31

Paramagnetic
Ferromagnetic

Curie point
Neel point

Magnetic Properties
Antiferromagnetic of Transition Metal
Temperature, K Complexes
3.1. INTRODUCTION
By studying the magnetic properties of a substance, we can get an insight into the distribution
of electrons in the constituent atoms or ions. We know that the magnetic properties like magnetic
moment and magnetic susceptibility arise due to the presence of unpaired electrons. For example,
the distinction between high spin and low spin complexes can be made on the basis of their magnetic
properties. We observe that most of the
transition metals and their salts and
complexes have unpaired electrons and
show magnetic properties. The unpaired
electron spins about its axis and
therefore shows magnetic properties. It
acts as a tiny magnet The molecules with
paired electrons are diamagnetic. This is
because the paired electrons have their
spins in opposite directions and their
magnetic fields cancel each other. The
picture is different in the case of
molecules having unpaired electrons.
The magnetic fields produced by Magnetic field
individual electrons in this case are not
cancelled, rather they reinforce each other.
Broadly there are two types of magnetic behaviour shown by substances.
1. Paramagnetic substances
Substances having unpaired electrons are called paramagnetic substances. Such substances are
attracted by the external magnetic field. Greater the number of unpaired electrons, greater the
paramagnetic character. Most of the transition metals, their salts and complexes are paramagnetic
in nature.
2. Diamagnetic substances
Substances which do not possess unpaired electrons (their electrons are paired) do not show
any magnetic moment. Such substances are repelled by external magnetic field. This is because, the
magnetic fields produced by paired electrons are neutralised and no net magnetic field is produced
by them.

58

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 59

Origin of paramagnetic moments

The magnetic properties of a substance arise from electrons and nucleus. However, the
contribution of magnetic behaviour from electrons is 1850 times that of nucleus because mass of
proton is about 1850 times that of electron. Therefore, the contribution of nucleus to magnetic
moments is neglected and the magnetic behaviour observed is mainly due to the electrons.
There are two ways in which the electron creates the magnetic moment.
(i) Each electron can be treated as a small sphere of negative charge spinning on its axis. The
spinning of charge produces magnetic moment.
(ii) An electron travelling in a closed path around a nucleus also produces magnetic moment
like an electric current flowing in a circular loop of wire.
The magnetic moment due to spin of the electron on its axis is termed spin magnetic moment
of the electron and the magnetic moment due to motion of the electron around the nucleus is termed
orbital magnetic moment. Therefore, observed magnetic moment of an atom or ion is the sum of
the spin magnetic moment and orbital magnetic moment.
We shall first discuss the magnetic moment due to the spin of the electron.
The magnetic moment is expressed in terms of units called Bohr Magneton, abbreviated as
B.M. The magnetic moment for an electron having charge e and mass m is given by the relation.
eh
s =
4 mc
where h is Planck’s constant and c is the velocity of light.
The value of s for an electron as obtained by the above expression is 9.274 × 10–21 erg
–1
gauss . This is taken as one unit of magnetic moment called Bohr Magneton. Thus, Bohr magneton
is defined as
eh
1 B.M. = (1)
4 mc
The magnetic moment, s of a single electron is given by the relation
s = 2 s( s  1) (2)

1
where s is the spin quantum number = .
2
1
Substituting the value of s as , equation (2) reduces to
2
11 
s = 2  1  3 = 1.732 B.M.
2  2 
Thus, atom or ion having one unpaired electron (e.g. H, Cu2+) should have spin magnetic
moment of 1.732 B.M. from the electron spin alone. For atoms or ions having multiple unpaired
electrons, the overall spin moment is given by
s = 2 S ( S  1) (3)
where S is the sum of the spin quantum numbers for the individual electrons. For example, Ti3+ has
1 1
only one unpaired electron so that S = , Cr3+ has four unpaired electrons so that S = 4  = 2
2 2
and so on.

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 60 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

Eq. (3) may also be written as

s = 4S ( S  1) (4)
Now we can calculate magnetic moments for different number of unpaired electrons
For one unpaired electron,
1
S =
2

1 1 
 s = 4  1  3 = 1.732 B.M.
2  2 
For two unpaired electrons,
1 1
S =    1
2 2
 s = 4  1(1  1)  2 2 = 2 × 1.414 = 2.828 B.M.
For three unpaired electrons,
S = 3/2

33 
 s = 4    1 = 3.87 B.M.
22 
There is more conveneint direct method to calculate the magnetic moment using the relation
s = n (n  2) B.M. (5)
where n is the number of unpaired electrons. We can verify the validity of eq. (5) as under :
For one unpaired electron :
s = 1(1  2)  3 = 1.732 B.M.
For two unpaired electrons :
s = 2(2  2)  2 2 = 2 × 1.414 = 2.828 B.M
Table 3.1 gives calculated values of s for the different number of unpaired electrons.
Table 3.1. Spin only magnetic moments for different number of unpaired electrons.
No. of unpaired electrons s (B.M.)
1 1.73
2 2.84
3 3.87
4 4.90
5 5.92
6 6.93
7 7.94
We observe that there is a fair agreement between the experimental values of magnetic moments
of some transition metal ions and the values obtained from the spin only formula. However in some
cases, experimental values differ from the spin only values. The reason being that in addition to spin

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 61

of the electron, orbital motion of electron also contribute to the magnetic moment. In these cases,
we use the following equation to calculate the magnetic moment.
S + L = 4S ( S  1)  L( L  1) (6)
where S is the resultant spin angular momentum and L is the resultant orbital angular momentum
quantum number. A comparison has been made in Table 3.2 between the observed values and values
obtained from the spin-only relation for the magnetic moments.
We find from the table that observed values of  are frequently greater than s and are never
more than S + L. This means that the contribution to magnetic moments due to orbital motion of
electrons is positive although very small. A very small different in the values means that the orbital
moments are completely or partially quenched (neutralised). This is because the electric field of
ligands (atoms, ions or molecules) surrounding the metal ion restrict the orbital motion of the
electrons.
Table 3.2. Magnetic moments of some metal ions of transition series
Magnetic moment (B.M.)
Ion No. of unpaired Spin only Observed
electrons value value
Sc2+ 0 0 0
Ti3+ 1 1.73 1.7—1.8
Ti2+ 2 2.83 2.8—3.1
V2+ 3 3.87 3.7—3.9
Cr2+ 4 4.90 4.8—4.9
Mn2+ 5 5.92 5.7—6.0
Fe2+ 4 4.90 5.0—5.6
Co2+ 3 3.87 4.3—5.2
Ni2+ 2 2.84 2.9—3.4
Cu2+ 1 1.73 1.9—2.1
Zn2+ 0 0 0
However, the situation is different with second and third row transition elements particularly
the lanthanides where the unpaired electrons occupy 4 f orbitals. Here the orbital motion of the
electrons is not quenched. Here, the 4 f orbitals are shielded by the 5s and 5p subshells . Thus orbital
contribution to the magnetic moment is not quenched. Here both the spin and orbital motion of the
electrons contribute to the total magnetic moment.

