E-Content

B.Sc. 3rd Year

Inorganic Chemistry Paper-I

Unit-II

Chapter-3rd

Magnetism In Transition Metal Compounds

Dr. Anil Kumar

Associate Professor,

Department of Chemistry,

Harish Chandra P G College,

Maidagin Varanasi, UP-221001

e-mail: [email protected]
Magnetism In Transition Metal
Compounds
In transition metal compounds or complexes generally following five type of magnetism are
found.

1. Paramagnetism 2.Diamagnetism

3. Ferromagnetism 4. Antiferromagnetism 5. Ferrimagnetism

1. Paramagnetism- When a substances placed in magnetic field of strength H. If the field in

substance is greater than H, the substance is paramagnetic. It is easier for magnetic line of force
to travel through paramagnetic material than through a vacuum. Thus paramagnetic material
attract line of forces and if it is free to move a paramagnetic material will move from weaker to
stronger part of magnetic field. Paramagnetism arises as a result of unpaired electrons in
atoms, molecules or ions. Unpaired electrons are the main source of paramagnetism. For
example- Ti3+, Mn2+, Cu2+,Au3+,etc.

Origin of paramagnetism - We know from elementary physics any moving charge particle
create magnetic field . The electron has two type of motion and produces two type magnetic
moment. One is orbital motion due to motion of electron round the nucleus in own orbit create
orbital moment. Another is spin motion due to spin of electron in own axis produce spin
moment. The effective magnetic moment is obtained by adding the magnetic moment due to
orbital motion i.e. orbital magnetic moment, μl and due to spin motion i.e. spin magnetic
moment, μs of electrons given as :

μeff = μL + μS = √L(L+1) + √4S(S+1)

Orbital magnetic moment, μL = gL√L(L+1) and spin magnetic moment μs = gs√S(S+1)

Dia magnetism is much weaker than paramanetism i.e. 10-100 time weaker.

2. Diamagnetism- If the field in the substance is less than H, and then the substance is
diamagnetic. Diamagnetic material tends to repel line of force. It is harder for magnetic lie of
force to travel through diamagnetic material than through vacuum ad such material tends to
move from a stronger to a weaker part of magnetic field. In diamagmetic compound, al the
electron spis are paired that is in d-subshell, all electrons are completely filled or completely
vacant (d10, d0). Ex. Sc3+, Ti+, Zn2+, Cd2+,etc.

3. Ferromagnetism- It should be noted that Fe, Co, Ni is ferromagnetic. Ferromagetic material

may be regarded as special case of paramagnetism in which the moment on individual atom
becomes aligned and all points in the same direction. When this happens, magnetic property is
greatly enhanced. These substances show permanent magnetism even after magnetic field is
removed. Such substances are called ferromagnetic substances. In case of ferromagnetic
substances, the alignments of all magnetic moments are in same direction (parallel direction)
↑↑↑↑↑↑ and such substances have definite value of their magnetic moments. This is only
difference from paramagnetic substances. Thus a ferromagnetic substances can be defined as
that substance in which alignment of all magnetic moments are in same direction that is
parallel. Ferromagnetism like paramagnetism is also due to the presence of unpaired electrons
but ferromagnetic material show permanent magnetism even in the absence of magnetic field.
Ferromagnetic substances are very important in technology. For example- Cr2O3 is used as
ferromagnetic tapes in cassette recorder.

4.Antiferromagntism- Antiferromagetic substance is that in which number of magnetic

moment vector aligned in one direction is equal to magnetic moment vectors aligned in
opposite direction ↑↓↑↓↑↓ and hence such substances have zero value for resultant
magnetic moment. In other words we can say that in an antiferromagnetic substance, half of
the magnetic moment vectors are aliged in one direction while the remaining half magnetic
moment vector aligned in opposite direction. Transition metal oxide namely, V2O3, Cr2O3, MnO,
Mn2O3, FeO,Fe2O3, CoO, Co3O4 and NiO show antiferromagnetic character. Cupric acetate
monohydrate is also example of antiferromagnetic substances.

