Nuclear Magnetic Resonance

Spectrometry

Chap 19
 Environmental Effects

(1) Chemical Shift

• Nearby electrons and nuclei generate small B fields

which tends to oppose Bapplied:

Bo = Bapplied – σBapplied

where σ ≡ screening constant

It is the local field Bo that interacts with magnetic moments!


 Larmor  Bo (1   )
• Now, resonance condition: 2
Abscissa Scales for NMR Spectra

• In terms of chemical shift, δ

ν ref  ν sample
δ x 10 6 ppm
ν ref

• Almost impossible to measure absolute Bo

• Measure change in Bo relative to internal

standard: Tetramethylsilane (TMS)
 High Resolution NMR Spectrum of Ethanol
Fig. 19-12

High field
Low field
Low shield High shield

in ppm

Bo
Chemical Shift (cont’d)

• Diamagnetic currents by electrons tend to

oppose Bapplied

• Nucleus is then “shielded” from Bapplied

• ∴ Bapplied must be increased to cause resonance

• Shielding proportional to electron density

Diamagnetic Current Shielding of a Nucleus
Fig. 19-14

Bo = Bapplied – σBapplied
Chemical Shifts and Electronegativity of Halogens

• Shielding
∝ electron density

• Shielding
∝ 1/electronegativity
of adjacent halogen
 Effect of Magnetic Anisotropy

• Unsaturated hydrocarbons

• Local diamagnetic effects do not explain

proton chemical shifts

e.g.: CH3 - CH3 (δ = 0.9)

CH2 = CH2 (δ = 5.8)

CH ≡ CH (δ = 2.9)
 Deshielding of Ethylene and Shielding of Acetylene

Brought About by Electronic Currents

Fig. 19-16
(δ = 2.9)

(δ = 5.8)
Magnetic Anisotropy Combined with
Electronegative Group Results
in Very Large δ For Protons

Aldehydes:

δ ≈ 10 – 11

Far down
field
Ring Current Deshielding of Aromatic Protons
Fig. 19-15

Aromatics:
δ ≈ 7 – 13

• Far down field

• Effect is absent
or self-cancelling
in other ring
orientations
(2) Spin-Spin Splitting

• Result of coupling interaction between

2 groups of protons

Multiplicity

TMS

The fine structure

Effect of methylene protons on resonance of methyl protons

Opposes Bapplied
Enhances Bapplied

Resonance at Resonance at
higher Bapplied lower Bapplied

• The ± magnetic effect transmitted to methyl protons

• Methyl peak split into a triplet by methylene

• Triplet with 1:2:1 intensity ratio

Effect of methyl protons on resonance of methylene protons

Enhances Bapplied

3:1 intensity
ratio

Resonance at
lower Bapplied
• The ± magnetic effect transmitted to methylene protons

• Methylene peak split into a quartet by methyl protons

• Quartet with 1:3:3:1 intensity ratio

Rules Governing Spin-Spin Splitting

• Equivalent nuclei do not interact

• Coupling constants decrease with separation

of groups (< 4 bond lengths)

• Multiplicity = n+1 where n = mag equivalent

protons on adjacent atoms

• Approximate relative areas of a multiplet are

symmetric about midpoint of band

• Coupling constant J is independent of Bo

 Summary of Information from NMR

• The screening constant (σ) determined from the

chemical shift (δ)

• The spin-spin coupling constant (J) determined

from the fine structure (unaffected by Bapplied)

• Motional information determined from the

nuclear spin relaxation times, T1 and T2