Synthesis and characterization of
Vanadyl acetylacetonate complex
[VO(acac) 2 ]
Group 1
Roll No.- 1 to 7
INDEX
◦ Introduction
◦ Theory
◦ Procedure
◦ Calculation
◦ Result
◦ Characterization
◦ References
Apparatus Required- Chemical required-
Conical flask Vanadium pentoxide
Beaker conc. Sulphuric acid
Buchner funnel ethanol
acetylacetone
◦ Reaction Involved- V2O5 + 2H2SO4 + C2H5OH —> 2VOSO4
+3H2O + CH3CHO
VOSO4 +2acacH + Na2CO3 —> VO(acac)2 + Na2SO4 + H2O + CO2
Color samples
Vanadium Oxide Vanadyl complex
◦ THEORY
Vanadium belongs to group 5 and its
atomic no –23. Vanadium exhibits four
common oxidation states +5,+4,+3,+2 .
Acetylacetone- It is classified as a 1,3-
diketone. Acetylacetonate ion contains
two O atoms which allow this ligand to
function as a bidentate ligand.
◦ Acetylacetone(2,4-pentadione) is a diketone. The carbon atom of the CH 2
group is between the 2 carbonyl group is α -carbon and the hydrogen attached
to it are acidic. This is due to the presence of 2 electron withdrawing carbonyl
compounds. The α-hydrogen may be easily lost to water to produce an anion
stabilized by resonance as shown below:
◦ Keto enol form of acac
◦ Acac
is a weak acid ,deprotonation can be facilitated by reaction with Bronsted
–Lowry base(CO3)2- . Deprotonation results in a bidentate ligand.
◦ Resonance forms stabilize neutral and anionic forms of ligand.
Oxygen atoms are the Lewis bases in this ligand with -1 charge.
◦ The acetylacetonate anion can then act as a ligand towards the oxovandium
cation to produce VO(acac)2.This ligand bonds to the metal ion through both
its oxygen atom and hence a six membered aromatic ring is produced as shown
below:
◦ Oxidation state of V = +4
◦ Structure- Square pyramidal
◦ Paramagnetic
◦ Refluxing with pyridine causes further metal-ligand coordination
and produces VO(acac): py . IR spectroscopy is useful then in
distinguishing between the vibrational energy of the dark blue-
green VO(acac)2 and greyish VO(acac):py.
◦ In the solid state ,VO(acac)2-type complexes are five coordinate ;
however ,upon dissolution in organic solvents , the vanadium
coordinates or donor ligand in the vacant site , generating
products expressed as [VO(acac) 2L] where L = coordinated
ligand.
PROCEDURE
1. 0.5g of vanadium(V) oxide was taken in a conical flask and then 0.8ml of conc. sulfuric
acid was added to that followed by the addition of 2.5ml ethanol solution.
2. The reaction mixture was heated on water bath and stirred to obtain a dark blue solution.
The solution of vanadium(V) oxide and its reduction to vanadium (IV) was completed 30
minutes .
3. The solution was filtered and the filtrate was taken in a fresh beaker.
4. Acetylacetone was added dropwise to the filtrate with shaking.
5. The solution was neutralized by adding 2g of sodium carbonate dissolved in 2-3ml of
distilled water was added slowly to avoid excessive frothing.
6. The resulting mixture should be cooled in a ice water bath and the precipitated product
was washed with cooled water and then filtered using suction pump .