5.Ferrimagnetism- A ferrimagnetic substance is that in which number of magnetic moment

vectors aligned in parallel and antiparallel direction is unequal ↑↑↑↓↑↓ and hence such
substances have some value of net magnetic moment. Example of substances which show
ferrimagnetic behavior are Fe3O4 and ferrites having general formula M2+Fe3+2O4 (M2+ = Mg2+,
Cu2+, Zn2+, etc).

Effect of temperature on ferromagnetic, ferrimagnetic and antiferromagnetic substances:

By the increase of temperature the order of alignment of magnetic moment vector in

ferromagnetic, antiferromagnetic and ferrimagnetic substances get changed and hence the
substances become paramagnetic. For example-

1. Fe3O4 which is ferrimagnetic at ordinary temperature show paramgnetic character at

850K.
 2. V2O5 transform from antiferromagnetic to paramagmetic at 150K.
3. NiO transforms from atiferromagnetic state to paramagnetic state at 395K.
4. CrO2 transform from ferromagnetic state to paramagnetic state at 395K.

Magnetic susceptibility-
When a substance is placed in magnetic field of strength H, the flux of magnetic induction B
within the substance is given by

B=H+4πI ……(1)

Where I is termed as intensity of magnetization. Dividing both side of equation by H,

B/H = H/H + 4πI/H = 1+ 4π I/H = 1 + 4πχ (χ -Chi)

Or, B/H = 4π χ …..(2)

Where the ratio B/H is called magnetic permeability of substances and χ is magnetic
susceptibility per unit volume. Susceptibility per unit volume, χ is given by χ = I/H and the extent
to which the material is susceptible to the external magnetic field or susceptible to
magnetization. It may be noted that I and H are in the same unit, χ become dimensionless
quantity. By placing B/H = P and I/H = χ in the equation 2, we get P = 1+4πχ.

Gram Susceptibility

In the practice, susceptibility is usually expressed in per unit mass that is gram specific or
weight susceptibility (χg) rather than per unit volume. Χg is given by

χg = volume susceptibility/density = χ/d

The molar susceptibility χM is given as

Χm = Gram susceptibility x Molecular weight

Χm = (χ/d) x M

Curie Law:
Pierre Curie found that the major magnetic susceptibility χ is inversely proportional to absolute
temperature and this is called Curie Law.

ΧM α 1/T or χM = C/T where C = constant which is equal to Nμeff2/3k.

This constant is characteristic of substance and is called Curie constant and the expression is
called Curie expression. From this equation it is evident that the plot of χM values against 1/T
will give us straight line of slope C which intercepts the origin. Although, many paramagnetic
substances obeys Curie’s Law.

Curie-Weiss Law
It is determined by χcorrM = C/T-θ where θ is the temperature at which line cuts the T axis and is
called Weiss constant. If the value of θ is positive i.e. above 0K, the substance is said to be
ferromagnetic and if θ is negative, that is below 0K, the substance is said to be
antiferromagetic.

Method for determining magnetic susceptibility- The method for determining

magnetic susceptibility can be divided into two groups .

1. Uniform magnetic field type 2. Nonuniform magnetic field type.

Most of the balances are used for the measurement of magnetic susceptibility are of uniform
type. Example-Guoy method, Bhatnagar-Mathur method, Quincke method,etc while the
method used in non uniform method magnetic field method are Curie method, Curie-
Cheneveau’s method, NMR method etc.

1.Guoy method- This method was suggested by Gouy 1889. This is used to measure
magnetic susceptibility of various substances. In this method about 0.5 -1.0g sample in
form of powdered solid, \liquid or solution of moderate concentration are used.

Principle- This method is based on the fact that the magnetic field exerted on the sample is
directly proportional to difference in masses when the field is switched on and off.

Method- The Gouy method is more often used. Here the sample may be presented as a long
rod of material. A solution, or glass tube packed with powder. One end of sample is placed in
uniform magnetic field and other end in very low or zero field. The forces observed here are
much larger and can be measured using a modified laboratory balance.

F= ½ A. χ H2 …..1

Where A is the cross sectional area of the tube and H is the intensity of magnetic field and χ is
volume susceptibility. This expression is valid only if the measurement done in vacuum.
However if the sample is surrounded by air then the susceptibility of air much be substracted
from the measured susceptibility. In the case we shall use this equation.

