CHEM F343

Magnetism
 Magnetic Properties of Transition Metals
 Much of our understanding of transition metals comes from magnetic
data.

 Molecules with only closed shells of electrons have no inherent magnetic

properties. But, when placed in a magnetic field, a small magnetic
moment will be induced opposed to the field. These diamagnetic
molecules are, therefore, repelled by the magnetic field.

 Most transition metals do have unpaired electrons. These paramagnetic

compounds do have magnetic properties resulting from both the spin and
orbital motion of the unpaired electron. They are attracted into a
μa μb
magnetic field.
 Magnetic Properties of Transition Metals

Origin of Paramagnetism from Classical Physics:

Spin angular momentum; the spinning charge gives rise to a

magnetic moment, μ, in the direction perpendicular to the spin.

Orbital angular momentum; due to the electron spinning around the

nucleus.

μa μb
 Magnetic Moment
• The magnetic moment of a single electron, μs, is given (according to wave
mechanics) by μs = g√ s (s + 1) B.M.
where g = gyromagnetic ratio ≈ 2
s = absolute value of the spin quantum number
B.M. = Bohr-magneton (eh/4πme)

• For example, Ti+3 (d1) μs = 2√ ½ (½ + 1) = 1.73 B.M.

• Also, μs = √ n (n + 2) B.M. where n = number of unpaired electrons.
• For a multielectron case, μs = g√ S (S + 1) B.M. where S = total spin
quantum number
• For example, Mn+2 (d5) h.s., μs = 2√ 5/2 (5/2 + 1) = 5.92 B.M.

— — — — —
S = ½+½+½+½+½ = 5/2
 Magnetic Moment

μs = √ n (n + 2) B.M. where n = number of unpaired electrons.

when n = 1 μ = 1.73 B.M.
n = 2 μ = 2.83 B.M.
n = 3 μ = 3.87 B.M.
n = 4 μ = 4.90 B.M.
n = 5 μ = 5.93 B.M.
ΔH = B – Ho Ho = Applied mag. Field
B = Induced field inside the sample
ΔH = -ve (diamagnetic)
4I = B – Ho ΔH = +ve (paramagnetic)
I = intensity of magnetisation
= Magnetic susceptibility per unit
4 = (B / Ho) – 1 volume (I / Ho)
= specific (mass) mag. susceptibility

=/d M = molar mag. susceptibility

MW = molecular weight

M =  . (MW)
 Instrumentation/Experimentation
• Don’t measure μobs directly, but do measure magnetic susceptibility, Χ, and
then calculate magnetic moment:

μobs = 2.828 √ X ● T(K) B.M.

 Using Magnetic Susceptibility Data

A chromium complex has X = 0.0100 at 300 K, what is its oxidation state?

μobs =
 Using Magnetic Susceptibility Data

• The following compounds have the indicated χ values at 300K. Describe the
structure of each.
1. [NiF6]-2 χ = 0.00
6-coordinate Ni+4 d6
could be either high spin or low spin
μobs =

2. Ni(PEt3)2Cl2 χ = 0.00
4-coordinate Ni+2 d8
could be either tetrahedral or sq. planar
μobs =

3. Ni(Ph3AsO)2Cl2 χ = 0.00333
4-coordinate Ni+2 d8
could be either tetrahedral or sq. planar
μobs =
 Using Magnetic Susceptibility Data

• The following compounds have the indicated X values at 300K. Describe the
structure of each.
1. [NiF6]-2 X = 0.00 ─ ─
6-coordinate Ni+4 d6 ─ ─ ─
could be either high spin or low spin
μobs =

2. Ni(PEt3)2Cl2 X = 0.00 ─
─
4-coordinate Ni+2 d8
─ ─ ─
could be either tetrahedral or sq. planar ─
μobs =
─ ─
─ ─

3. Ni(Ph3AsO)2Cl2 X = 0.00333
4-coordinate Ni+2 d8
could be either tetrahedral or sq. planar
μobs =
 Using Magnetic Susceptibility Data

• The following compounds have the indicated X values at 300K. Describe the
structure of each.
1. [NiF6]-2 X = 0.00 ─ ─ ─ ─
6-coordinate Ni+4 d6 ─ ─ ─ ─ ─ ─
could be either high spin or low spin
μobs =

2. Ni(PEt3)2Cl2 X = 0.00 ─
─
4-coordinate Ni+2 d8
─ ─ ─
could be either tetrahedral or sq. planar ─
μobs =
─ ─
─ ─

3. Ni(Ph3AsO)2Cl2 X = 0.00333
4-coordinate Ni+2 d8
could be either tetrahedral or sq. planar
μobs =
Theoretical Versus Experimental Moments
 Theoretical Versus
Experimental Moments

• Look at Ion, S, μs, and observed moments.

• Notice that for many ions, the μs and the μobs values are fairly consistent, for
others, the μs is not even close.
• This is because μs is a “spin-only” momentum.
• For some transition metals, there is an orbital angular momentum contribution.
• The magnetic moment for these situations is given by:

μS+L = √4S(S + 1) + L(L + 1)

 Theoretical Versus Experimental Moments

• Look at Ion, S, μs, and observed moments.