7. Dry the product and weighed it .
8. The dried product was recrystallized from chloroform solution .
9. Report the % yield and determine its melting point .
Calculation
• Density of sulphuric acid = 1.83 gram/ml
• Molecular mass of ethanol =
98.079gram/mole
• We know that, density = mass/ volume
• 1.83 = mass / 0.8 ml ( given in
procedure)
• Mass of sulphuric acid = 1.464 gram
• Moles = mass/ molecular mass
• n = 1.464/ 98.079
• n= 0.0149 moles
• Therefore number of moles of sulphuric acid is 0.0149 moles
• Similarly for millimoles 0.0149 * 10³ milli moles
• Calculation of Amount of Acetyl acetatonate (acac) used:
• V2O5 : acacH = 1:4
• One mole of V2O5 react with 4 moles of (acacH)
• Amount of vandyl pentoxide used = 0.5 gram
• Molecular mass of vandyl pentoxide= 181.88 gram /mole
• Moles of V2O5 is : 0.5/ 181.88
• n = 0.00274 moles
• Number of moles of vandyl pentoxide is 0.00274 moles
• Now, 0.00274 moles of vandyl pentoxide react with 4*0.00274 moles of
acetylacetonate
• Therefore total number of moles of (acac) = 0.0108moles
• Amount of acetyl acetatonate used :
• Molecular mass of acac = 100.13 gram/mole
• Therefore amount of acac used is = 0.0018*100.13
• Mass of acac = 1.0814 gram
Calculation of yield
• V2O5: VO (acac)2 = 1:2
• We know that amount of V2O5 is 0.5 gram and Molecular mass is 181.88gram/mole
• Therefore number of moles of V2O5 is 0.5/181.88
• Moles of V2O5 = 0.00274 moles
• 0.00274 moles of V2O5 react with 2*0.00274 moles of VO(acac)
• Hence number of moles of vandyl acetyl acetatonate is 0.0054 moles
• Molecular mass of VO(acac) is 265.15 gram/mole
• Therefore amount of VO(acac) is 0.0054*265.15
• Weight of VO(acac) = 1.483gram
• Yield of complex is 1.483 gram
Result
• Colour of Vandiumpentaoxide = Oragne ( solid)
• Colour of vandyl acetyl acetatonate= Dark blue green (solid)
• Theoretical yield = 1.483 gram
• Melting point VO(acac)2 = 258°C, 498F, 531K
• Boling Point VO(acac)2 = 174°C, 346F, 447 K
• Solubility of VO(acac)2 in CHCl3, Benzene , CH2Cl2 etc.
Characaterization
1. IR Spectroscopy
Infrared Spectroscopy:-
• Infrared spectroscopy is the measurement of the interaction of infrared radiation with matter by
absorption, emission, or reflection. It is used to study and identify chemical substances or functional
groups in solid, liquid, or gaseous forms.
Principle of IR:-
When the energy in the form of IR is applied,
And if the applied IR frequency= Natural frequency of vibration, the absorption of IR takes place and a
peak is observed.
Molecules are excited to the higher energy state from the ground state when they absorb IR radiation.
When a compound is exposed to IR radiation, it selectively absorbs the radiations resulting in vibration of
the molecules of compound, giving rise to closely packed absorption bands, called as IR absorption
spectrum. The bands correspond to the characteristic functional groups and the bonds present in a
chemical substance. Thus, an IR spectrum of a compound is considered as the fingerprint for its chemical
identification.
Note:- Only molecules containing covalent bonds with dipole moments are infrared active.
• Fourier transform infrared spectroscopy is a technique
used to obtain an infrared spectrum of absorption or
FTIR:- emission of a solid, liquid or gas. The main aim is to
measure the amount of light absorbed by a sample at
each wavelength.
• It is a non-destructive, time saving method, can detect
range of functional groups and is sensitive to
change in molecular structure.
• KBr is used as a carrier for the sample in IR spectrum.
Because, KBr has a transmittance of 100 % in the range
of wave number (4000-400 cm-1 ). Therefore, it does not
exhibit absorption in this range .
FT-IR spectrum of
[VO(acac)2] complex
Characteristic band
995 cm-1 V=O bond stretching
1558-1377 cm-1 CO stretching
1535-(1320-1270) cm-1 CH3 bending
1200-1000 cm-1 (CH3-C) vibration mixed with the out of plane
vibration
• V=O stretch at 995 cm-1 in VO(acac)2 shifts to 965 cm-1 in pyridine
complex.