3.2. MEASUREMENT OF MAGNETIC PROPERTIES

The magnetic moments cannot be measured directly. We first measure the magnetic
susceptibility () from which it is possible to measure magnetic moment.
The magnetic susceptibility is a measure of the capacity of a substance to take up
magnetisation in an applied magnetic field. If a substance is placed in a magnetic field of strength
H, then magnetic induction or magnetic flux density, B within it, is given by
B = H + 4 I (1)
where I is called the intensity of magnetisation. Intensity of magnetisation (I) represents the extent
to which a sample can be magnetised when placed in a magnetic field. It is defined as the magnetic
moment per unit volume of the magnet (magnetic substance)

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 62 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

Magnetic moment
I =
Volume
If a is the area of cross-section of the magnetic substance and 2l is the length of the substance
then I becomes
m  2l m
I = 
a  2l a
Therefore intensity of magnetisation is also defined as the pole strength per unit area of cross-
section of the material. The ratio B/H, called magnetic permeability of the substance can be given
as :
B I
= 1  4 (2)
H H
Dividing both sides by H, we obtain
B
= 1 + 4  (3)
H
 is called the magnetic susceptibility per unit volume
Magnetic permeability is the ability of a material to permit the passage of magnetic lines of
force through it. In other words, magnetic permeability (B/H) gives the ratio of the density of lines
of force within the substance to the density of such lines in the same region in the absence of the
substance. Therefore, the volume susceptibility of vacuum is obviously zero because in vacuum
B/H = 1 so that, from eq. (3)
1 = 1 + 4 or  = 0
The susceptibility of a diamagnetic substance is negative because lines of force from induced
dipole cancel out the lines of force due to applied field and B/H is less than 1.
Paramagnetic substances have the flux is greater within the substance than it would be in vacuum
and thus paramagnetic substances have positive susceptibilities.
Susceptibility may be expressed in two forms, specific susceptibility and molar susceptibility
given by the following relations


Specific susceptibility ,  =

where  is the density.
M
Molar susceptibility, M =

where M is the molecular mass of the substance.

Measurement of magnetic moment

Two commonly used methods of determination of magnetic moment are described hereunder.
(i) Gouy method
(ii) Faraday method.
1. Gouy’s method
Gouy’s balance named after the scientist who devised it is generally used to measure
paramagnetism. Finely powdered substance or solution is taken in a pyrex glass tube called Gouy

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 63

tube (Fig. 3.1). The substance is weighed first without magnetic field and then in the presence of
magnetic field. If paramagnetic, the substance will weigh more in the presence of a magnetic field
than in its absence. The increase in weight gives a measure of paramagnetism of the substance. Larger
the number of unpaired electrons in a substance, greater is the increase in its weight in a magnetic
field. The susceptibility is calculated from the difference in weight of the sample when the magnet
is off and when it is on.

Fig. 3.1. Gouy’s method of measuring paramagnetism.

Calculation of magnetic moment

The Gouy procedure offers a convernient method for measuring magnetic susceptibility. The
sample in the form of a cylinder is suspended in a non homogeneous magnetic field and the force
exerted on the sample is determined by weighing. The force acting on the sample is given by
1
F = A  H2 (4)
2
where A = is the cross sectional area of the cylinder
H = Intensity in the central homogenous part of the magnetic field
 = volume susceptibility
The above equation is valid only if the measurements are done in vacuum. However, if the
sample is surrounded by air, then the susceptibility of air () must be subtracted from the measured
susceptibility. In that case, we shall use the equation
1
F = AH2 ( – ) (5)
2
where  = volume susceptibility of air
Now, the Gouy tube itself develops a force which is always present. Therefore, to calculate the
actual force acting on the sample, the force acting on the Gouy tube is subtracted from the observed

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 64 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

force. This force is negative because of the diamagnetic material of the tube. It is denoted by , then
eqn. (5) becomes
1
F = AH2 ( – ) +  (6)
2
For a sample of constant length and cross sectional area, the factor AH2 is constant. Now if
the density of the sample is introduced, the above equation may be rewritten as :
  BF 
106  = (7)
w
where  = constant allowing for the displaced air and is equal to 0.029 × specimen volume
and is expressed in mg.
w = weight of sample expressed in gram.
F = Force on the sample and is equal to F – ; both F and  are given in mg.
 = tube calibration constant.
The apparatus is calibrated by making measurements on a substance whose susceptibility is
accurately known. The standard substance commonly used for calibration is mercury
tetrathiocynatocobaltate (II), Hg [Co(CNS)4]. Its susceptibility is 16.44 × 10–6 at 20°C.
By making measurements with this standard substance the constant  is first calculated.
Substuting the values of , ,  and F on a given sample of weight w, the susceptibility  can be
calculated using eq. (4)
Since the amount of sample taken in the Gouy’s tube is quite large, the forces are large and
therefore, even a chemical balance can measure the changes in mass.
However the disadvantage is that it requires perfect uniform packing of the substance in the
Gouy’s tube. Correct results are not obtained if the Gouy’s tube has not been packed uniformly.
2. Faraday’s method
If only a small amount of the substance (in mg) is available, then Faraday’s method is perhaps
more suitable for magnetic moment measurement. The sample that is suspended in an inhomogeneous
 H 
field such that H0   is constant over the entire volume of the sample. The set up of Faraday’ss
 x 
apparatus is shown in Fig. 3.2. The sample is suspended between magnet poles that have been
H
carefully shaped so that the value of H0 remains
x
constant over the region occupied by the sample. A sample
(0.1 – 10 mg) of the substance is placed in a magnetic field
of constant gradient,

Fig. 3.2. Schematic diagram of Faraday balance for A modern computerised

measuring magnetic susceptibility magnetic measuring system

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 65

H
and the force acting on the sample is measured directly with the help of an electrobalance. If
x
a sample of mass m and specific susceptibility  is placed in a non-uniform field H, then the sample
will experience a force (f ) along x as :

 H 
f = m H0   (8)
 x 
The force can be measured by weighing the sample in the absence and presence of the field.
The difference between the two weights is equal to f. The matter is simplified by carrying out
experiment on a standard of known susceptibi l i ty such as Hg[ Co(CNS) 4 ], mercury
tetrahiocyanatocobaltate (II) which has susceptibility as  = 16.44 × 10–6 at 293 K.
With same magnetic field and gradient for both the standard (s) and unknown (), it is not
necessary to know the precise values of other quantities. Hence, we have
fs fu
=
ms  s mu u

fu ms  s
or u = (9)
f s  mu
The molar susceptibility of the sample, m can be calculated using the value u.
This method has the advantage that it can be used with very small quantity of the substance
for measurement and the sample need not be homogeneous.
This method gives us specific susceptibility directly. The Gouy’s method gives volume
susceptibility, which has to be converted to specific susceptibility. The conversion poses a problem
because it requires accurate value of density, which is difficult to obtain for solids because the values
vary with the packing of the substance.
Diamagnetic correction
The measured magnetic susceptibility will consist of contributions from paramagnetic and
diamagnetic susceptibilities. Therefore, the measured susceptibility is corrected by subtracting the
diamagnetic contribution from it.
Paramagnetic susceptibility = Measured suscepibility – Diamagnetic susceptibility

