Experimental Physical Chemistry 329

Magnetic Susceptibility Measurements of Solids*

INTRODUCTION:

Magnetism is a property characteristic of all materials that contain electrically charged

particles. A moving electrical charge (i.e. electric current) gives rise to a magnetic field in a
material. The contribution of nucleons to the magnetic field in substances is small and requires
special instrumentation to observe. For the purpose of this laboratory the effect from nucleons is
neglected, thus magnetism may be considered to be entirely of electronic origin. In an atom, the
magnetic field is due to the coupled orbital and spin magnetic moments associated with the
motion of electrons. The orbital magnetic moment is due to the motion of electrons around the
nucleus whereas the spin magnetic moment is due to the precession of the electrons about their
own axes. The resultant of the orbital and spin magnetic moments of the constituent atoms of a
material gives rise to the observed magnetic properties. Knowledge about the magnetic properties
of materials is an important aspect in the study and characterization of substances. Unlike many
other, commonly employed analytical methods, magnetic property characterization is a
non-destructive technique.

THEORY
Often magnetic properties of materials are studied by applying a magnetic field and
measuring the induced magnetization in these materials. The magnetic induction, B, that a
substance experiences when placed in an applied external magnetic field, H, is given by the
expression:

Β = H + 4πM (1)

where M is the magnetic moment of the compound per unit volume or the Magnetization.
The volume susceptibility of the compound, χv, is defined as the ratio of the induced magnetic
moment per unit volume to the applied field:
χv = M/H (2)

*Z.S. Teweldemedhin, R.L. Fuller and M. Greenblatt

Department of Chemistry, Rutgers, The State University of New Jersey, Piscataway, NJ 08855

1 01/22/03
 The two most important responses observed are characterized as diamagnetic and
paramagnetic moment (Fig. 1). As shown in this figure, the applied magnetic field remains
unaffected in a vacuum but is attracted by a paramagnetic, and repelled by a ideal diamagnetic
media.

(a) (b)

(c)
Fig. 1
Behavior of Applied Magnetic Field in Different Media :
(a) Vacuum (b) Paramagnet (c) Ideal Diamagnet

In diamagnetic materials , all the electrons in the atoms are paired (e.g. H2(g), NaCl(s) ) and the
resultant magnetic moment is zero due to the absence of unpaired electrons. The external
magnetic field induces a current whose associated magnetic field is directed opposite to the
applied field. The induced magnetic moment associated with this field is called a diamagnetic
moment and is negative relative to the applied magnetic field and independent of temperature.
The magnitude of the diamagnetic susceptibility is usually small, in the range of 10-6 c.g.s units.
All inert gases and most organic compounds are examples of diamagnetic materials.
 APPLIED FIELD, H = 0

FIGURE 2
Random Orientation of Magnetic moments in Paramagnetic Material

In paramagnetic materials, the constituent atoms have unpaired electrons resulting in a net
magnetic moment. Generally at room temperature, the individual magnetic moments are
randomly oriented as shown in Fig. 2 above. If an external magnetic field is applied to these
randomly oriented intrinsic magnetic moments, they will tend to become alligned in a direction
parallel to the external magnetic field.

The magnetic moment induced in such materials by the application of an external magnetic
field is called a paramagnetic moment. The magnitude of the susceptibility of paramagnetic
substances is in the range of 10-3 to 10-6 c.g.s units and is positive. Typical paramagnetic
compounds include gaseous compounds like molecular oxygen (O2) and nitric oxide (NO), vapors
of alkali metals and certain salts of transition and rare-earth metals.

