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Introduction
A magnetic field causes unpaired electrons to tend to align with the field. The resulting
magnetization M (magnetic dipole moment per unit volume) induced in a substance is proportional to
applied field H:
M = χ H. (1.)
The constant of proportionality χ is the volume susceptibility, which is unit less. From the chemist’s point
of view, this quantity gives insight into the number of unpaired electrons present, although other effects
(orbital magnetic moment, diamagnetic ligands and ions) complicate the picture. Substances having
unpaired electrons are called paramagnetic and have values of χ around +10−4. Diamagnetic substances,
those lacking unpaired electrons, have χ around –10-6. mks and cgs units for quantities related to
magnetic susceptibility are summarized in Table 2. We will use cgs units here because of the convenience
of working with cm3 and g.
Because heat affects the alignment of electrons, paramagnetic substances follow the Curie law
approximately:1
N µ
2
χ M = A eff . (2.)
3kT
χM is the molar susceptibility, defined below (equation 5). It is the quantity that will be determined in
this experiment. µeff is the effective magnetic moment. From equation (2) (ref. 1),
µeff /β = 2.83 mol1/2 cm−3/2 K−1/2 χ M T . (3.)
β is the Bohr magneton, a convenient unit of magnetic moment whose value is given in Table 2 below.
In the first transition series, orbital contribution to magnetic moment “is almost completely
quenched by the ligand fields.” 1 In this case, µeff is related to spin only and
µeff /β ≈ 2 [S (S + 1)]1/2 = [n (n+2)]1/2 , and
n(n+2) ≈ 8.01 mol cm−3 K−1 χM T, (4.)
in which S is total spin and n is the number of unpaired electrons of the transition metal ion.
Gram and molar susceptibilities
The gram susceptibility χg (units cm3 g−1) and the molar susceptibility (units cm3 mol−1) are
χg = χ/ρ, and
χM = M × χ/ρ, (5.)
in which χ is the volume susceptibility, M is the molar mass and ρ is the bulk density.
Example:
χM of CuSO4.5H2O = 1460×10-6 cm3 mol−1, so
χ g = 1460 × 10 −6 cm 3 mol −1 × mol = 5.847 × 10 −6 cm 3 g −1 .
249.7g
Dr Amit Kumar, Centro Química Estrutural
Instituto Superior Técnico
NMR method2
NMR can be used to measure magnetic susceptibility. The presence of a paramagnetic ion in
solution causes a change in local magnetic field and therefore a shift in proton resonance lines for a
reference molecule such as t-butanol. Since the paramagnetic ion strengthens the local magnetic field,
the shift will be upfield (to the left).
In a typical experiment2,3 the paramagnetic substance is dissolved in a 10% solution of t-butanol in
D2O and the solution is placed in an NMR tube. The mass fraction of solute must be accurately known.
In addition, some butanol/D2O solution is sealed in a capillary tube which is placed in the NMR tube as a
reference. The signal will consist of the unshifted methyl proton resonance at ~1 ppm (from the capillary
tube) plus a second line shifted by the paramagnetic ion. A pair of lines at ~5 ppm from H2O will
probably also be present.
The shift, in ppm, caused by the paramagnetic ion is
∆H 2π
= ( χ solution − χ solvent ) . (6.)
H 3
∆H/H × 106 is the shift in ppm. The volume susceptibility of the solution is
χ(solution) = [χg(solute)×p + χg(solvent)×(1 − p)] × ρ , (7.)
in which p is the mass fraction of solute in the solution and ρ is the density of the solution.
Example
For a 10% solution of t-butanol in D2O (see Table 2),
χ(solution) = [−0.77×0.10 + (−0.64)×0.9] 10−6cm3g−1 × 1.07g cm−3
= −0.70×10−6.
If CuSO4.5H2O is dissolved at 5% by mass in D2O, then
−6 −6
1.10g
χ(solution ) = 4.7 ×10 cm × 0.05 + − 0.64 × 10 cm × 0.95 ×
3 3
cm
3
g g
= −0.41×10 − 6 .
The expected shift in magnetic resonance would be
∆H = 2π (− 0.41 × 10 −6 − ( −0.70 × 10 −6 ) )
H 3
= 0.61 × 10 −6 = 0.61ppm.
*
In mks units, force = ½Aχµ0(H2−H02), with χ(mks) = 4πχ(cgs). The quantity A(H2−H02)/2g is
sometimes called the instrument constant.