F= ½ A.H2 (χ-χ’)…..2 where, χ’ is 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 force. This force is negative because of the diamagnetic material of the tube. It is
denoted by δ. The equation 2 becomes-

F= ½ A.H2 (χ-χ’) + δ ……..3

For the sample of constant length and cross sectional area the factor, AH2 is constant. Now if
the density of sample is introduced the above equation may be written as

106χ = (α+βF’)/W where α=constant allowing the displaced air and is equal to 0.029

W= weight of sample expressed in gram.F’ = Force on the sample and is equal to F-δ but F and δ
are given in milligrams. β= tube calibration constant.

The apparatus is calibrated by making measurement on a substance whose susceptibility is

accurately known.

The standard substance commonly used for calibration is mercury tetrathiocyanatocobalt (II)
Hg[Co(SCN)4]. Its susceptibility is 16.44 x 10-6 at 20°C.

2. Bhatnagar-Mathur Method:
Bhatnagar and Mathur in 1928 modified the Gouy balance such a way that it may measure
susceptibility of liquid. This method is based on the fact that the force acting on the sample is
directly proportional to magnetic pull producing a displacement of pointer when the magnetic
field is on. Bhatnagar and Mathur used a balance in this method contains a silver spiral S’ which
is suspended from a brass hook at the top and the sample A is suspended from the lower end of
the spiral in such a way that the lower end of the sample lies in the region of strong and
uniform magnetic field. P is the thin pointer attached to the spiral. The displacement of pointer
P is measured with the microscope provided with a scale.

Theory and calculation

When the sample is placed between two poles of strong magnetic field the vertical magnetic
pull on the sample is given by the following relation.

Fx=1/2(χ1-χ2)AH2 ………1 A= area of cross section of the sample

In this balance the strong magnetic field pulls the sample which pulls the spiral producing a
displacement of pointer. Reading is taken when the magnetic field is on and off. Thus the force
is given by
 Fx= (L/s)g …..2

Where L is the displacement of pointer and s is the displacement of pointer produced by 1

gram of the sample. From equation 1 and 2 we get

1/2(χ1-χ2)AH2 = (l/s)g or χ1=χ2+(2lg/sAH2)

where χ1 and χ2 are the volume susceptibility of sample and surrounding medium.

3. Quincke’s method
This method was suggested by G. Quincke in 1885. It was suitable for liquid, aqueous solution
and some gases. This method is based upon the principle of the fact that when magnetic fiels is
applied on the liquid placed in capillary tube the meniscus fall if the liquid is diamagnetic and
rises if it is paramagnetic. The apparatus in this method is shown in figure it consists of U-tube
(ABCDE) in which CD is a capillarytube placed in uniform magnetic field of strength 25000
oerested. The field near C is 50-100 oerested which is negligible. When the field is applied the
liquid rises and fall in the capillary tube, the liquid is paramagnetic and diamagnetic in nature,
respectively.

Theory

When a strong and uniform magnetic field is applied at upper end of capillary tube the liquid
rises if it is paramagnetic or fall if it is diamagnetic in nature. Letus Δh is the change in the
height of the liquid then the corresponding hydrostatic pressure will be given by following
relation

P = Δhdg ………1

Force = Pressure x Area

 F = Δhdg x A ……..2 where A = area of cross section of tube

Equation- 2 represents the vertical force ΔFx. Hence, Fx = Δhdg x A. The vertical force
due to change in hydrostatic pressure will be balanced by magnetic pull i.e.

F = Δhdg x A = ½ (χ1-χ2)AH2 or χ1-χ2 = (2dgΔh)/H2 ……..3

Every step of the equation divided by d

χ1/d -χ2/d = (2dgΔh)/dH2 or χ-χ0 = (2dgΔh)/H2 ……4 Since, χ = χ/d is the gram susceptibility.

Thus the magnetic susceptibility of a liquid can be measured with help of this equation where χ
and χ0 are the mass susceptibility of the liquid of density d and gas and vapour of density d0
above the liquid.