The alignment of the magnetic moments of a paramagnetic substance under an applied

magnetic field is opposed by the thermal motion of the magnetic ions which tends to randomize
the moments. Hence the observed paramagnetic susceptibility of a substance increases with
decreasing temperature since the effect of thermal motion is minimized at lower temperatures
(Fig. 3). According to Curie's Law,

C
χM = T (3)

the susceptibility of a paramagnetic substance is inversely proportional to temperature where C is

the Curie constant. The variation of the inverse magnetic susceptibility (χ-1M
) with temperature is
linear. The slope of this line is equal to 1/C. The value of C is related to the number of unpaired
electrons present in the compound by the following expression:

(8C)1/2 = g [S (S + 1)]1/2 = [n (n + 2 )]1/2 (4)

where Lande's factor, g ≈ 2.0 for an electron or ion with no orbital contribution to the
magnetic moment and S, is the resultant spin quantum number, (it is the total spin angular
momentum of all the unpaired electrons in the system), and n is the number of unpaired electrons
in the system ( i.e S = n/2 ). Eq. 4, is generally valid for compounds of most of the first row
transition metals, where the orbital contribution to the magnetic moment is completely quenched
and only the spin contribution, S need be considered. This will be discussed in more detail
subsequently.

1/χ
χ

Temperature Temperature

(a) (b)

Fig. 3
(a). Magnetic susceptibility and (b). inverse magnetic susceptibility
dependence on temperature of a paramagnetic material.

Fig. 3 shows the plot of χ Vs T and 1/χ Vs T (T in absolute temperature, K) typical for a
paramagnetic substance in which orbital contribution to the susceptibility is negligible.

Paramagnetic materials, besides having unpaired electrons, contain paired electrons in the
inner (closed) shells of the constituent atoms. The presence of these paired electrons make
diamagnetism an inherent property of all materials. Thus the magnetic moment measured is in
fact the sum of both paramagnetic (positive quantity) and the associated diamagnetic (negative
quantity) moment. Since the presence of an intrinsic magnetic moment in a substance results in a
large paramagnetic moment, the diamagnetic effects are often neglected in the calculations.
However, if the paramagnetic and diamagnetic moments of the substance under investigation are
of comparable magnitude, and where accurate measurements are desired, corrections due to the
diamagnetic contributions are made to the measured magnetic moments.

So far we have considered paramagnetic substances in which there are no significant

interactions between the magnetic moments of its atoms. However, magnetic moments of
individual atoms in many substances do interact with each other in several different ways. In
these materials, Curie's law is not obeyed; often, the magnetic behavior of these substances is
best described by a Curie-Weiss law which takes into account the interactions among the
individual magnetic moments:

C
χM = (5)
(T - θ)

where θ is the Weiss constant (or paramagnetic Curie temperature).

Interactions of magnetic moments in condensed systems (i.e solids) will in most cases lead
to different types of magnetic ordering, characteristic of the substance. This is shown in Fig. 4
where the net spin on each atom is represented by an arrow aligned "with" or "against" the applied
external magnetic field. The type of magnetic interactions present in a particular substance is
primarily determined by the nature of the constituent ions and chemical bonds. The magnetic
interactions between the individual magnetic moments result in a net stabilization energy. The
two most common types of magnetic ordering or interactions are called ferromagnetism and
antiferromgnetism. In ferromagnetic substances, the magnetic moments of adjacent atoms are
aligned parallel to one another below a certain critical temperature (known as the Curie
temperature, Tc) as shown in Fig. 4a. This type of magnetic ordering is characterized by a
spontaneous magnetization of the substance below Tc even in the absence of an external
magnetic field. Iron, nickel and cobalt and some rare-earth metals, as well as some compounds
and alloys of these elements are typical examples that show ferromagnetic ordering.

In antiferromagnetic substances, the individual magnetic moments are aligned antiparallel to

one another below a certain critical temperature, (known as Néel temperature, TN ). This
interaction gives no net magnetization when the neighboring atoms have magnetic moments of
identical magnitude as shown in Fig. 4b. Most compounds of the transition elements such as
MnO, MnF2, FeCl2 and elements such as chromium, α-manganese and some rare-earth metals
such as cerium, praseodymium, neodymium, samarium, and europium display antiferromagnetic
ordering. Compounds that exhibit ferromagnetic or antiferromagnetic type of magnetic ordering
often obey the Curie-Weiss law (Eq. 5) at temperatures well above the transition temperatures
(ordering temperature, Tc or TN).