3.3. RELATIONSHIP BETWEEN MAGNETIC SUSCEPTIBILITY

AND MAGNETIC MOMENT
The magnetic susceptibility obtained after correction is related to magnetic moment,  (in B.M.)
as :

N0 2
M = (1)
3kT
where k is Boltzmann constant
N0 is Avogadro number
T is absolute temperature
Rearranging equation (1)
3k
2 =  M  T
N0

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 66 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

3k
or  =  M  T
N0
= k M  T (where k is constant)

3k
The constant comes out to be 2.828.
N0
Thus, magnetic moment can be calculated from the magnetic susceptibility using the relation:
 = 2.828  M  T B.M. (2)

3.4. VARIATION OF MAGNETIC SUSCEPTIBILITY WITH

TEMPERATURE
Magnetic susceptibility of a substance is dependent on
temperature. Pierre Curie showed that paramagnetic
susceptibilities vary inversely with temperature and follow the
behaviour as shown by the following equation :
C C
M = or T =
T M
where T is the absolute temperature and C is a constant
characteristic of the substance and is known as Curie constant.
The above expression is called Curie’s law.
Thus, if we plot M against absolute temperature, a
parabolic curve is obtained as shown in Fig. 3.3(a). However,
if we plot reciprocal of M (i.e. 1/M) at different temperatures
against absolute temperature, a straight line with slope C is
obtained (Fig. 3.3(b)). This curve should pass through the origin.
However, it is observed that in many cases, the line does not pass
Pierre Curie with wife Marie
through the origin. It cuts the temperature axis either below or
Curie in their laboratory
above 0°K. This required some modification of Curie equation.

M 1
M

T (K) T (K)
(a) (b)

1
Fig. 3.3. (a) Plot of M vs T(k) (b) Plot of vs T(k)
M
It was modified as
C
M =
T

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 67

where  is the temperature at which the line cuts the T-axis. This modified equation is called Curie
- Weiss law and  is known as Weiss constant. The Weiss constant takes into account the
intermolecular interactions. Magnetic moments can now be calculated by the equation

 = 2.828 M (T  )

Ferromagnetism and Anti-ferromagnetism

In addition to paramagnetic and diamagnetic substances, we also come across ferromagnetic
and anti-ferromagnetic substances. These substances show dependence on both temperature and
field strength. Their main features can be understood in terms of Curie or Curie-Weiss law. The
temperature dependence of ferromagnetism and anti-ferromagnetism is shown in Fig. 3.4 (a) and 3.4
(b) respectively.
The inspection of curve 3.4(a) shows that there is some discontinuity in the curve at the
temperature marked Tc. This temperature is called Curie temperature. Above this temperature, the
ferromagnetic substance follows the Curie or Curie-Weiss law and therefore, exhibits simple
paramagnetism (Refer to Fig. 3.3a). Below this temperature, the magnetic susceptibility behaviour
is different and depends upon the field strength.
Inspection of curve 3.4 b shows that for anti-ferromagnetic susbstances, there is a characteristic
temperature, TN called the Neel temperature. Above this temperature, the substance follows Curie
or Curie-Weiss law (Again refer to Fig. 3.3a) and shows simple paramagnetism. Below Neel
temperature the magnetic susceptibility decreases with decrease in temperature.

Antiferromagnetic Substances

Fig. 3.4. (Behaviour of (a) ferromagnetic and (b) anti-ferromagnetic substances with temperature.

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 68 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

The abnormal behaviour in ferromagnetic and anti-ferromagnetic substances can be explained

in terms of interionic interactions. These interactions have magnitudes comparable to thermal energies
at the Curie or Neel temperature and increase in magnitude as the temperature is lowered.
In the case of anti-ferromagnetism, the magnetic moments of the ions in the lattice tend to
align themselves in a manner so as to cancel one another and give zero magnetic moment. Above
the Neel temperature, thermal energy is large (kT) and prevents the effective alignment of the
magnetic moments. MnO, MnO2, FeO, NiO, etc belong to this category. A pattern of alignment of
magnetic moments in anti-ferromagnetic substances is shown in the picture below
In ferromagnetic substances above the Curie temperature, thermal energies are able to randomise
the orientations. But, below TC, alignment becomes dominant and the susceptibility increases rapidly
with decreasing temperature. Ni, Co, CrO2, etc belong to this category.
The arrangement in paramagnet substances is quite random as in the picture below
In yet another class of magnetic substances known as ferrimagnetic substances, the magnetic
moments are aligned in parallel and anti-parallel directions in unequal numbers resulting in net
magnetic moment. Magnetic oxide Fe3O4 and ferrites belong to this category.

Paramagnetic Ferromagnetic

Anti- Ferrimagnetic
ferromagnetic

Alignment of magnetic moments in ferro, anti-ferro, ferri and paramagnetic substances

3.5. ORBITAL CONTRIBUTION TO MAGNETIC MOMENT
Some complexes of transition metals (particularly from first transition series) give a magnetic
moment much higher than s. This is due to the orbital contributions to magnetic moment. The
spin angular momentum of an electron is independent of its surroundings and therefore, the spin
moment of an unpaired electron remains, unaffected by changes in chemical bonding of the
compound provided that there is no spin pairing because of bonding. On the contrary, the orbital
angular momentum of the electron depends upon the chemical environment. The orbital
contribution to magnetic moment may get compensated or quenched. A as result, the observed
magnetic moments are very close to spin-only magnetic moment values. The quenching of orbital
angular momentum can be easily explained on the basis of crystal field theory of bonding in
transition metal complexes.

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 69

The unpaired electrons in a first transition series are present in the 3d orbitals. A transition metal
ion has five 3d orbitals which are degenerate. An electron possesses as angular momentum along
a given axis if it is possible to transform its orbital by rotation around this axis into another orbital
which is equivalent to it in shape, size and energy. This circulation of electron is equivalent to a
current flowing and therefore, it produces a magnetic effect.
Thus, for orbital contribution to magnetic moment, there must be two or more degenerate
orbitals which can be inter converted by rotation about a suitable axis and these orbitals must
be unequally occupied.
The orbital angular momentum along the given axis possessed by the electron in such an
orbital is equal to the number of times the orbtial gets transformed into the equivalent orbital during
a rotation of 90° around that axis. If the orbital degeneracy is lost by chemical bonding or crystal
field effects, the orbital contribution to the total magnetic moment is partially or completely
quenched.
Consider a free metal ion in which all the d-orbitals are degenerate. An electron in
d orbital will contribute to orbital angular momentum equal to 2 units of h/2 along
x2  y 2
z-axis because a rotation of d x2  y 2 orbital by 45° around the z-axis takes it to equivalent
dxy orbital (Fig. 3.5)

Remember:
d and dxy are
x2  y 2
four lobed orbitals.