If the tube AB is sufficiently larger diameter and the susceptibility of vapour χ0 above the liquid
is negligible. Then the equation 4 becomes χ = (2dgΔh)/H2

4. Curie Method- This method is based on non uniform magnetic field type. Curie
devised magnetic balance known as Curie balance to study the variation of
susceptibility with temperature. This gives a clear knowledge among paramagnetic,
diamagnetic and ferromagnetic substances. The principle of this method is based on
the fact that if a sample is placed in non uniform magnetic field, a force is exerted on
the sample giving a displacement which is measured in terms of Torque required to
bring the sample back to its original position. Let us consider a small volume dv of
the sampe, the force exerted on the sample dFx is given by equation

dFx = ( χ1-χ2)dvHy∂Hy/∂x ……1

The total forceexerted on the sample may becalculated by integrating equation 1

∫dFx= ∫( χ1-χ2)dvHy∂Hy/∂x

Fx = ( χ1-χ2)dvHy∂Hy/∂x …..2 but w = v x d or v = w/d …..3 χ = χ 1/d and χ0 = χ2/d …..4

Substituting the value from equation 3 and 4 in equation 2.

Fx = ( χ-χ0)wHy∂Hy/∂x ……5

χ and χ0 are gram susceptibility of sample and surrounding medium respectively.

W is the weight of the sample. In equation 5, all quantity except ∂Hy/∂x can be known easily. To
measure this quantity a test coil and ballistic galvanometer is used.

5. Cheneveau Method- In 1910, Cheneveau modified the Curie balance as shown in

the figure.

It consists of torsion of AB suspended by fine wire from torsion head C. The end B of the arm
AB support the sample which move freely between the poles of permanent magnet. The
magnet may move forward or backward with respect to sample due to its magnetic
susceptibility sample is either repelled or attracted. The magnet is slowly turned so as to recede
from the sample till the deflection is maximum. This reading is noted for both side of zero. For
calibration distilled water is used as a standard substance. The observations are recorded first
for the empty tube and then with the samples in it. The susceptibility is calculated from the
following relations

χ/χ1 = (m1x ± x2)/ (mx1 ± x2)

Where, χ1 is the susceptibility of known substance of known susceptibility, m1 is mass of known
substance, m is mass of sample of unknown susceptibility (χ), x is deflection from unknown
substance, x1 deflection of reference substance and x2 is deflection from empty tube. The
positive sign for x2 is used when the empty tube have susceptibility opposite to that of test
substance.
 6. NMR Method
This is useful method to measure magnetic susceptibility. The dissolved paramagnetic
substance causes a shift (ΔH) in the resonance line of inert reference molecule. Thus,

ΔH/H = (2π/3)Δχ ……1

Where, Δχ is the change in volume susceptibility. Actually a paramagnetic substance is dissolved

in water containing 2% tertiary butanol which acts as reference standard. For external
reference and aqueous solution of 2% tertiary butanol is used in capillary tube. Methyl proton
of tertiary butanol in two solutions would resonate at two places due to difference in volume
susceptibility of two solution the resonance line of paramagnetic substance is observed at high
field. The gram susceptibility χg of the solute is given by the following equation

Χg = ΔH/H(3/2πc) + χ0 + d0-ds/c ………………2

Where, χ0 is the gram susceptibility of solvent, c is concentration of solute in g/mL of solution,
d0 is the density of the solvent and ds is the density of solution.

Spin only Formula and correlation of μs and μeff.:

The effective magnetic moment is obtained by adding the magnetic moment due to orbital
motion i.e. orbital magnetic moment, μl and due to spin motion i.e. spins magnetic moment, μs
of electrons given as

Orbital magnetic moment, μL = gL√L(L+1) and spin magnetic moment μs = gs√S(S+1)

Here, gL and gS are the Lande splitting factors for orbital and spin magnetic moments. Since the
μL gL = 1 for μsgS =2, then μL and μS are given by

μL = √L(L+1) ……………..1 μLS= 2√S(S+1) = √4S(S+1) ………………..2

The μeff is given by the addition of equation 1 and equation 2

 μeff = μL + μS = √L(L+1) + √4S(S+1) ……..3

This equation is generally used to calculate the value of μeff of the ions of metal of first
transition series. For the ions with S term symbol example Mg2+ and Fe3+ ions. L = 0 i.e. L = 0 for
S term symbol. There is no contribution of orbital magnetic moment to μeff for the ions which
containing S term symbol. For the ions which have L = 0, the equation 3 giving the value of μeff
becomes as