(a) (b)

(c)
FIGURE 4
Types of Magnetic Ordering: (a). Ferromagnetic (b). Antiferromagnetic (c). Ferrimagnetic.

Ferrimagnetism is another prevalent type of ordering of the magnetic moments . In a

ferrimagnetic substance, although the individual magnetic moments of adjacent atomic particles
are aligned antiparallel, they are not of equal magnitude (i.e. when the type of interacting
neighboring atoms are different), e.g. Fe3O4 (FeO·Fe2O3).

As expected, the magnetic response becomes stronger, as the number of unpaired electrons
present increases. Hence it is customary to measure experimentally the magnetic susceptibility of
a substance as a function of its weight, χg:
 χg = χv /ρ (6)

where χg, the mass susceptibility of the compound, is the induced magnetic moment per unit
mass per unit applied magnetic field, and ρ is the density of the material.

The mass susceptibility of the compound is related to the molar susceptibility, χM:

χM = χg·MW/Z (7)

where MW is the molecular weight of the compound and Z is the number of moles of
magnetic ions per formula weight of the compound. The molar magnetic susceptibility of a
compound having isolated magnetic ions with no magnetic interactions is given by (assuming total
quenching of orbital moments):

NAβ2g2S(S+1)
χM = 3kBT , (8a)

In the above expression, NA is Avogadro's number, kB is the Boltzmann constant, and β is a

constant unit called the Bohr magneton (BM). Note that Eq. 8a is similar to that shown by Curie's
law which was derived from experimental observations, giving the Curie constant C;

NAβ2g2S(S+1)
C = 3kB , (8b)

As discussed above, in condensed systems e.g. liquids and solids, generally there are some
magnetic interactions between the magnetic ions such that a modified Curie's law known as the
Curie-Weiss law is applied:

NAβ2g2S(S+1)
χM = , (9)
3kB(T - θ)

In substances with interacting magnetic moments and where the orbital contribution to the
magnetic moments is significant, the molar susceptibility is given by

NAβ2g2J(J+1)
χM = , (10)
3kB(T - θ)

here the resultant total angular momentum, J, is given by:

 J(J+1) = L(L+1) + S(S+1) (11)

and the value of g factor is given by Landé's equation:

S(S+1) - L(L+1) + J(J+1)

g = 1 + 2J(J+1) , (12)

The quantum number L, is the resultant orbital angular momentum of all unpaired electrons
present in the atom (i.e. L is zero for a completely filled orbital). However for most compounds of
the first row transition metal series, the orbital contribution to the magnetic moment is negligible,
such that J = S and Eq. 10 is identical to Eq. 9. In these and other compounds of the transition
metal series the metal ions are typically surrounded by strong ligands that quench the orbital
contribution to the magnetic moment.
Eq. 9 can be further simplified by defining µ 2 as g2S(S+1) and combining all of the
eff
constants to give:
NAβ2 µeff
2 2
µeff

χM = 3k  ≈ 0.125 (13)
 B  (T - θ) (T - θ)

This equation allows us to calculate the effective magnetic moment of an ion, µeff , which can
be rewritten as:

µeff = 2.828[ χM (T - θ)]1/2 (14)

where χM, the molar susceptibility, is obtained from Eq. 7 and T is the temperature in Kelvin.
INSTRUMENTATION:

In this experiment, the method to be used in the measurement of the magnetic susceptibilty
of substances is based on the principle of stationary sample but moving magnet. Here, the balance
{i.e. Johnson Matthey Magnetic Susceptibility Balance (MSB)}, measures the force that the sample
exerts on a suspended permanent magnet, unlike the Gouy balance which measures the equal and
opposite force which a magnet exerts on the sample.