Fig. 3.5. Circulation of electron density about z-axis (perpendicular to the plane) in dxy and
d orbitals.
x2  y 2
This means that a rotation of d x2  y 2 orbital by 90° around z-axis will carry this orbital into dxy
orbital two times. Similarly, we can also say that an electron in dxy orbital will contribute to orbital
h
angular momentum of 2 in the units of along z-axis. In a similar manner, an electron in dxz orbital
2
h
will have an orbital angular momentum equal to 1 unit of along z-axis because dxz orbital gets
2
transformed into an equivalent dyz orbital by rotating the dxz orbital around x-axis by an angle of 90°.
The situation is different in d z 2 , it cannot be transformed into any other equivalent orbital by rotation
around z-axis and therefore, its has zero orbital angular momentum along z-axis.

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 70 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

When the metal ion is surrounded octahedrally by six, the degeneracy of d-orbitals gets
disturbed. The dxy and d x2  y 2 orbitals acquire different energies and therefore, are non equivalent.
As a result, an electron in d x2  y 2 orbital cannot be equated with an electron in dxy orbital. In other
words, the d x2  y 2 orbital cannot be transformed into dxy orbital and vice versa by rotation of the
orbital along z-axis. Thus, the electron in d x2  y 2 orbital will cease to have orbital contribution along
the z-axis.
Quenching of Orbital Angular Momentum in Octahedral Complexes
In octahedral field of ligands, the five d-orbitals get split into two sets, t2g (d xy d yz d zx ) and
eg (d x 2  y 2 , d z 2 ). Therefore, the equivalence of d x2  y 2 and dxy orbitals disappears and
consequently, their orbital contribution gets quenched. However, there will be some contribution of
orbital angular momentum along z-direction because dxz and dyz orbitals are still equivalent in energy
in octahedral field. Therefore, an electron in dxz or dyz orbital will contribute an orbital angular
moment along z-axis in octahedral complexes. Thus, a metal ion with electrons in t2g orbitals would
make some contribution along the z-direction to the overall magnetic moment (eff) of the complex.
The direction of the applied magnetic field is also taken to be z-axis by convention. However, if t2g
or eg orbitals are half filled or fully filled i.e. having one or two electrons each, their rotational
transformation into one another becomes invalid. For example, the dxz orbital cannot be transformed
by rotation into equivalent dyz orbitals because this has an electron already. Thus, the orbital magnetic
moment will be zero.
Following the above principles, we can predict that metal ions having the configurations d1 (t2g1)
and d2(t2g2) will have orbital contribution but the complex with d3(t2g3) configuration will not have
any orbital contribution. Table 3.3 lists the electronic configurations of the central metal atom in which
the orbital contribution is present or absent in high spin and low spin octahedral complexes with d1
to d2 configurations.
Table 3.3. Orbital contribution in octahedral complexes
No. of electrons High spin octahedral Low spin octahedral
dn Electronic Orbital Electronic Orbital
Configuration contribution configuration contribution
d1 t2g1 yes t2g1 yes
d2 t 2g yes t2g2 yes
d3 t2g3 no t2g3 no
d4 t2g3 eg1 no t2g4 yes
d5 t2g3 eg2 no t2g5 yes
d6 t2g4 eg2 yes t2g6 no
d7 t2g5 eg2 yes t2g6 eg1 no
d8 t2g6 eg2 no t2g6 eg2 no
d9 t2g6 eg3 no t2g6 eg3 no
Orbital contribution in Tetrahedral Complexes
In the case of tetrahedral complexes, the five d-orbitals split into two sets t2 and e orbitals. The
2
t 2 orbitals (d xy d yz and d z ) have higher energies than orbitals (d x2  y 2 and d z ). Thus in
tetrahedral complexes, the metal ions having the following configurations will not have orbitals
contribution :

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 71

d1(e1), d2(e2), d5(e2 t23), d6(e3 t23) and d7(e4 t23)

On the otherhand, the tetrahedral complexes having the following configurations will have orbital
contribution :
d3(e2 t21), d4(e2 t22), d8(e4 t24) and d9(e4 t25).
These are given in Table 3.4
Table 3.4. Orbital contribution in tetrahedral complexes
No. of Electronic Orbtial
electrons Configuration Contribution
d1 e1 no
d2 e2 no
d3 e2 t21 yes
d4 e2 t22 yes
d5 e2 t23 no
d6 e3 t23 no
d7 e4 t23 no
d8 e4 t24 yes
d9 e4 t25 yes
The above principle explains why tetrahedal complex of one transition element possesses
orbital contribution to the magnetic moment, while another element does not.
For example we find that the magnetic moments of Co(II) tetrahedral complexes (d7) are nearer
to the spin only values as expected. On the other hand, the magnetic moments of Ni(II) complexes
of tetrahedral geometry (d8) are more than the spin only values as expected. In some cases, there
may be contribution from spin-orbital coupling. In such cases we calculate the magnetic moments
by using the following equation :

 
eff =  0  1   
 
Here 0 = Spin only magnetic moment
 = Constant
 = Spin-orbit coupling constant positive for n < 5 and negative
 is the difference in energy level between the ground state and higher state. The values of 
and  are given for some metal ions in Table 3.5. It may be noted that the value of  is positive or
negative. This explains as to why the value of the magnetic moment measured is smaller in some
cases and greater in other cases than the spin only value–although the number is fairly small in the
first category.

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 72 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

Table 3.5. Spin orbital coupling constant (l) and a values of some transition metal ions
Metal No. of   Stereochemistry
ion electrons
Ti3+ 1 54 2 Tetrahedral
V3+ 2 108 4 Tetrahedral
Cr3+ 3 91 4 Octahedral
Cr2+ 4 57 2 Octahedral
Mn3+ 4 88 2 Octahedral
Fe3+ 5 88 0
Mn2+ 5 80 0
Fe2+ 6 –102 2 Tetrahedral
Co2+ 7 –177 4 Tetrahedral
Ni2+ 8 –315 4 Octahedral
Cu2+ 9 –829 2 Octahedral

Temperature Independent Paramagnetism (TIP)

The complex ions such as MnO4–, CrO42–, [Co(NH3)6]3+, etc. have no unpaired electrons. These
systems are not expected to show any orbital magnetic moment and are expected to be diamagnetic.
However, they show weak paramagnetism. This happens because of the coupling of the ground state
of the system with the excited states of high energy under the influence of magnetic field. As a result
of coupling, the complexes show some orbital magnetism. As a result such substances are no more
diamagnetic. As this paramagnetism does not depend upon the thermal population of levels unlike
simple paramagnetism, it is called temperature independent paramagnetism or TIP. But it resembles
diamagnetism in the sense that it is not due to any magnetic dipole existing in the molecule. But it
is induced when the substance is placed in the magnetic field. It also resembles diamagnetism in its
temperature independence and it has magnetic susceptibility of the order of diamagnetic substances.
For diamagnetic transition metal ions it is very important in determining the position of NMR
resonance.