• Notice that for many ions, the μs and the μobs values are fairly consistent, for
others, the μs is not even close.
• This is because μs is a “spin-only” momentum.
• For some transition metals, there is an orbital angular momentum contribution.
• The magnetic moment for these situations is given by: μL
μS
μS+L = √4S(S + 1) + L(L + 1)

where L = total orbital angular

momentum quantum number.
 Magnetic properties

Magnetic moment (μ):

µs = μ(spin-only) = n(n + 2)

µS-L = μ(spin-orbit) = 4S(S+1) + L(L+1)

Where n = number of unpaired electronss.

S = Total spin angular momentum quantum number
L = Total orbital angular momentum quantum number
Theoretical Versus Experimental Moments
 Theoretical Versus Experimental Moments

• Examples:
Ti+3 d1 — — — — — L=2
L = 2 + 1 + 0 + -1 + -2
note numbering
V+3 d2 — — — — — L=2+1=3 and
L = 2 + 1 + 0 + -1 + -2 order of filling

Co+2 d7 — — — — — L=2+1+0=3
L = 2 + 1 + 0 + -1 + -2

Mn+2 d5 — — — — — L = 2 + 1 + 0 + -1 + -2 = 0
L = 2 + 1 + 0 + -1 + -2

• Compare to μS+L on Table.

• Notice that μobs values are still less than μS+L; this is because μS+L assumes
a free ion (i.e. a metal with no ligands).
• With ligands the orbital motion is “quenched”.
 Magnetic Properties for Lanthanides and Actinides

μ = g[J(J+1)]1/2

g = 1+ { [J(J+1)+S(S+1)-L(L+1)] / [2J(J+1)]}

Where S = Total spin angular momentum quantum number

L = Total orbital angular momentum quantum number
J = Total spin-orbital angular momentum quantum number
Calculate the magnetic moment of Pr3+ ion.
Pr3+ (f2 system)

ground state term symbol 3H4.

μ = g[J(J+1)]1/2

where S=1, L=5 and J=4

g = 1+ { [J(J+1)+S(S+1)-L(L+1)] / [2J(J+1)]} = 0.8

μ = g[J(J+1)]1/2 = 3.58 BM
 Magnetic Materials

Every material consists of atoms; atoms consist of electrons spinning around them,
similar to a current carrying loop that generates a magnetic field.
Every material responds to a magnetic field.
Strictly speaking, there is so such thing as a “nonmagnetic” material.
 Magnetic Dipoles and Magnetic Moments

• The magnetic behavior of materials can be traced to the

structure of atoms.
• Bohr magneton - The strength of a magnetic moment of an
electron (μB) due to electron spin.

Bohr magneton = qh / 4πme = 9.273 x 10-24 A m2

 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning ™ is a trademark used herein under license.

Origin of magnetic dipoles: (a) The spin of the electron produces a magnetic field with
a direction dependent on the quantum number ms. (b) Electrons orbiting around the
nucleus create a magnetic field around the atom.
ORIGIN OF MAGNETISM IN MATERIALS

A moving electric charge, macroscopically or “microscopically” is

responsible for Magnetism

Nuclear spin Weak effect

Unpaired electrons required

Origin of Magnetism Spin of electrons
for net Magnetic Moment

Orbital motion of electrons

Magnetic Moment resultant from the spin of a single unpaired electron

→ Bohr Magneton = 9.273 x 1024 Am2
 CHEM F343

Magnetic Materials
 Magnetic Materials
Every materials in the world responds to the presence of a magnetic field.

Magnetic materials are used to construct:

 Electrical Motors
 Generators
 Transformers
 Computer disks
 Loudspeakers
 Microphones
 Land-line telephones
 Tape-based video recorders

 Fundamental basis for responses of certain materials to the presence of

magnetic fields.
 Properties and applications of different type of magnetic materials.
A current passing through a coil sets up a magnetic field H with a flux density B. The
flux density is higher when a magnetic core is placed within the coil.
Magnetization, Permeability, and the Magnetic Field

 Magnetic Field (H) - Magnetic fields are created by

magnetized material and by moving electric charges
(electric currents).
 Magnetic permeability(μ) - The ratio between inductance
or magnetization and magnetic field. It is a measure of
the ease with which magnetic flux lines can ‘‘flow’’
through a material.
 Magnetization (M) - The total magnetic moment per unit
volume.
 Magnetic susceptibility (χ) - The ratio between
magnetization and the applied field.
Material in a Magnetic Field

 The response of a material to a Magnetic Field H is called Magnetic

Induction or flux density B
 The relationship between B and H is a property of the material
 In some materials and in free space B is a linear function of H but in
general it is much more complicated and sometimes it is not even
single valued

B  0 ( H  M ) B  [Weber / m2 ]  [Tesla]

