Paramagnetism

Narrabundah College
 Transition Metals
The Transition Metals, d-block elements, in particular the first row, contain metals which have similar
properties and characteristic features. Most patterns can be explained by consideration of the electrons in the
outer shells or energy levels.

One of the characteristics of transition metals is that they can be paramagnetic.

Paramagnetism is caused by the presence of unpaired electrons in the d-orbitals, and results in these
elements/complexes being weakly attracted by a magnetic field.

The more unpaired electrons that are present, the stronger the magnetic property.

Paramagnetism is weak magnetism that a substance has when it contains unpaired electrons.

When all electrons in the substance are paired the substance is called diamagnetic.

Knowing if a substance is or is not paramagnetic can be useful to help in the determination of shape in some
complexes.

To test the degree of magnetism, a Gouy balance can be used. The more unpaired electrons present, the
greater the attraction to the magnets, which can be seen on the scale. Using this, the number of unpaired
electrons can be determined.
Transition Metals
 Transition Metals
Paramagnetism is easily observed in the salts of some of the first-row transition metals (manganese through
nickel). These metal ions have unpaired electrons in degenerate d orbitals as predicted by Hund's rule and thus
exhibit paramagnetism.

But strong-field ligands can split the energy levels of the d orbitals so that they are no longer degenerate. Salts
of these ions that have strong-field ligands are diamagnetic. Water is not attracted to the magnet poles; water is
diamagnetic.

In the following slides we can see an example of simply determining paramagnetic character of a range of salts.

A series of compounds in small vials is brought close to the poles of a large, strong permanent magnet.
The vials contain a number of compounds
(NaCl, MnSO4, FeSO4, CoCl2, NiSO4, ZnSO4, K4[Fe(CN)6], [Co(NH3)6]Cl3, [Ni(NH3)6]Cl2, and H2O)
and they are hung from a thread.

When the magnet is brought near, some of the vials are attracted. A ruler is used to measure the deflection of
the thread from the vertical, which correlates with the number of unpaired electrons.
Transition Metals
 Transition Metals
NaCl
When a sample of sodium chloride is brought near the poles of the magnet, there is no attraction of the sodium
chloride to the magnet, even when the vial strikes the magnet. There are no unpaired electrons in sodium
chloride and sodium chloride is diamagnetic.
 Transition Metals
MnSO4
Manganese(II) sulphate is strongly
attracted by the magnet, which
shows that it is paramagnetic.
Manganese ions in manganese(II)
sulphate have five unpaired
electrons.
 Transition Metals
FeSO4
Iron(II) sulfate pentahydrate can be
brought closer to the magnet than
the manganese(II) sulfate
monohydrate, but eventually it
swings toward the magnet. This
compound is not as strongly
paramagnetic as the manganese(II)
sulfate. Iron(II) ions have four
unpaired electrons.
 Transition Metals
CoCl2
Cobalt (II) chloride can be brought
closer to the poles than the iron (II)
sulphate or the manganese (II)
sulphate before it swings toward the
magnet. Cobalt (II) ions have three
unpaired electrons.
 Transition Metals
NiSO4
When nickel (II) sulphate is brought
near the poles of the magnet, it
appears to have about the same
attraction as the cobalt (II) chloride,
perhaps slightly less. Nickel (II) ions
have two unpaired electrons.
 Transition Metals
ZnSO4
Zinc (II) sulphate is brought near
the poles of the magnet. As in the
case of the sodium chloride, there
is no attraction between the zinc
sulphate and the magnet. The
degree of paramagnetism of these
compounds of the transition metals
can be correlated with the number
of unpaired electrons in their metal
ions.
 Transition Metals
K4[Fe(CN)6]

A sample of potassium
hexacyanidoferrate(II) is shown to
be diamagnetic. The d orbitals in
the iron (II) ions are split by the
strong crystal field of the cyanide
ligands, allowing all six electrons to
pair.
 Transition Metals
[Co(NH3)6]Cl3
Hexaamminecobalt(III) chloride is
not attracted to the poles of the
magnet. As in the case of the
hexacyanoferrate(II) ion, the strong
field of the ammonia ligands splits
the d orbitals and allows all
electrons to pair.
 Transition Metals
[Ni(NH3)6]Cl2
Hexaamminenickel(II) chloride is
attracted weakly to the poles of the
magnet. It has two unpaired
electrons.
 Transition Metals
H2O
A sample of liquid water is tested
and it is not attracted to the magnet
poles; water is diamagnetic.
Task
Transition Metals
Classify each compound below as either paramagnetic or diamagnetic

a) [CoCl4]-

b) [Zn(H2O)6]2+

c) [Mn(H2O)6]2+

d) Which ligand generates a stronger magnetic octahedral complex ion when bound to Fe2+: H2O or CN- ?

e) In [ZnI4], the zinc ion has eight valence electrons, d8. If it is found to be diamagnetic, does it occupy a tetrahedral or square
planar geometry?

f) For each of the following coordination complexes, identify if it is paramagnetic or diamagnetic?

i) octahedral, low spin, d4

ii) octahedral, low spin, d6

iii) tetrahedral, high spin, d4

iv) square planar, low spin, d8

Transition Metals
Answers

Classify each compound below as either paramagnetic or diamagnetic

a) [CoCl4]- Cobalt is 3+ ion, so there are 6 d electrons. Chlorido is a weak ligand and will not force pairing,

there are four unpaired electrons ∴ (in a tetrahedral structure) paramagnetic.

b) [Zn(H2O)6]2+ There are no unpaired electrons so is diamagnetic.

c) [Mn(H2O)6]2+ Five unpaired electrons, so paramagnetic.

d) [Fe(H2O)6]2+ the iron ion is a d6, water is a weak ligand ∴ Δ is small, CN is 6,

∴ octahedral splitting

In [Fe(CN)6]4- the iron ion is still d6 but the cyanide is a strong ligand
so Δ is large, CN still 6 so octahedral splitting

Therefore with H2O as ligand, the complex will be more paramagnetic, more unpaired electrons
Transition Metals
Answers
e) The splitting pattern for the two geometries differ and hence the electron configuration from adding the 8
electrons will differ. The tetrahedral geometry has two unpaired electrons and the square planar geometry has
zero. Since [ZnI4] is diamagnetic, ∴ it must have square planar geometry.

f) For each of the following coordination complexes, identify if it is paramagnetic or diamagnetic?

i) octahedral, low spin, d4 paramagnetic

ii) octahedral, low spin, d6 diamagnetic

iii) tetrahedral, high spin, d4 paramagnetic

iv) square planar, low spin, d8 diamagnetic