3.6. MAGNETIC BEHAVIOUR OF FIRST ROW TRANSITION

METAL COMPOUNDS
An attempt has been made to study the variation of orbital contribution along the first transition
series.
The magnetic moments of the compounds of first transition series in common oxidation states
are given in Table 3.6. Magnetic moments due to spin only ( ms) as well as magnetic moments due
to spin and orbital contributions (mS + L) are also also given.

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 73

Table 3.6. Magnetic moments of metal ions of first transition series

Ion Outer No. of S L S S + L Obversed
configuration unpaired
electrons
Sc3+, Ti4+, V5+ 3d0 0 0 0 0 0
Ti3+, V4+ 3d1 1 1/2 2 1.73 3.0 1.7—1.8
Ti2+, V3+ 3d2 2 1 3 2.84 4.47 2.76
V2+, Cr3+ 3d3 3 3/2 3 3.87 5.20 3.86
Cr2+, Mn3+ 3d4 4 2 2 4.90 5.48 4.80
Mn2+, Fe3+ 3d5 5 5/2 0 5.92 5.92 5.96
Fe2+ 3d6 4 2 2 4.90 5.48 5.1—5.6
Co2+ 3d7 3 3/2 3 3.87 5.20 4.4—5.2
Ni2+ 3d8 2 1 3 2.84 4.47 2.9—3.4
Cu2+ 3d9 1 1/2 2 1.73 3.0 1.7—2.1
Cu+, Zn2+ 3d10 0 0 0 0 0 0
We observe that the magnetic moments of compounds of first half of transition series are fairly
close to their calculated spin only magnetic moments and are quite different from calculated magnetic
moments based upon spin and orbital contributions. However, in the later half of the compounds of
first transition series, the observed values are slightly higher than the calculated spin only values.
This means that in the first transition series, orbital contribution to the magnetic magnetic moments
is negligible.
Two information can be useful in establishing details of electronic structure and stereochemistry.
We discuss below the important features of some complexes of first transition series with different
dn configurations
d1 system
Titanium (III) octahedral complexes having t2g1 configuration such as [Ti(H2O)6]3+ are coloured
and paramagnetic. These have magnetic moment of 1.8 B.M. at room temperature. This value is
higher than the expected spin only value of 1.73 B.M. and is attributed to the partially quenched
orbital contribution.
d2 system
The metals ions having d2 system with t2g2 configuration such as V(III) octahedral complexes
are also expected to have some orbital contribution to magnetic moment. However, the observed
magnetic moment values of V(III) octahedral complexes are in the range of 2.7 to 2.8 B.M. and are
even less than the expected spin only value of 2.84 B.M. This observation is not easy to explain and
is attributed to the presence of some distortions which split the ground state term 3T2g (refer to
electronic spectra of transition metals). (Chapter 4)
d3 system
Chromium (III) octahedral complexes are most extensively studied compounds in this category.
The observed magnetic moment values at room temperature lie in the range 3.70 to 3.84 B.M. The
magnetic moment arising from spin only value of 3.87 B.M. agrees fairly well with the observed
values and is independent of temperature. However, the reduced values of magnetic moments are
observed in some bridged complexes such as [(NH3)5 Cr(–OH) Cr(NH3)5] X5 (where X = Cl or
Br) and [(NH3)5 Cr–O–Cr(NH3)5]4+ and are temperature dependent.

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 74 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

d4 system
Chromium (II) octahedral complexes have d4 or t 2g3 e g1 configurations. The complex
[Cr(SO4)2]2+ has magnetic moment of 4.90 B.M. which agrees with the spin-only value. Low spin
octahedral complex like K4[Cr(CN)6]. 3H2O having the configuration t2g4 shows the magnetic
moment in the expected range of 2.74 to 2.84 B.M. (spin only with partial orbital contribution).
However, chromium (II) acetate dihydrate, Cr2(CH3COO)4.2H2O is one of the most stable chromium
compounds and is diamagnetic. This suggests that all the four unpaired electrons take part in Cr-
Cr bonding in the form of quadrupole Cr Cr bond, thereby leaving no unpaired d-electron on Cr--
atoms.
d5 system
Octahedral complexes of Mn(II) and Fe(III) with t 2g3 e g2 configuration belong to this
configuration. These are high spin complexes and show magnetic moments in the expected range of
spin only value of 5.92 B.M. However, some oxo bridged species of Fe(II) like those of Cr(III) show
values lower than 5.92 B.M. This is explained due to the antiferromagnetic interactions between
the electron spins of two metal ions transmitted across Fe-O-Fe bridge.
d6 system
This system includes iron (III) octahedral complexes of high spin having the configuration t2g4
2
eg . It has 4 unpaired electrons and has magnetic moment around 5.5 B.M. which agrees well with
orbital contribution to spin only value of 4.9 B.M. Some distortions produced values in the range
of 5.2 to 5.4 B.M. However, low spin Fe(II) complexes having the configuration t2g6 are diamagnetic.
Most of the cobalt (II) complexes of t 2g6 configuration show diamagnetism. However,
octahedral complexes such as K3[CoF6] are high spin having the configuration t2g4 eg2 and having
the magnetic moment equal to 5.8 B.M. This explained in terms of spin only value having some
orbital contribution.
d7 system
Cobalt (II) having d7 system forms a number of complexes which are less stable than those of
Co(III). These complexes may be tetrahedral or octahedral. Most cobalt (II) complexes are high spin
but CN – produces low spin complexes. A low spin octahedral complex will have the
configuration t2g6 eg1. The magnetic moments of tetrahedral cobalt (II) having configuration e4 t23
lie in the range of 4.4 to 4.8 B.M. at room temperature. The spin only magnetic moment value is
3.87 B.M.
d8 system
Nickel (II) d8 octahedral complexes such as [Ni(H2O)6]2+ with t2g6 eg2 configuration have
magnetic moment of 3.2 B.M. at room temperature. This is explained on the basis of spin-orbital
complexes. Similarly, the [Ni(acac)2] complex is octahedral and shows a normal magnetic moment
of 3.2 B.M. like other Ni(II) complexes. However, it shows normal magnetic moment down to about
80K but below this temperature, the magnetic moment increases from 3.2 B.M. to 4.1 B.M. at 4.3
K. This is attributed to ferromagnetic coupling.
Ni(II) tetrahedral complexes having e4 t24 configuration have orbital contribution and the
observed magnetic moment values in the range 3.2 to 4.1 B.M. can be explained on the basis of
orbital contribution to magnetic moment.
The magnetic properties of complexes can be very useful in establishing details of structure and
stereochemistry. The Ni(II) complexes provide an example of usefulness of magnetic properties. For
example consider the complex [Ni(py)4] (ClO4)2. This can be prepared under the slightly different
conditions and two complexes of this composition have been isolated. One is yellow and diamagnetic

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 75

while other is blue with a magnetic moment of 2.9 B.M. The blue complex can be assigned an
octahedral structure. The yellow complex is most likely the square planar complex in which
perchlorate ions are not coordinating. However, five coordinate geometry with a single coordinate
ClO4– ligand cannot be excluded on the basis of magnetic data.