M
   Magnetic Susceptibi lity
H
m
M M  Magnetization  Magnetic Moment (m) per unit volum e
V
 Example: Theoretical and Actual Saturation
Magnetization in Fe

Calculate the maximum, or saturation, magnetization that we

expect in iron. The lattice parameter of BCC iron is 2.866 Å .
Compare this value with 2.1 tesla (a value of saturation flux
density experimentally observed for pure Fe).
Based on the unpaired electronic spins, we expect each
iron atom to have four electrons that act as magnetic dipoles.
The number of atoms per m3 in BCC iron is:
SOLUTION (Continued)
The maximum volume magnetization (Msat) is the total
magnetic moment per unit volume:

To convert the value of saturation magnetization M into

saturation flux density B in tesla, we need the value of μ0M. In
ferromagnetic materials μ0M >> μ0H and therefore, B  μ0M.
Saturation induction in tesla = Bsat = μ0Msat.
 Classification of Magnetic Materials

The manner in which the response of electrons and atoms in a material is scaled to
determine whether a material will be strongly or weakly magnetic and gives rise to
many type of magnetic phenomena.

• Ferromagnetism
• Ferrimagnetism
• Diamagnetism
• Paramagnetism
• Antiferromagnetism
• Hard magnet
Figure. The effect
of the core material
on the flux density.
The magnetic
moment opposes
the field in
diamagnetic
materials.
Progressively
stronger moments
are present in
paramagnetic,
ferrimagnetic, and
ferromagnetic
materials for the
same applied field.
 Ferromagnetism:
In a normal paramagnetic material, the atoms containing the unpaired electrons
are magnetically dilute, and so the unpaired electrons in one atom is not aligned
with those in other atoms. However, in ferromagnetic materials, such as metallic
iron, or iron oxides such as magnetite (Fe3O4), where the paramagnetic iron atoms
are very close together, they can create an internal magnetic field strong enough
that all the centers remain aligned:

unpaired electrons unpaired electrons aligned in their

oriented randomly unpaired electrons own common magnetic field
a) paramagnetic,
magnetically
dilute in e.g.
[Fe(H2O)6]Cl2.
Fe separated by
diamagnetic atoms b) ferromagnetic,
atoms
as in metallic
Fe or some
Fe oxides.
a) b)
Ferromagnetism and
Paramagnetism
 Ferromagnetism - Alignment of the magnetic moments
of atoms in the same direction so that a net
magnetization remains after the magnetic field is
removed.
 Ferrimagnetism - Magnetic behavior obtained when ions
in a material have their magnetic moments aligned in an
antiparallel arrangement such that the moments do not
completely cancel out and a net magnetization remains.
 Diamagnetism - The effect caused by the magnetic
moment due to the orbiting electrons, which produces a
slight opposition to the imposed magnetic field.
 Antiferromagnetism:
electron spins in opposite
directions in alternate metal atoms
antiferromagnetism
Here the spins on the
unpaired electrons
become aligned in
opposite directions so
that the μeff approaches
zero, in contrast to
ferromagnetism, where
μeff becomes very large.
An example of anti-
ferromagnetism is found
in MnO.
 Antiferromagnetism - Arrangement of magnetic
moments such that the magnetic moments of atoms or
ions cancel out causing zero net magnetization.

 Paramagnetism – positive magnetism in the presence of

magnetic field and this effect will be lost as soon as the
magnetic field is removed.

 Superparamagnetism – Ferromagnetic and ferrimagnetic

material below a certain size behave as paramagnetic.

 Hard magnet – Permanent magnets, retain their

magnetization.
Figure. The crystal
structure of Mn0
consists of
alternating layers of
{111} type planes of
oxygen and
manganese ions. The
magnetic moments of
the manganese ions
in every other (111)
plane are oppositely
aligned.
Consequently, Mn0 is
antiferromagnetic.
Paramagnetism illustrated:

Prentice-Hall © 2002
 Curie’s Law
In a paramagnetic material the magnetization is directly proportional to the
external applied magnetic field (H0) and inversely proportional to the absolute
temperature (T).

M = C H0 / T
C = Curie’s constant
The equation loses its validity as T approached zero.
As T decreases M increases to some saturation value.
M = C H0 / T
 Magnetization Versus Absolute T for a
Ferromagnetic Substances
Below the Curie Temperature, Tc, the magnetic moments in domains remain aligned
and behavior is ferromagnetic. Above Tc the magnetic moments become unaligned
due to the thermal agitation and the material becomes paramagnetic.

Curie-Weiss Law:

χm = C / (T – Tc)
HYSTERESIS
 Magnetic properties

connection
balance to balance
Gouy balance for
determining
the magnetic
Gouy
susceptibility
Tube

sample
of materials
thermometer

north south

electromagnet
 Classification of Magnetic Materials

The manner in which the response of electrons and atoms in a material is scaled to
determine whether a material will be strongly or weakly magnetic and gives rise to
many type of magnetic phenomena.

• Ferromagnetism
• Ferrimagnetism
• Diamagnetism
• Paramagnetism
• Antiferromagnetism
• Hard magnet