after recrystallization is 0.6794 g with percentage yield of 33.19%.
V2O5, VO(acac)2 and VO(acac)2Py are coloured compounds because they absorb light
in the visible region. The energy of the absorbed photon corresponds to the energy gap
between vanadium ions d-orbitals. The colour of the compound observed is complementary
to that of the absorbed light.
The percentage yield for VO(acac)2 was 54%. This amount of yield is above 50 % and
considered to be moderate.. Theoretically, more time is required to leave the mixture to stand
in an ice bath for crystallisation after Na2CO3 is added in order to produce a higher yield of
VO(acac)2. More amount of base may be added to favour the formation of the desired product
as well.
As the reagents may be toxic, gloves were worn to protect the hands. This is
especially important when handling corrosive reagents such as concentrated sulphuric acid.
The experiment was carried out in the fume hood to prevent any inhalation of harmful
organic vapours. The flammable reagents such as pyridine, toluene and acetylacetone were
also placed away from naked flames. The most significant precaution in the entire
experiment is that men are to be cautious during handling the pyridine as it can cause
infertility and chronic exposure can cause harm. Boiling chips were added during reflux to
avoid bubbling. Lastly, a magnetic stirrer should be added to the round bottom flask to further
ensure homogenous mixing of the reagents, thereby speeding up the reaction.
From the IR spectra, it was observed that the V=O stretching mode of VO(acac)2 was
at 997 cm-1 while that of VO(acac)2Py, 937 cm-1. The addition of pyridine into the square
geometric VO(acac)2 complex caused the vibration frequency of V=O stretching to decrease
by 60 cm-1. When the pyridine forms coordinate bond with the VO(acac)2, it introduces a lone
pair of electrons from nitrogen into the d-orbital of the oxovanadium ion. This increases the
electron density around the vanadium ion and thus, results in electron-electron repulsion
between the V=O bond. V=O bond lengthens and weakens in order to minimise the repulsion.
Therefore, the band shifts to a lower wavenumber. The difference between these two spectra
is that in the pyridine adduct spectrum has more addition peaks compared to VO(acac)2
complex. This may be attributed to the presence of pyridine which affects the absorption
peaks due to the distortion of the adjacent bonds. However, the 997 cm-1 peak still appeared
in the pyridine adduct spectrum which means that the pyridine adduct is not pure and the
reaction was not totally completed. In general, the two spectra are fairly similar for the two
complexes having similar structures.
Exercise:
2. Structure of aquabis(acetonato)oxovanadium(IV).
Conclusion:
Reference:
Chemical Safety Data: Pyridine. 2017. Chemical Safety Data: Pyridine. [ONLINE]
Available at:http://www.edu.upmc.fr/chimie/chiminorga/MSDS/Pyridine.htm.
[Accessed 27 March 2017].
Pyridine - Wikipedia, the free encyclopedia. 2017. Pyridine - Wikipedia, the free
encyclopedia. [ONLINE] Available at: https://en.wikipedia.org/wiki/Pyridine.
[Accessed 27 March 2017].