3.7. MAGNETIC PROPERTIES OF OCTAHEDRAL COMPLEXES

BASED ON CRYSTAL FIELD THEORY
The filling of d-orbitals in presence of weak ligand and strong ligand is shown in Table 3.7.
In a weak ligand field d-orbital will be occupied singly before any pairing of electrons takes place.
This is because the energy difference between t2g and eg orbitals will be too small to affect the issue.
– – – – –
In the field of weak ligands (such as F , OH , Cl , Br . I etc.) the crystal field splitting is
small so less energy is required to feed the fourth electron into a eg orbital than to pair it with one
of the t2g orbitals. Hence it will be more favourable energetically to occupy the upper eg level and
have a high spin complex rather than to pair of electrons with one of t2g orbitals. Here 0 (octahedral)
is less than pairing energy P, i.e., o < P or pairing energy P is more than splitting energy (o) i.e.,
P > o.
– –
In a field of strong ligands such as CN , NO2, en, NH3 or CNS , the crystal field splitting is
quite large. Thus o, the difference between the energies of eg and t2g orbitals is quite significant,
so electron pairing takes place. The electrons would rather pair in lower energy t2g orbitals rather
than occupying higher energy eg orbitals. Splitting energy o is more than pairing energy i.e., 0 >
P or paring energy is less than splitting energy i.e., P <o.
There is a significant difference in the arrangement of d 4, d 5, d 6
and d 7
metal ion
configurations in a weak and a strong field as shown in Table. 3.7:
Table 3.7. Octahedral complexes
No. of Weak Field (High spin) Strong Field (Low Spin)
Electrons t2g eg t2g eg
1  
2    
3      
4       
5        
6        
7         
8          
9          
In these arrangements the number of unpaired electrons is greater in a weak field than in a strong
field because the strong field forces the electrons to pair. Complexes with weak ligands are high spin
complexes and are paramagnetic in nature while those with strong ligand fields are low spin
complexes and are diamagnetic in nature, High spin complexes having more unpaired electrons have
high paramagnetism than low-spin complexes which have fewer unpaired electrons.

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 76 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

3.8. MAGNETIC PROPERTIES IN TETRAHEDRAL COMPLEXES

BASED ON CRYSTAL FIELD THEORY
The filling of d-orbitals in certain ions surrounded by tetrahedral ligands in weak and strong
fields is shown in Table 3.8.
Table 3.8. Tetrahedral complexes.
No.of Weak Field (High Spin) Strong Field (Low Spin)
Electrons eg t2g eg t2g
1  
2    
3     
4      
5        
6         
7          
8          
9          

It is clear from the table that the configurations of d 3,d 4, d 5 and d 6 ions may form high and
low spin complexes. But in actual practice only high spin complexes are formed. This is due to the
fact that crystal field splitting t is quite small and is always less than the pairing energy, i.e.,
t < P .Therefore high spin and paramagnetic complexes are formed.
Example. How does crystal field theory explain the diamagnetic behaviour of Ni(CN)4]2–
and paramagnetic behaviour of [NiC14].
Solution. Cyanide ion is a strong field ligand. It splits the d orbitals into dx2– y2
three sets of orbitals with varying energies as shown aside: dxy
Eight electrons in Ni2+ ions are filled in the orbitals as shown above.
Energy

Because of large value of splitting energy, electrons don’t occupy higher dz 2

energy dx2 – y2 orbitals. Thus, there are no unpaired electrons and the complex
is diamagnetic. Chloride is a weak ligand causing only a small splitting.
Electrons occupy different orbitals giving tetrahedral geometry. Complex is dxz dyz
paramagnetic due to presence of unpaired electrons.

SOLVED CONCEPTUAL PROBLEMS

Example 1. Cu ions are coloured paramagnetic while Zn2+ ions are colourless and
2+

diamagnetic. Explain.
Solution. The electronic configuration of Cu2+ and Zn2+ are :
Cu2+ : 3d2; Zn2+ : 3d10
Cu2+ has one unpaired electron and therefore is paramagnetic. On the other hand, Zn2+ has
all electrons paired and therefore, is diamagnetic.

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 77

Example 2. Define magnetic susceptibility. Predict whether the molar magnetic susceptibility
is independent or dependent on the applied magnetic field for the following types of substances :
paramagnetic, diamagnetic, ferromagnetic and antiferromagnetic.
Solution. Magnetic susceptibility is a measure of the capacity of a substance to take up
magnetisation in applied magnetic field. The magnetic susceptibility per unit volume is represented
M
as . The molar susceptibility m =

While ferromagnetic and antiferromagnetic substances are dependent on applied magnetic
field, paramagnetic and diamagnetic susbtances are not.
Example 3. Cu (I) is diamagnetic whereas Cu (II) is paramagnetic.
Solution. In Cu (II), the outermost electronic configuration is 3d9 and therefore, it has one
unpaired electron. Hence, it is paramagnetic. However, in Cu (I), the outermost electronic
configuration is 3d10. There is no unpaired electron and therefore, Cu (I) is diamagnetic.
Example 4. Calculate in Bohr magneton the expected magnetic moment for the following
ions (spin magnetic moment) :
(i) Fe3+ (ii) Ni2+ (iii) Cu+
Solution. Spin magnetic moment is given as :
 = n (n  2) B.M.
where n is number of unpaired electrons.
(i) Fe3+ : [Ar] 3d5 No. of unpaired electrons = 5
 = 5(5  2)  37 = 5.96 B.M.
2+ 8
(ii) Ni : [Ar] 3d No. of unpaired electrons = 2
 = 2(2  2)  2 2 = 2.828 B.M.
+ 10
(iii) Cu : [Ar] 3d No. of unpaired electrons = 0
 = 0
Example 5. Which ion should exhibit a larger magnetic moment : Mn2+ or V2+ ?
Solution. Mn2+ : [Ar] 3d5
V2+ : [Ar] 3d 3
Mn2+ has five unpaired electrons whereas V2+ has three unpaired electrons. Therefore, Mn2+
has higher magnetic moment.
Example 6. On the basis of crystal field theory, account for the following : While
[Fe(H2O)6]3+ is throughly paramagnetic, [Fe(CN)6]3– is less paramagnetic.
Solution. This is because H2O is a weak ligand and 0 < P and therefore no spin pairing takes
–
place and the complex obtained is strongly paramagnetic. In the case of CN which is a strong ligand
0 > P and, therefore, electrons pair up leaving only one d-electron. This gives a weak paramagnetic
complex. This is shown in as under :