In the experiment that follows, the mass susceptibility of a compound, χg, to be used in Eq. 7
is calculated from the quantities obtained using the Magnetic Susceptibility Balance (MSB) by the
following formula:

LCbal (R-Ro)
χg = (15)
(m·109)

where Cbal is the calibration constant of the balance, L is the length in centimeters (cm) of a
well-packed sample in the tube, m is sample mass in grams (g), R is the reading obtained for the
tube plus sample, Ro is the empty tube reading (normally a negative value i.e. diamagnetic).

The Magnetic Susceptibility Balance (MSB) must be calibrated with the standard compound,
HgCo(SCN)4 which has a χg = 16.44 x 10-6 c.g.s. at 20°C. This first measurement is required for
the calculation of the calibration constant of the balance, Cbal, in Eq. 15.

EXPERIMENTAL PROCEDURE

1. Turn the Range Knob to x1 scale and let the MSB warm up for ~10 min.
2. Adjust the MSB to read 000 using the Zero knob when no tube is inside the tube guide.
3. Place the empty tube into the tube guide of MSB, and record the reading, Ro
(normally a negative value i.e. diamagnetic).
4. Remove the empty tube from the MSB and weigh it carefully on a balance to the
nearest milligram; record the mass of the empty tube in grams, mt.
5. Prepare your sample for measurement by grinding (if not already in a powdered form).
Sample must be ground to a fine powder in a mortar and pestle.

6. Introduce your sample into the preweighed empty tube and tap (the sample tubes
 are expensive, made of brittle quartz materials; so tap them gently to avoid breakage) on a
wooden bench several times to achieve densely packed (i.e
minimum empty space between grains) sample. The length of the well packed
sample in the tube should be between 2.5 - 3.5 cm (or a length appropriate to the diameter of
the tube being used, as suggested by the manufacturer of the MSB).
7. Place the packed tube into the tube guide in the MSB, wait for stable reading
before recording this first reading, R1. If the reading is off-scale, remove the
packed tube, set the Range Knob to x10 scale and then rezero the MSB before putting
back the packed sample. Record your reading, but remember to multiply
this reading by 10.
8. Remove the packed tube from the MSB and tap it several times to further
compress the solid in the tube and remove any trapped air.
9. Place the packed tube back into the tube guide in the MSB, and record a second reading,
R2. If this second reading (R2) is not the same as the first reading (R1),
then repeat further the tapping/measuring sequence until two successive
readings are the same. Even packing gives constant reading hence tap the
sample tube gently till a constant reading is indicated.
10. Take the temperature reading, T, of the area around the MSB; remove the packed tube from
the MSB and measure the sample length in the tube in centimeters, L.
11. Immediately, measure the mass of the packed tube on a balance and record its
mass in grams, mt,s ; find the actual mass of the sample (m) in the packed tube in grams by
subtracting the mass of the empty tube (mt) from this value ; i.e
m = mt,s - mt

12. Do another measurement of the same sample by repacking the same tube and
following the procedures above. (Note: data for the same empty tube, i.e. R0
and mt should remain the same).
13. Clean the tube by tapping out the powder, followed by several washings with a
squirt bottle filled with soapy water. Finally rinse and dry with acetone.
References:

1. S. V. Vonsovskii, Magnetism; Vol. 1, Translated by R. Hardin; ed 1974; Ketter Publishing

House Jerusalem Ltd., Israel.

2. Russel S. Drago; Physical Methods in Chemistry, ed. 1977, W. B. Saunders Co. USA.

3. E. Konig; Landolt-Bornstein; Magnetic properties of coordination and organo-metallic

transition metal compounds; Group II, Vol. 2; editors K.-H. Hellwege and A. M. Hellwege;
1966, Springer-Verlag, Berlin.

