The Evans method
Measuring magnetic susceptibility
by NMR—application
Created by Adam R. Johnson, Harvey Mudd College (adam_johnson@hmc.edu) and posted on
VIPEr on June 9, 2016. Copyright Adam R. Johnson, 2016. This work is licensed under the Creative
Commons Attribution-NonCommercial-ShareAlike License. To view a copy of this license visit
http://creativecommons.org/licenses/by-nc-sa/4.0/
Magnetic Susceptibility
• Magnetic susceptibility is the ratio
between magnetization M of the
material in a magnetic field and the field
intensity H:
• M = χ·H.
• Diamagnetic materials have χ < 0
• Paramagnetic and ferromagnetic
materials have χ > or >> 0
Magnetic Field in an NMR
• H” is the component of applied field due to given
concentration of paramagnetic ions in solution
• H” = H1 + H2
• H1 = Lorentz or cavity field of induced magnetization
in a sphere around the paramagnet = (4π/3)M
• H2 is demagnetizing field, opposing applied field; H2 =
-αM (α depends on sample geometry and relative
orientation of sample tube and external field)
• H” = [(4π/3)-α]M
• But M = χH
• So H”/H = [(4π/3)-α] χ
• Given: H”/H = [(4π/3)-α]χ
• But ∆H”/H = ∆f/f
• ∆f/f = [(4π/3)-α]χ
• Finally, add a correction term for the
magnetic susceptibility of the solvent
and for the change in density of solution
vs. solvent. This was all derived using
mass susceptibilities (χm)
Δf χ 0 (do − ds )
χm = + χo +
⎛ 4π ⎞ m
⎜ − α ⎟ fm
⎝ 3 ⎠
History
• Originally developed for permanent
magnet application
• Applied field perpendicular to sample
α = 2π
−3Δf χ (d − d )
χm = + χo + 0 o s
sample sample rotation 2π fm m
3 Δf χ (d − d )
magnet χm = + χo + 0 o s
2π fm m
applied field
∆f = peak separation (Hz)
f = NMR frequency (Hz)
m = mass per cm3
χm = mass susceptibility
History
• Modern instrumentation: coaxial
superconducting magnet
• Applied field parallel to sample
α=0
sample 3Δf χ (d − d )
sample rotation χm = + χo + 0 o s
4π fm m
magnet
∆f = peak separation (Hz)
applied field
f = NMR frequency (Hz)
m = mass per cm3
χm = mass susceptibility
Relationship to number of
unpaired electrons
χpT = constant for simple paramagnets (Curie Law)
N A g2 β 2 1
χ PT = [S(S +1)] = 0.50157[S(S +1)] ≈ [S(S +1)]
3kB 2
1
χ PT ≈ n(n + 2)
8 χP = paramagnetic susceptibility
8 χ PT ≈ n(n + 2) T = absolute temperature (K)
NA = Avogadro’s number
g = magnetogyric constant for electron
β = Bohr magneton
kB = Boltzmann constant
S = Total spin Quantum number
n = number of unpaired electrons
Must include Russell-Saunders coupling for 2nd or 3rd row
And also spin-orbit coupling for f block (CGS units)
Effective magnetic moment†
3kB
µeff = 2
( χ PT ) ≈ 7.9933( χ PT ) ≈ 2.827 χ PT
N Aβ
3kB 3kB N A g 2 β 2
µeff = 2
( χ PT ) = 2
( [S(S +1)]) ≈ 4S(S +1)
N Aβ N Aβ 3kB
µeff ≈ 2 S(S +1) = n(n + 2)
µeff is independent of temperature and unitless but is
usually reported in units of Bohr magneton: µB
χP can be measured at any T and related to n or S
†The Chemist’s magnetic unit (CGS units)
Evans’ method
• Using 1H NMR to determine
magnetic susceptibility NMR tube
– NMR tube
• Sample solution
• Capillary with pure solvent Capillary with
pure solvent
– NMR spectrum collected
Sample solution
• NMR solvent in capillary (shifted peak)
• NMR solvent in tube (reference peak)
– Use peak shift to calculate unpaired
electrons
Commonly published equation
• Use c for concentration (mol·L-1 = M)
• Ignore solvent diamagnetism
• Ignore density correction
• Combine constants
• Ignore sign of ∆f; take positive value
−3Δf 1000cm 3 m' −3000Δf 477Δf
χm = · · = =
4π fm L n 4π fc 2 fc
∆f = peak separation (Hz) n = moles
f = NMR frequency (Hz) c = molar concentration
m = mass concentration (g/mL) χm = molar susceptibility
m’ = mass
Diamagnetic correction
• One unpaired electron can be detected
even in a large molecule because the
magnitude is ~1000 times greater
• For careful work with large molecules,
correct observed susceptibility for
presence of paired e-
χ =χ +χ
• χD tabulated
meas P D
χ =χ −χ
P meas D
• χD opposite sign to χP!