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 78 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

3d 4s

Fe atom (3d64s2)

Fe3+ atom (3d54s2)

d-electrons in Fe atom and Fe3+ ion.

d

d

o large
o small

d
d

(a ) (b ) (c )
3+
Occupation of d-electrons in Fe ion under different ligand fields (a) Free ion,
3–
(b), In weak octahedral field, e.g., [Fe(H2O)6]3+, (c) In strong cotahedral field e.g., [Fc(CN)6]
Example 7. Predict which of the following configurations are expected to have orbital
contribution in tetrahedral field :
(i) d2 (ii) d4 (iii) d8 (iv) d7 (v) d9
Solution. The following configurations are expected to have orbital contribution in tetrahedral
field :
(ii) d 4 (iii) d 8 (v) d 9
Example 8. What is magnetic susceptibility ? How does it vary with temperature ?
Solution. Magnetic susceptibility is a measure of the capacity of a substance to take up
magnetisation in applied magnetic field. The magnetic field per unit volume is represented as . The
molar susceptibility is given as :
M
Xm =

where M is the molecular mass and  is the density.
Magnetic susceptibility of a substance varies inversely with temperature as :
1 C
Xm = or X m 
T T
where T is absolute temperature and C is a constant known as Curie’s constant.
The variation of Xm with temperature for paramagnetic substance is shown below :

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 79

Example 9. Give examples of two species which show temperature independent

paramagnetism.
Soution. (i) CrO42– (ii) MnO4–
Example 10. Do you expect the complex [Cr(CH3COO)2  H2O]2 to be diamagnetic or
paramagnetic ?
Solution. This complex is diamagnetic due to quadrupole bonding between Cr – Cr.
Example 11. List the main configuration in octahedral field where orbital contributions are
(i) quenched (ii) not quenched
Solution. Orbital contributions to magnetic moment in octahedral field are quenched in the
following configurations :
(d3) t2g3 , (d6) t2g6 due to half filled and completely filled configurations.
Orbital contribution to magnetic moment in octahedral field are quenched :
High spin : d3(t2g)3, d4(t2g3 eg1), d5(t2g3 eg2), d8(t2g6 eg2), d9(t2g6 eg3)
Low spin : d6(t2g6), d7(t2g6 eg1)
Orbital contribution to magnetic moment is not quenched.
High spin : d1(t2g1), d2(t2g2), d6(t2g4 eg2), d7(t2g5 eg2)
Low spin : d4(t2g4), d5(t2g5)
Example 12. Predict which of the following configurations are expected to have orbital
contribution in high spin octahedral field : d1, d3, d6, d8.
Solution. The following configurations are expected to have orbital contribution in high spin
octahedral field : d1 and d6
Example 13. On the basis of crystal field theory, account for the following:
While [CoF6]3– is paramagnetic, [Co( NH3)6]3– is diamagnetic.
The [CoF6]3– ion is an example of high spin (outer orbital) complex while [Co(CN)6]3– is a
low spin (inner orbital) complex. Both have octahedral geometry and the magnetic preperties are
–
explained below on the basis of the field strength of the CN ligand.
In a free Co atom (3d7 4s2) and a Co3+ ion (3d6 4s0) the electrons are arranged as follows:
3d 4s
Co atom      
Co3+ ion      
In an octahedral complex, however the five d-orbitals split up into t2g and eg orbitals in the
–
[CoF6]3– ion. The energy difference o between the two sets of orbitals is not great enough (as F
is a weak field ligand) to cause any spin-pairing ( o < P) so that the arrangement of the five
d-orbitals is as shown in the figure below. There are four unpaired electrons and the complex ion
is strongly paramagnetic.
3– –
In the [Co (CN)6] ions, the stronger field of CN ion causes a greater energy difference (o)
between t2g and eg orbitals. As a result spin pairing occurs because P <o. The five d-orbitals are
arranged as show in below :

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 80 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

d

d

o large
 o small

d

d

(a) (b) (c)

Arrangement of d electrons in free Co3+ ion and under different ligand fields (a) Free ion
(b), In a weak octahedral field, (c) In a strong octahedral field.

EXERCISES
(Including Questions from Different University Papers)
Multiple Choice Questions (Choose the correct answers)
1. Ferromagnetic substance behaves as simple paramagnetics
(a) below Curie temperature (b) below Neel Temperature
(c) above Curie temperature (d) above Neel temperature.
2. The number of unpaired electrons in chromous acetals [Cr(CH3COO)2H2O]2 are
(a) 0 (b) 2 (c) 3 (d) 4
3. In which of the following configuration, the orbital contribution is quenched in octahedral
field ?
(a) t2g4 eg2 (b) t2g6 eg1 (c) t2g4 (d) t2g5 eg2
4. [Ti(H2O)6] represents the system
(a) d2 (b) d1 (c) d3 (d) d5
5. The spin only magnetic moment for Co ion is 2+

(a) 4.90 B.M. (b) 3.87 B.M. (c) 2.84 B.M. (d) 1.73 B.M.
6. Which of the following ion will have maximum s value ?
(a) Fe2+ (b) Cr3+ (c) Fe3+ (d) Co2+
7. Ferromagnetic materials show normal paramagnetic behaviour
(a) below TC (b) below TN (c) above TC (d) above TN
8. Which of the following is expected to be diamagnetic
(a) CrCl3 (b) CuCl2 (c) ZnCl2 (d) CuSO4 ?
9. Substances having paired electrons are
(a) ferromagnetic (b) antiferromagnetic
(c) diamagnetic (d) paramagnetic
10. If k is the magnetic susceptibility per unit volume,  is the density and M is the molecular
weight then molar susceptibility is
(a) M/ (b) /M (c) M/ (d) /M
11. In the first transition series, the divalent compound having maximum magnetic moment is
of
(a) Mn (b) Fe (c) Cu (d) Cr

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 81

12. Which of the following: configuration will not have orbital contribution in tetrahedral
geometry ?
(a) d 2 (b) d 4 (c) d 8 (d) d 9

ANSWERS
1. (c) 2. (a) 3. (b) 4. (b) 5. (b) 6. (c)
7. (c) 8. (c) 9. (c) 10. (a) 11. (a) 12. (a)

Short Answer Questions

1. Give one advantage each of Guoy method and Faraday method.
2. Calculate the magnetic moment (spin only) for the complex K4 [Mn (NCS)6].
3. Define magnetic susceptibility. Name a method used to measure it.
1
4. Draw the curves of M vs T(k) and vs T(K)
M
5. What is the calculated s value for Fe2+ high spin ion ?
6. Define ferromagnetic substance and give one example.
7. State the stereochemistry of Cu2+, Mn3+ and V3+
8. How are magnetic permeability and magnetic susceptibility related ?
9. Calculate the spin magnetic moment of V3+ ion.
10. What is meant by quenching of orbital angular momentum.