• In the range 1200-1000 cm-1, the IR spectra contain bands attributed
to (CH3-C) vibrations mixed with out of plane vibrations( distortions of
the C-C-C angles),i.e., the vibration associated with the deviations of
methyl groups from the planes of the ligand rings. The in-plane
vibrations of the cyclic fragments manifest themselves at frequency of
950 cm-1. These vibrations involve simultaneous stretching of the C-C
bonds and changes in the angles between these bonds. The vibration
of C-C exo bonds are observed at slightly lower frequencies in the range
characteristic of the V(CC) vibrations. The frequency of the vibrations
associated with the deviations of the C-H bonds from the ring plane is
approx. equal to 800 cm-1.
Fig: FT-IR spectrum of [VO(acac)2] complex.
TGA (Thermal Gravimetric Analysis)
It is a branch of analytical science where the It is a thermo-analytical method. Principle- A technique in which the mass of
properties of analyte are studied as they sample is measured as a function of
change with temperature. temperature/time.
Instrumentation
• Small amount of sample is heated at constant heating rate or held at
constant temperature(isothermal measurement).
• For TG method we require a thermo-balance.
• Thermo-balance- It is used to detect or record the change in mass of
substance/analyte which is being heated.
• The result of TGA is displayed at TGA curve of %mass Vs
temperature/time.
DTG Curve
• It is a rate of change of mass with respect to temperature/time Vs
temperature/time.
• Simply a first derivative of %mass Vs temp./time.
• DTG curves tells more easy way to visualize the decomposition
temperature or time.
• Area under the DTG curve will give the mass change
TGA & DTG Curve
• Heating rate
• Sample mass
Factors affecting TG • Furnace atmosphere
curves • It is useful for solid samples only.
• Processes with no change in mass
will not observe. eg.- Melting
Interpretation of TGA curve
•TGA curves of different reactions -
•A- Thermal decomposition with the formation of gaseous product.
•B- Corrosion ,oxidation of metals.(formation of non volatile oxides,M2O3 ,
MO)
•C-combustion of carbon black on switching on to gases from nitrogen to
oxygen.
•D-Multi-step decomposition.
•E- Explosive (steep decrease) decomposition
UV-Vis Spectroscopy
•UV-visible spectroscopy is type of absorption spectroscopy in
which light of ultraviolet visible region (200-800nm) is absorbed
by the molecule which results in the excitation of the electrons
from the ground state to higher energy state.
•Principle:-
The principle is based on the measurement of spectrum of
a sample containing atoms / molecules. Spectrum is a graph
of intensity of absorbed or emitted radiation by sample versus
frequency (ʋ) or wavelength ()ג.
Important terminologies
in UV – Vis Spectroscopy
• Chromophore
• Auxochrome
• Bathochromic or red shift
• Hypsochromic or blue shift
• Hyperchromic effect
• Hypochromic effect
Factors affecting the position and shape of UV bands
• Effect of conjugation
• Effect of solvent
• Effect of pH
• Effect of temperature
Factors affect the absorbance in UV- Vis spectroscopy
• Concentration
• Path length of the substance
Characterization:-
UV – Vis spectrum of complex recorded in DMF from 200-800 nm.
Absorption maximum observed at 235 and 284 nm is due to the
intraligand π- π* and n - π* transitions. A broad band
appeared with its absorption maximum at 430 nm are due to
d –d transitions that observed in the visible region.
Fig :- UV-Vis spectrum of VO(acac)2 complex.
References:-
• Asadi, M., Ghatee, M.H., Torabi, S., Mohammadi K., & Moosavi, F. (July 2010). Synthesis,
characterization, ab initio calcultions thermal behaviour and thermodynamics of some
oxovanadium(IV) complexes involving O,O-and N,N-donor moieties. J. Chem.Sci., 122(4),
539-548
• Nenashev, R.N., Mordvinova, N.E., Zlomanov, V.P., & Kuznetsov, V.L, (2015), Inorganic
Materials, Original Russian Text, 51(9),891-896.
• Fedorova, E.V., Rybakov, V.B., Senyavin, V.M., Anisimov, A.V., & Aslanov, L.A. (2005).
Synthesis and structure of Oxovanadium (IV) Complexes [VO(Acac)2] and [VO(Sal:L-aniline)
(H2O)]. Original Russian Text, 50(2), 224-229.
Thank You