μeff = √4S(S+1) BM………4 Now, S = ½ x n = n/2 Here, n = number of unpaired

electrons. Putting the valu of S in equation 4, then

μeff = √4n/2(n/2+1) = √n(n+2) BM …….5

Since the value of μeff given by equation 4 and 5 is that which contains only contribution made
by spin magnetic moment resulting from the spin motion of the electrons, it is called spin only
magnetic moment i.e. μspin only whose value thus given as

μspin only = √4S(S+1) BM = √n(n+2) BM …….6

This formula represented by equation is called spin only formula and the value of magnetic
moment calculated from this formula is called spin only value. The magnetic moment due to
spin magnetic moment, the orbital magnetic moment is largely suppressed or quenched. Due to
the electrostatic field of other atoms, ions or molecules surrounding metal ions. The metal ions
restrict the motion of electrons around the nucleus.

Orbital contribution to magnetic moment:

For f-block elements especially in Lanthanides, the unpaired electrons in n-2 f orbital are quite
deeply seated and hence are well shielded by 5s and 5p electrons from the effect of other
atoms in their compounds (crystal field effect) consequently the effective magnetic moment
Ln3+ ions with the exception of Sm3+ ions are given by following equation provided that
ground state symbol of Ln3+ ions as

μeff = μJ = g √J(J+1) BM where g = Lande splitting factor are

given as

𝑱( 𝐉+𝟏)+ 𝑺(𝐒+𝟏)−𝐋(𝐋+𝟏)
g=1+ S = resultant spin quantum number
𝟐𝐉( 𝐉+𝟏)

L = resultant orbital quantum number and J = resultant inner quantum number which is
obtained by coupling of L and S. In lanthanide, the spin contribution S and orbital contribution L
couple together to give new quantum number, J.
J = L-S, when the shell is less than half field and J = L+ S, when the shell is more than half field.

L-S coupling: It is also known as Russel-Saunder’s coupling. According to this coupling

1. All the l vectors (𝑎𝑛𝑔𝑢𝑙𝑎𝑟 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 𝑞𝑢𝑎𝑛𝑡𝑢𝑚 𝑛𝑢𝑚𝑏𝑒𝑟) of the electron couples
together electro statically to give the resultant vector, L called resultant orbital angular
momentum quantum number. Different values of l ( small) μeff = μL + μS = √L(L+1) +
√4S(S+1) defines the state of electron only while those of L defines the state of free
atom or ion as a whole. L is always an integer including 0. Different values of l are
represented by capital letters known as Mulliken’s notation as shown here

Values of L = 0 1 2 3 4 5………….

Mulliken notation = S P D F G H…………. L = +1+1, 0 0, -1-1 = 0 when the

p orbital is fulfilled

2. Similarly, all s vectors (𝐬𝐩𝐢𝐧 𝐚𝐧𝐠𝐮𝐥𝐚𝐫 𝐦𝐨𝐦𝐞𝐧𝐭𝐮𝐦 𝐪𝐮𝐚𝐧𝐭𝐮𝐦 𝐧𝐮𝐦𝐛𝐞𝐫)

Also combined to give the resultant spin angular momentum quantum number S which is an
integer or half integer depending on the number of electrons involved and the direction of
the spin vectors, s = half of the number of unpaired electrons n i.e. s = n/2. The value of S
for electrons in other completely filled s, p, d or f orbital is zero. For completely filled p-
orbital for which L =1, S =0. The value of S = +1/2-1/2, +1/2-1/2, +1/2-1/2 = 0.

3. 2S+1 is known as multiplicity of L state. This quantity gives the permitted value of J for a
given value of L and J is called resultant inner quantum number obtained by coupling of
L and S where L and S vectors couple together, they give the the resultant vector J which
is known as resultant inner quantum number or total angular momentum number of the
atom. The process of L-S coupling may be representing as

s1 + s2 + s3 +……… + l1 + l2 + l3…. = S+L=J

The value of J are 2S+1 when L≥S and 2L+1 when L≤ S

When L=0, J can have only one value J = S .The value of J always positive never
negative.

