Results
= 1.4g/ 270.296g.mol-1
Theoretical mass = n × M
= 5.1795×10-5 ×353.17
= 1.8292g
= 0.7705g/ 1.8292g
= 42.12%
The results of the Sherwood magnetic balance for Fe(acac)3 and K3[Fe(CN)6]
Fe(acac)3 K3[Fe(CN)6]
= 5.05×10-7 c.g.s
= 5.05×10-7 × 368.35
= 1.86×10-4 cm3/mol
Diamagnetic susceptibility = 125.66 + 6 × 163.36 + 3 × 187.24
= 1667.54
= 1.86×10-4 cm3/mol
= 0.66 BM
For tris(acetylacetonato)iron(III)
= 2086.01
= 3.37×10-5 cm3/mol
=
0.28 BM
Discussion
The prepared tris(acetylacetonato)iron(III) has the pale red shiny color and weighed o.0.7705 g.
This intense pale red shiny colour was due to ligand to iron charge transfer. The colour also
means that the complex absorbs at blue-green spectrum ranging from 20000 – 21000 cm -1.
From the results above it is now known that tris(acetylacetonato)iron(III) is a weak-field
ligand because it gave lower magnetic moment due to unpaired electrons (lower spin state).
The potassium hexacyanoferrate(III) is a strong-field ligand. The magnetic moment explains
the splitting of d-orbitals the weak field ligand has the lower energy gap between t2g and eg levels
thus pairing electrons is not favored because it requires more energy than promoting an electron to
eg level (Δo<P). And compounds of that nature show a greater paramagnetic property. Whereas the
strong field ligand have Δo >P thus pairing electrons is more favored than promoting an electron
into an e.g. level thus have lower paramagnetic properties.
Conclusion
The main objective of this experiment was successful since the tris(acetylacetonato)iron(III) was
synthesized and found to be 0.7705 g in weight. It appeared to be pale red in color and it was very
shiny. The determined magnetic moment of 0.28 BM which is lower compared to 0.66 BM which
is that of potassium hexacyanoferrate(III) and this is due to weak-field in acac ligand.
Answers to questions
1. The corrected molar susceptibility for [Fe(acac)3] and K3[Fe(CN)6] are 3.37×10-
5
cm3/mol and 1.86×10-4cm3/mol respectively. The calculations are shown above in the
results.
2. The observed magnetic moments for acac and cyanide complexes are 0.28 BM and
0.66 BM respectively also calculations are in the results section.
4. Acac is didantate ligand that coordinates to a metal centre using two oxygen atoms;
thus forming a six membered ring with pi-electrons from oxygen being delocalized
thus stabilizing the complex.
5.
6. The [Fe(acac)3] complex got a high spin due to the number of unpaired electrons i.e.
5 electrons and that describes the extent of d-orbitals splitting. Also acac being a
weak ligand it results in less splitting of d-orbitals i.e. the energy require to pair
electrons is much greater than the energy gap between t2g and eg set of orbitals. This
scenario is mathematically explained using LFSE equation:
=0
The K3[Fe(CN)6] complex comprises of strong ligands thus reducing the number of
unpaired electrons therefore the complex shows low spin. The low spin state is caused by
the strength with which the ligand bonds to a metal centre; if a ligand is strong the splitting
energy gap (Δo) is much smaller than the energy that results from pairing electrons. The
energy of pairing electrons (P) results from electrostatic repulsion from electron which
carries the same charge.
= -2.0 Δo + P
7. The magnetic moment of a compound mainly depends on the number of unpaired
electrons. This is done by summing the spin quantum number for unpaired electrons
then deduce the magnetic moment by the following equation: S = sum of spin
quantum number. μs=2.000x[S(S+1)]1/2
The Fe(acac)3 complex got 5 unpaired electrons therefore the S = 5/2
The experimental obtained magnetic moment value for an acac complex is 0.28 BM.
However the obtained value for K3[Fe(CN)6] is 0.66BM and this value is greater than the
calculated value. From these results the spin only assumption failed and that the orbital
magnetic moment is substantial as well. The magnetism differs from the spin only value and
the angular also contributes to the observed value as there is half filled orbital which
degenerate with paired electron orbitals. Therefore the electrons can migrate around the
centre of complex hence generating the angular momentum and magnetic moment. That
leads to the availability of orbital and that is related by rotation symmetry to occupied
orbitals. The complexes have an odd number of electrons thus meeting the criteria of
contribution by angular momentum.
8. The observed magnetic moments illustrates that the cyanide ligand lies higher in the
spectrochemical series i.e. in the stronger field ligands. Whereas the acac ligand is in the
weaker field ligands (low in the spectrochemical field). This could be explained considering
the favourability of electron pairing which reduces the paramagnetic moments, and due to
that magnetic moment would be lowered. That contrasts with weak field ligands that show
higher magnetic moments because the electron pairing is not favored.
References