General Questions
1. (a) What is the origin of magnetism ? How is magnetic susceptibility measured ?
(b) The expected magnetic moment of K4[FeF6] is 5 B.M. How will you account for this
on the basis of valence bond theory ?
(c) Write short note on ferromagnetism and antiferromagnetism.
2. (a) Discuss the phenomenon of orbital contribution to magnetic moment. Give electronic
configurations in which orbital contribution is quenched in Oh field.
(b) Show that 4S (S  1) and n(n  2) are equivalent expressions.
3. (a) What is magnetic susceptibility and how does it vary with temperature ?
(b) What do you understand by diamagnetic - paramagnetic equilibrium in solid
complexes ?
4. (a) What is magnetic susceptibility ? How does it vary with temperature ?
(b) Why does Mn(II) ion shows maximum magnetic character amongst the divalent ions
of first transition series ?
(c) What do you understand by the term diamagnetic correction ?
(d) What is temperature independent paramagnetism ?
5. (a) Discuss briefly the Gouy’s method for measuring magnetic susceptibility.
(b) Dicuss the magnetic behaviour of first row transition metal compounds.
(c) Discuss the behaviour of ferromagnetism and antiferromagnetism with temperature.

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 82 CHEMISTRY FOR DEGREE STUDENTS–III (INORGANIC CHEMISTRY)

6. (a) Give a brief account of diamagnetism, paramagnetism, ferromagnetism and

antiferromagnetism.
(b) What is meant by temperature independent paramagnetism ? Explain.
7. (a) What is the origin of paramagnetism in transition metal compounds ?
(b) Calculate in Bohr magneton the expected magnetic moment for the following ions (spin
magnetic moment only)
(i) Fe3+ (ii) Mn2+ (iii) Ni2+ (iv) Cu+
8. (a) How do you explain the ferromagnetic properties of iron, cobalt and nickel ?
(b) Discuss briefly the Gouy’s method for measuring magnetic susceptibility.
9. (a) What is meant by quenching orbital angular momentum and what are its consequences ?
Give electronic configuration in which orbital contribution is quenched in octahedral
and tetrahedral complexes.
(b) Calculate s and S + L for 3d2.
(Hint. S = 1 and L = 3).
10. (a) Define paramagnetism, diamagnetism, ferromagnetism and antiferromagnetism.
(b) Discuss Gouy’s method for measuring magnetic susceptibility.
11. Discuss the phenomenon of orbital contribution to magnetic moment and give brief
application of this phenomenon to 3d-metal complexes.
12. The magnetic moment of transition elements can be calculated from the relation :
(S + L) = 4S ( S  1)  L(L  1)
Explain the various terms involved.
13. (a) Describe Gouy’s method for measuring magnetic susceptibilities.
(b) What do you understand by the terms paramagnetism and diamagnetism ? Predict the
magnetic moment for octahedral complexes of Fe2+ with strong field ligands and with
weak field ligands.
14. (a) Calculate spin only magnetic moment for Co2+ ion.
(b) What is temperature independent paramagnetism ? Explain.
(c) Describe briefly quenching of orbital angular momentum in tetrahedral complexes.
(d) Discuss the variations of magnetic susceptibility with temperature.
15. (a) What do you understand by magnetic susceptibility ?
How does it vary with temperature ?
(b) Calculate the magnetic moments (spin only) for the following ions :
(i) [Mn (NCS)6]4– (ii) [Fe (H2O)6]3+ (iii) Ni2+
Which of the above ions do you expect to be coloured ?
(c) “Cu2+ ions are coloured and paramagnetic while Zn 2+-ions are colourless and
diamagnetic. Explain.
16. (a) What is meant by temperature independent paramagnetism ?
(b) Calculate, in Bohr magnetons, the magnetic moment expected from spin only for the
ions : V4+, Cr+3, Fe3+ and Ni3+.
17. (a) Discuss the variation of magnetic susceptibility with temperature
(b) What do you understand by the term diamagnetic correction ?
(c) Why we consider spin only formula for finding the magnetic moment of 3d-complexes ?
(d) What is temperature independent paramagnetism ?

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 MAGNETIC PROPERTIES OF TRANSITION METAL COMPOUNDS 83

18. (a) What is magnetic susceptibility ? How does it vary with temperature ?
(b) Calculate the magnetic moment of Cr3+ ion by the spin only formula
19. (a) Discuss magnetism in
(b) Ni complexes
(c) Hydroxo, oxo and bridged complexes of Cr(III).
20. (a) Discuss origin of magnetism in substances
(b) Derive the relationship between magnetic susceptibility and magnetic moment
21. (i) Explain antiferromagnetic susbtance
(ii) Name one antiferromagnetic substance
22. (a) Discuss the relationship between magnetic moment and magnetic susceptibility.
(b) The complexes of first transition series are mainly high spin, while those of second and
third translation series are of low spin type. Explain.
(c) The complex [Ni(CN)4]2– is diamagnetic but [NiCl4]2– is paramagnetic
23. (a) Calculate magnetic moment (spin only) of K4[Mn(CNS)6] complex
(b) Discuss variation of magnetic susceptibility with temperature
24. (a) What is the origin of paramagnetism ?
(b) How magnetic susceptibility varies with temperature ?
(c) Calculate magnetic moment for the complex K4[Mn(CNS)6] (Spin only value)
25. (a) Discuss Gouy’s method for measuring magnetic susceptibility. How magnetic
susceptibility varies with temperature ?
(b) What do you understand by spin and orbital contribution to the magnetic moments ?
(c) Calculate the expected values of magnetic moments in B.M. from spin only formula of
Ni2+, Zn2+, Cr3+ and Fe3+ ions.
26. (a) The net paramagnetism in a substance is slightly less than the true paramagnetism. How
will you explain this behaviour ?
(b) Which of the following metal ions are expected to show magnetic moment close to 1.73
B.M.: Cu+ , Ti3+ , Fe2+, Cr3+ ?
(c) What do you understand by diamagnetic-paramagnetic equilibrium in solid complexes ?
(d) Discuss Gouy’s method for measuring magnetic susceptibility. How magnetic
susceptibility varies with temperature ?

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