4. John B. Goodenough; Magnetism and the Chemical Bond, ed. 1963; John Wiley & Sons
Inc.; USA.

5. C. J. O'Connor; Magnetochemistry-Advances in Theory and Experimentation, edited by

E. Stiefel.

6. Magnetic Susceptibilty Balance Instructional Manual; Johnson Matthey Inc., Wayne, PA;
P. O. # 041-1-0168, 1991.

7. J. Woolcock and A. Zafar; J. Chem. Educ. 69, A176, 1992.

8. David P. Shoemaker, et al; Customized Experiments in Physical Chemistry, 6th edition; p

109. McGraw Hill, USA.

Suggested Readings:

1. C. Kittel; Elementary Solid State Physics: A Short Course; ed. 1962, John Wiley & Sons
Inc.; USA.

2. Carlin, R. L. , Magnetochemistry; Springer; Berlin, 1986.

 8. HgCo(SCN)4 and Ni(en)3S2O3 are pure samples donated to us by
Prof. H. Schugar; Chemistry Department; Rutgers University, New
Brunswick, NJ. HgCo(SCN)4 can be prepared following the procedure
suggested by Figgis and Nyholm, J. Chem. Soc., 4190 (1958).

B. Calculations and Worked Examples:

1. Calculation of the calibration constant, Cbal:

a). HgCo(SCN)4 has a χg = 16.44 x 10-6 c.g.s. at 20°C

4981
χg at T °C = (283 + T) x 10-6 c.g.s

then at T = 21.0 °C, χg is;

4981
χg = (283 + 21) x 10-6 c.g.s = 16.38 x 10-6 c.g.s

b). Refer to table 1, data No. 1 for HgCo(SCN)4;

LCbal (R-Ro)
χg = ; on rearranging;
(m·109)

χg (m·109)
Cbal = L (R-Ro)

Hence for T = 21.0 °C, Cbal becomes;

16.38 x 10-6 (0.5082 x 109)

Cbal = 3.25 (2120-(-31)) = 1.19076

c). χg for Ni(en)3S2O3 refer to table 1, data No. 2;

LCbal (R-Ro) 3.30 x 1.19076 (750 - (-31))

χg = =
(m·109) (0.2787 x 109)
 that is; χg = 11.01 x 10-6 c.g.s at T = 21.0 °C

Compare this value of χg for Ni(en)3S2O3 with the value given in litrature, i.e.
χg at 20.0 °C = 11.04 x 10-6 c.g.s. and since

2759
χg at T °C = (230 + T) x 10-6 c.g.s; then

2759
χg at 21.0 °C = (230 + 21) x 10-6 c.g.s = 10.99 x 10-6 c.g.s

2. Worked Examples : refer to table 1, data for α-MnS (data No. 4)

LCbal (R-Ro) 3.15 x 1.19076 (8840 - (-27))

χg = 9 =
(m·10 ) (0.5358 x 109)

that is; χg = 62.07 x 10-6 c.g.s at T = 23.0 °C

Hence χM for this compound can be calculated using eq. 7 ;

that is; χM = χg·MW/Z = 62.07 x 10-6 x 87.002 g/mol, since Z = 1 for α-MnS

therefore ; χM = 5.40 x 10-3 emu/ mol

To calculate the effective magnetic moment,µeff , we make use of eq. 14;

µeff = 2.828 (emu/mol K)-1/2 [ χM (T - θ)]1/2

= 2.828 (emu/mol K)-1/2 [ 5.40 x 10-3 emu/ mol (296 - (-490) K]1/2
= 5.83 BM

The students will study a series of first row transition metal compounds to determine the
oxidation state of the ion in each compound and the number of unpaired electrons, from the
measurement of the magnetic susceptibility. The compounds will include various transition metal
complexes varying in different number of d-electrons. The students will directly measure the mass
susceptibility of each compound using a Magnetic Susceptibility Balance (MSB, Johnson Matthey
model). Given the values of Curie constant (θ) for each compound, the students will be able to find
the effective magnetic moment of the manganese ion from the measured values of the molar
susceptibility of each compound using Eq. 14. , hence wil be able to calculate the number of
unpaired electrons.