Magnetic moment from magnetic susceptibility:

𝐍𝟎𝛍𝟐𝛍𝟎
Paramagnetic susceptibility, χp is given by χp = ……1 where N0 is Avogadro
𝟑𝒌𝑻
Number, μ = magnetic moment, k = Boltzmann constant, μ0 = permeability, T = absolute
temperature.
 The value of χM calculated from the experimental value of χg. It is an algebraic sum of χp, χTIP
(Temperature independent paramagnetism) and χdia (diamagnetic susceptibility).

ΧM = χp+ χTIP + χdia …………2

Generally we do not usually know the value of χTIP. Corrected molar susceptibility, χM corr
which is equal to χM – χdia is also used in place of χP in equation 1. The value of magnetic
moment obtained by putting χM corr in place of χp in equation 1 is called effective magnetic
moment and hence is represented by μeff, the equation 1 becomes

𝑵𝟎 𝛍𝟐𝐞𝐟𝐟 𝟐𝛍𝟎 𝟑𝒌𝑻𝝌𝒄𝒐𝒓𝒓

𝑴
χM corr = or μeff = √
𝟑𝒌𝑻 𝑵𝟎 𝝁𝟎

On substituting the value of k and N, we get

μeff = 2.83 √𝝌𝒄𝒐𝒓𝒓

𝑴 𝑻 ……..3

magnetic moments are expressed in Bohr Magneton (BM)

1BM = h/4πmc = 9.27 x 10-21 erg/Gauss where h= Planck’s constant, e = electronic charge, v
= velocity of light and m = mass of electron.

Uses of magnetic moment values:

The number of unpaired electron present in d-orbital of central metal ion of given complex
compound can be determined with the help of experimental magnetic moment values of
complex compounds. The number of unpaired electrons thus determined can be used to
predict

1. Whether a given four coordinated complex is square planar (dsp2 hybridized) or

tetrahedral (sp3). To make it clear let us consider the geometry of [Ni(CN)4]2- ion has
n=0 diamagnetic and is square planar due to dsp2 hybridization while [NiCl4]2- has n=2,
paramagnetic and is tetrahedral due to sp3 hybridisation.
2. Whether the given six coordinated compound is inner orbital complex i.e d2sp3
hybridized or outer orbital complex i.e. sp3d2 hybridized. To make it clear, consider the
number of unpaired electrons in d-orbital. For example in Fe(CN)63- ion has n=1
paramagnetic and is inner orbital octahedral complex due to d2sp3 hybridization while
FeF63- ion has n=5 i.e number of unpaired electrons = 5 and is outer orbital octahedral
complex due to sp3d2 hybridisation.

Questions.

Explain the following

 a. L-S coupling.
b. [FeF6]3- has much higher magnetic properties than [Fe(CN)6]3-.
c. [Ni(CN)4]2- is diamagnetic and square planar while [NiCl4]2- is paramagnetic and
tetrahedral.]
d. Quenching of orbiotal angular momentum
e. Lande splitting factor.

2. a. Describe the method of Gouy’s for the measurement of magnetic susceptibilities of

substance.

b. What are the origin of paramagnetism and diamagnetism?

3. a. What are μs and μL+S values? Explain why are μeff values close to μs values for majority of 3d
metal complexes?

b. What is Curie’s-Weiss Law? Give significance of Weiss constant.

4. How is magnetic susceptibility measured by Bhatnagar-Mathur method?

5. Describe the method of Quincke’s for the measurement of magnetic susceptibilities of

substance.

6. Describe the Curie’s method of the measurement of magnetic susceptibilities of substance.

7. Describe the Cheneveau and NMR method for the measurement of magnetic susceptibilities
of substance.

Multiple Choice Questions

1. The spin only magnetic moment for Mn2+ is

a. 5.91 BM b. 4.89 BM c. 3.87 BM d.1.73 BM
2. Which of the following has maximum magnetic moment values
a. Mn3+ b. Fe3+ c. Co2+ d. Cu2+
3. The number of unpaired electrons in [Co(NH3)6]Br3 is
a. 1 b. 2 c. 3 d. 0

Answers

1. a, 2. b, 3. d

References

1. Chemistry for degree students, B.Sc. II year, Dr. R. L. Madan

2. Inorganic Chemistry Vol III, Dr. S.C. Tripathi and Dr. Upendra Tripathi
3. Inorganic Chemistry, J.D. Lee